JP2010085501A - Liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal display device capable of obtaining satisfactory display characteristics by reducing a reflection light component from an inner part of a liquid crystal cell becoming obvious when reflectivity on a viewing surface of a liquid crystal panel is reduced by using an optical function film and thereby reducing reflection of external light. <P>SOLUTION: In the liquid crystal display 100 which includes a liquid crystal panel 10 having a liquid crystal layer 15 interposed between transparent substrates 11 and 13 and polarizing plates 23 and 27 disposed on outer sides of the transparent substrates and an optical function film 29 disposed on at least one surface side of the liquid crystal panel 10 and suppressing reflection of external light and wherein a switching element 35 for driving the liquid crystal layer 15 is disposed in a matrix shape on an inner surface of either substrate of the pair of transparent substrates, a reflection preventing film is formed on either film of a conductive film forming a gate signal line in which a driving signal for driving the switching element 35 is input and a conductive film forming a source signal line in which a display signal to the liquid crystal panel 10 is input. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid crystal display device driven by a switching element.

  An active matrix type liquid crystal display device includes a liquid crystal panel having a liquid crystal layer sandwiched between a pair of transparent substrates and a polarizing plate disposed outside each of the pair of transparent substrates, and one of the pair of transparent substrates. A switching element represented by a TFT (thin film transistor) for driving a liquid crystal layer is arranged in a matrix on the inner surface of the substrate. On the substrate on which the switching element is arranged, a gate signal line to which a drive signal for driving the switching element is input and a source signal line to which a display signal is input are provided so as to intersect each other. The gate signal lines extend in the row direction, the source signal lines extend in the column direction, and TFTs are arranged at the intersecting points.

  In recent years, liquid crystal display devices have increased in screen size, and for example, optical function films such as antireflection films and antiglare films have been placed on the observation surface of liquid crystal panels to reduce the reflection of ambient light. (For example, refer to Patent Document 1). The antireflection film is configured such that the surface of the base film on which the hard coat layer is formed is coated with an inorganic dielectric thin film in multiple layers so that two kinds of reflected waves cancel each other out by interference. On the other hand, the anti-glare film has a scattering angle showing a maximum value of scattered light intensity of, for example, about 0.1 to 10 °, and the difference in refractive index between the light diffusion layer and the translucent particles contained therein is Has great characteristics. Thereby, the internal scattering and scattering angle of the light passing through the light diffusing layer are increased, and glare is suppressed. These films can prevent a decrease in contrast due to reflection of external light or reflection of an image.

As described above, in the liquid crystal display device, by using an optical functional film such as an antireflection film or an antiglare film, unnecessary reflected light components can be removed, and the displayed image quality can be improved. FIG. 22 shows an example in which the reflection of the observation surface of the liquid crystal panel is suppressed by the optical functional film. In the illustrated example, the surface reflection component is larger than the internal reflection component, and the surface reflection component determines the substantial reflected light distribution (surface + internal reflection). Therefore, in order to reduce this substantial reflected light distribution, an attempt was made to further reduce the surface reflectivity of the optical functional film, that is, to lower the reflectance and to increase the antiglare. Even if the property was reduced beyond a certain level, the reflected light intensity did not decrease. That is, when the optical function film has low reflectivity, the internal reflection component from the inside of the liquid crystal cell is dominant rather than the reflected light component on the observation surface of the liquid crystal panel. Thus, it was different from the case of using an optical functional film having strong surface reflectivity in which the internal reflection component was almost negligible. Therefore, when using a high-performance antireflection film / antiglare film, the strength of the internal reflection component determines the display quality of the liquid crystal display device.
JP 2004-306328 A

  The present invention has been made in view of the above circumstances, and its purpose is to reduce the reflected light component from the inside of the liquid crystal cell that becomes apparent when the reflectivity on the observation surface of the liquid crystal panel is reduced using an optical functional film. Accordingly, an object of the present invention is to provide a liquid crystal display device capable of reducing the reflection of external light and obtaining good display characteristics.

The present invention has the following configuration.
(1) A liquid crystal panel having a liquid crystal layer sandwiched between a pair of transparent substrates and a polarizing plate respectively disposed on the outside of the pair of transparent substrates, and arranged on at least one side of the liquid crystal panel for external light. And an optical functional film that suppresses reflection, and an active matrix liquid crystal display device in which switching elements for driving the liquid crystal layer are arranged in a matrix on the inner surface of one of the pair of transparent substrates. And
At least one of a conductive film forming a gate signal line to which a driving signal for driving the switching element is input and a conductive film forming a source signal line to which a display signal to the liquid crystal panel is input A liquid crystal display device in which an antireflection film is formed on the film.

  According to this liquid crystal display device, the reflectance on the display surface side is reduced by the optical functional film, and the reflection from the inside of the display that is dominantly manifested by the antireflection film formed on the conductive film. It is difficult to occur, and the reflected light from the inside which is observed to be cumulatively projected from the display surface is reduced.

(2) The liquid crystal display device according to (1),
The liquid crystal display device, wherein the antireflection film is one of a light-transmitting oxide film and a light-transmitting nitride film.

  According to this liquid crystal display device, by forming one of the light-transmitting oxide film and nitride film, the conductive film forming the gate signal line and the source signal line is reduced in reflection, and the liquid crystal display Reflection from inside the device is reduced.

(3) The liquid crystal display device according to (2),
A liquid crystal display device, wherein the oxide film includes a chromium oxide film.

  According to this liquid crystal display device, the chromium oxide film is provided on the conductive film forming the gate signal line and the source signal line, whereby the reflectance on the conductive film is reduced. If, for example, chromium oxide is used as the chromium oxide film, a strong film quality can be obtained, and corrosion resistance, oxidation resistance, wear resistance, and adhesion can be imparted. Further, by using a two-layer film of chromium and chromium oxide, a source electrode and a drain electrode can be formed simultaneously.

(4) The liquid crystal display device according to (2),
A liquid crystal display device, wherein the nitride film includes a tantalum nitride film.

  According to this liquid crystal display device, the reflectance on the conductive film is reduced by providing the tantalum nitride film on the conductive film forming the gate signal line and the source signal line. The tantalum nitride (TaN) film is obtained by performing reactive sputtering using tantalum (Ta) as a target and introducing nitrogen together with Ar.

(5) The liquid crystal display device according to any one of (1) to (4),
A liquid crystal display device in which the antireflection film is laminated in a multilayer shape.

  According to this liquid crystal display device, the reflectance can be made zero at a plurality of wavelengths. When the antireflection film is a single-layer film, the reflectance is zero at only one wavelength, and the reflectance rises steeply at both wavelengths of the wavelength, but it is reflected at multiple wavelengths by making the antireflection film multilayer. The rate can be made zero, and a reduction in reflectance in a wide wavelength range can be realized.

(6) The liquid crystal display device according to any one of (1) to (6),
The liquid crystal panel has a color filter formed in a number of lands corresponding to the switching element on the transparent substrate, and a light-shielding black matrix that fills the gaps between the adjacent color filters, A liquid crystal display device in which an antireflection film is formed at least on the arrangement region of the color filter excluding a light shielding region by the black matrix.

  According to this liquid crystal display device, when a conductive film is arranged in a display region that is not shielded by a black matrix, the surroundings are bright, and black display is performed, linearly polarized light that originally entered from the observation side and passed through the polarizing plate After passing through the liquid crystal layer, it is reflected on the conductive film, passes through the liquid crystal layer again, and reaches the polarizing plate. Since the polarization direction of the light reaching the polarizing plate does not change, the reaching light and the polarization direction of the polarizing plate are parallel and pass through the polarizing plate and reach the observer's viewpoint. That is, the brightness at the time of black display increases, and the contrast of the display image decreases remarkably. On the other hand, in the configuration of the present invention in which the antireflection film is provided on the conductive film, since the reflection on the conductive film is reduced, the linearly polarized light reaching the observer's viewpoint is reduced and the luminance is reduced. The contrast of the display image is increased without increasing.

(7) The liquid crystal display device according to any one of (1) to (6),
A liquid crystal display device, wherein the optical functional film is a thin film interference type antireflection film.

  According to this liquid crystal display device, when a thin film interference type antireflection film is provided on at least one side of the liquid crystal panel and the surroundings are bright, reflection of external light incident from the observation side is reduced on the outside of the liquid crystal layer. The amount of reflected light reaching the person's viewpoint is greatly reduced. This increases the contrast and improves the reflection.

(8) The liquid crystal display device according to any one of (1) to (6),
A liquid crystal display device, wherein the optical functional film is a light diffusion film having a light diffusion layer.

  According to this liquid crystal display device, a light diffusion film having a light diffusion layer is provided on at least one side of the liquid crystal panel, and when the surroundings are bright, reflection of external light incident from the observation side on the outside of the liquid crystal layer is reduced, The amount of reflected light reaching the observer's viewpoint is greatly reduced. Thereby, contrast is enhanced and reflection and antiglare properties are also improved.

  According to the liquid crystal display device of the present invention, an optical functional film that suppresses reflection of external light is provided on at least one side of the liquid crystal panel, and the conductive film that forms the gate signal line of the switching element and the source signal line are formed. Since an antireflection film is provided on at least one of the conductive films, the reflectivity on the surface of the liquid crystal panel is reduced by using an optical functional film that is a particularly high-performance antireflection film and antiglare film. Even in the case of a liquid crystal display device, the reflected light component from the inside that appears is reduced, the reflection of external light is reduced, and good display visibility can be obtained.

Hereinafter, a liquid crystal display device according to an embodiment of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of a liquid crystal display device for explaining an embodiment of the present invention.
The liquid crystal display device 100 mainly includes a liquid crystal panel 10 and a backlight 20 that is disposed on the back side of the liquid crystal panel 10 and emits light toward the liquid crystal panel 10. The liquid crystal panel 10 includes a liquid crystal layer 15 between a lower substrate 11 and an upper substrate 13, and a polarizing plate 23 is disposed on the outer side opposite to the liquid crystal layer 15 of the lower substrate 11 via a retardation film 21. A polarizing plate 27 is disposed outside the upper substrate 13 via a retardation film 25. Further, on the surface of the lower substrate 11 and the upper substrate 13 on the liquid crystal layer 15 side, a pixel electrode 17 for controlling the liquid crystal alignment of the liquid crystal layer and a common electrode 19 which is a transparent electrode are arranged to face each other (see FIG. In the example shown, only one pair is shown). A color filter layer CF is disposed between the common electrode 19 and the upper substrate 13. In addition, an antireflection film (here, an AR (Anti Reflection) film) that is an optical functional film is disposed on the observation side of the liquid crystal display device 100, that is, on the outer surface opposite to the liquid crystal layer 15 of the polarizing plate 27. Yes. The polarizing plates 23 and 27 include a polarizing film 31 and transparent protective films 33 and 35 disposed on the front and back surfaces of the polarizing film 31, respectively.

  That is, in the liquid crystal display device 100, the lower substrate 11 as a pair of transparent substrates, the liquid crystal layer 15 sandwiched between the upper substrate 13 and the polarizing plates 23 disposed on the outer sides of the transparent substrates 11 and 13, respectively. The liquid crystal panel 10 having 2727 and 31 and the optical function film 29 disposed on at least one side of the liquid crystal panel 10 to suppress reflection of external light are provided. An antireflection film (details will be described later) for reducing internal reflection is formed inside the liquid crystal panel 10.

In the liquid crystal panel 10, a large number of pixel electrodes 17 are arranged in a matrix, and a plurality of common electrodes 19 are arranged correspondingly. Each pixel electrode 17 is active matrix driven by a switching element provided at an intersection of a source signal line and a gate signal line wired in a matrix.
2 is a plan view of the main part of the liquid crystal display device shown in FIG. 1, and FIG. 3 is a cross-sectional view taken along line AA of FIG.
In the active matrix liquid crystal display device 100, switching elements 35 typified by TFTs (thin film transistors) for driving the liquid crystal layer 15 are arranged in a matrix on the inner surface of the lower substrate 11. The lower substrate 11 is provided with a gate signal line 37 to which a drive signal for driving the switching element 35 is inputted and a source signal line 39 to which a display signal is inputted so as to cross each other. The gate signal line 37 extends in the row direction, the source signal line 39 extends in the column direction, and the switching element 35 is disposed in the vicinity of the perpendicular intersection.

  The switching element 35 has a gate electrode 41 to be a gate signal line 37 on the lower substrate 11 shown in FIG. 3, and an insulating layer 45 and a channel layer 46 made of amorphous Si (a-Si) on the gate electrode 41. And a drain electrode 49 connected to the channel layer 46. The source electrode 43 is connected to the source signal line 39 as shown in FIG. The pixel electrode 17 provided in the display area of each pixel is made of a transparent electrode such as ITO, and the pixel electrode 17 is connected to the drain electrode 49 through the contact hole 47. A protective film 51 such as SiN is formed on the top layer of the layer configuration shown in FIG. Since the gate signal line 37, the source signal line 39, and the gate electrode 41, the source electrode 43, and the drain electrode 49 are each composed of a conductive film such as a metal thin film, the reflectance of light is high.

  The liquid crystal panel 10 includes a color filter layer CF having a color layer of a plurality of colors (three colors such as R, G, and B) and a black matrix. The color filter substrate having the color filter layer is an upper substrate. It is good also as a structure bonded together by 13 with the sealing material.

  In the liquid crystal panel 10 having the above configuration, a conductive film that forms a gate signal line 37 to which a drive signal for driving the switching element 35 is input and a source signal line 39 to which a display signal to the liquid crystal panel 10 is input. An antireflection film is formed on the surface. 3 shows a state in which the antireflection film 53 is formed on the source electrode 43 connected to the source signal line 39 and the antireflection film 53 is formed on the drain electrode 49 and the gate electrode 41. It was. As described above, the antireflection film 53 is formed on each of the gate signal lines 37 and the source signal lines 39 arranged in a lattice pattern, and the gate electrode 41, the source electrode 43, and the drain electrode 49 connected thereto. The internal reflection of the liquid crystal panel 10 is reduced. The antireflection film 53 may be formed on at least one of the gate signal line 37, the source signal line 39, and each electrode connected thereto. The gate signal line 37 and the source signal line 39 include the electrodes connected to each other.

  The antireflection film 53 can be at least one of a light-transmitting oxide film and a light-transmitting nitride film. By forming at least one of a light-transmitting oxide film (for example, Cr + CrO) and a nitride film (for example, Ta + TaN), a conductive film for forming a gate signal line 37 and a source signal line 39, a gate electrode 41, and a source The electrode 43 and the drain electrode 49 are reduced in reflection, and reflection from the inside of the liquid crystal display device 100 is reduced.

  The oxide film may include a chromium oxide film. By providing the chromium oxide film over the conductive film that forms the gate signal line 37, the source signal line 39, and the like, the reflectance on the conductive film is reduced. If, for example, chromium oxide is used as the chromium oxide film, a strong film quality can be obtained, and corrosion resistance, oxidation resistance, wear resistance, and adhesion can be imparted.

  The nitride film may include a tantalum nitride film. By providing the tantalum nitride film on the conductive film forming the gate signal line 37, the source signal line 39, and the like, the reflectance on the conductive film is reduced. When the reflectance of Ta is 60%, the reflectance can be reduced to 6% by providing TaN. The tantalum nitride (TaN) film is obtained by performing reactive sputtering using tantalum (Ta) as a target and introducing nitrogen together with Ar.

  The antireflection film 53 may be laminated in a multilayer shape. By making it multilayer, the reflectance can be made zero at a plurality of wavelengths. When the antireflection film 53 is a single-layer film, the reflectance is zero at only one wavelength, and the reflectance rises steeply at both wavelengths of the wavelength. Thus, the reflectance can be reduced to zero, and the reflectance can be reduced in a wide wavelength range.

  In the liquid crystal display device 100 including the liquid crystal panel 10 provided with the antireflection film 53 in this way, the reflected light component on the surface side of the liquid crystal panel is reduced by the optical function film 29, and the liquid crystal panel becomes apparent due to this. The reflected light component is reduced by the antireflection film 53 formed on the conductive film, and the internally reflected light component observed from the liquid crystal panel surface can be reduced.

  By the way, the liquid crystal panel 10 includes a color filter CF1 formed in a number of lands on the upper substrate 13 corresponding to the pixel electrodes 17 (see FIG. 1), as shown in a plan view of the color filter layer CF in FIG. , CF2, CF3, and a light-shielding black matrix BM that fills the gaps between adjacent color filters. The antireflection film 53 is preferably formed at least in the arrangement region of the color filters CF1, CF2, and CF3 excluding the light shielding region by the black matrix BM. That is, the antireflection film 53 is selectively formed on the region of the drain electrode 49 disposed in the color filters CF1, CF2, and CF3 and on the upper surface of the storage capacitor CS and the like located at the center of the pixel electrode.

  When the electrodes are arranged in the display area (color filters CF1, CF2, and CF3) that are not shielded by the black matrix, the surrounding environment is bright, and black display is being performed, the display brightness is high while displaying black due to reflection from the electrodes. It tends to increase and the contrast of the display image decreases. On the other hand, in the configuration in which the antireflection film 53 is provided on the electrode, since reflection on the electrode is reduced, the internal reflection component is reduced, the luminance at the time of black display is not increased, and the display image is displayed. Increases the contrast. Further, since the antireflection film 53 is disposed in the minimum necessary region, it is possible to suppress a decrease in light transmittance of the liquid crystal panel.

  The optical functional film 29 may be a light diffusion film. When a light diffusing film is provided on at least one side of the liquid crystal panel 10 and the surrounding environment is bright, external light incident on the liquid crystal panel 10 is scattered by the light diffusing film, and the outline of the reflection shape that can be visually recognized by the observer is blurred. (Edge information fades). Thereby, the intensity of visual reflection is reduced.

  Thus, according to the liquid crystal display device 100 of this configuration, the optical function film 29 that suppresses reflection of external light is provided on at least one side of the liquid crystal panel 10, and the gate signal line 37 and the source signal line 39 of the switching element 35 are provided. Since the antireflection film 53 is provided on the conductive film that forms the liquid crystal display device, the optical function film 29 having particularly excellent antiglare properties is used, and even in the liquid crystal display device in which the reflectivity on the surface of the liquid crystal panel 10 is reduced, The reflected light component from the inside of the liquid crystal panel 10 that becomes apparent can be reduced. Thereby, reflection of external light can be reduced and good display characteristics can be obtained.

Next, the result of verifying the effect of reducing surface reflection by the antireflection film and the antiglare film and the effect of reducing internal reflection by the antireflection film 53 will be described.
FIG. 5 is a schematic diagram showing a method for photographing the ceiling illumination reflected in the liquid crystal display device.
As shown in the figure, a liquid crystal display device 100 is arranged at a distance L _LAMP with respect to the ceiling illumination 55, and a fluorescent lamp image reflected on the liquid crystal panel is measured from the liquid crystal display device 100 at a distance L _CAM (45 cm). (Cybernet: Prometric camera) 57 was installed at an imaging angle θ _i and photographed. This photographed image is as shown in FIG. 6, for example. A fluorescent lamp image 59 reflected on the liquid crystal panel is included in the captured image 61, and a one-dimensional luminance profile along the x direction is generated from the captured image.

Here, an antireflection film (AR film 65) whose layer structure is shown in FIG. The AR film 65 is a three-layer thin film interference type antireflection film having excellent antireflection performance, and includes a transparent support 67, a low refractive index layer 69 located on one surface of the transparent support 67, and a low refractive index. Between the refractive index layer 69 and the transparent support 67, a high refractive index layer 71 having a higher refractive index than the low refractive index layer 69 is provided as a thin film layer. Further, a thin film layer (hereinafter simply referred to as “thin film layer” refers to these low refractive index layer, high refractive index layer and medium refractive index layer) between the high refractive index layer 71 and the transparent support 67. A medium refractive index layer 73 is provided. A hard coat layer 75 is provided between the intermediate refractive index layer 73 and the transparent support 67.
The transparent support 67, the medium refractive index layer 73, the high refractive index layer 71, and the low refractive index layer 69 have a refractive index that satisfies the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer

  Sample obtained by laminating an antireflection film on a black PET film in order to estimate the influence of reflection from the inside of the liquid crystal panel 10 when obtaining the display surface luminance profile of the liquid crystal display device to which the antireflection film is adhered. And a luminance profile not including an internal reflection component was obtained. The brightness profile obtained from this sample is used as the surface reflection component, the brightness profile obtained using the mounted product (liquid crystal panel 10) is used as the overall reflection component, and the internal reflection component is obtained by subtracting the surface reflection component from the overall reflection component. It was.

FIG. 8 is a graph (a) showing an intensity distribution of a relative luminance of a liquid crystal display device in which an AR film is adhered to the surface of the liquid crystal panel, and an AR film is adhered to the surface of the liquid crystal panel and an antireflection film is disposed on the conductive layer of the electrode. 5 is a graph (b) showing an intensity distribution of relative luminance of the liquid crystal display device provided in FIG.
As shown in FIG. 8A, by using the AR film 65 as the antireflection film on the surface of the liquid crystal panel, the relative luminance of the surface reflection component of the reflected light intensity can be suppressed to 30 or less at the maximum. Further, as shown in FIG. 8B, an AR film is used, and the conductive film for forming the gate signal line 37 and the source signal line 39, and the gate electrode 41, the source electrode 43, and the drain electrode 49 are used. By providing the antireflection film 53, the internal reflection component is reduced to about 1/3. As a result, the substantial reflection intensity obtained by adding the surface reflection component and the internal reflection component is reduced to about 2/3.

Next, another example of the optical function film 29 will be described. Here, an antiglare film was used in place of the antireflection film (AR film). A schematic layer structure of the antiglare film is shown in FIG. And the reflected light intensity distribution at the time of sticking the glare-proof film of the layer structure shown by the figure to the observation side surface of the liquid crystal panel 10 was calculated | required.
Here, an anti-glare film AGLR (Anti Glare Low Reflection) film 79 is formed by sequentially laminating a transparent support 81, a light diffusion layer 83, and a low refractive index layer 85, and translucent particles 87 on the light diffusion layer 83. What was included was used.

  FIG. 10 is a graph (a) showing a relative luminance intensity distribution of a liquid crystal display device in which an AGLR film is attached to the surface of the liquid crystal panel, and an antireflection film is attached to the electrode conductive layer while the AGLR film is attached to the surface of the liquid crystal panel. 5 is a graph (b) showing an intensity distribution of relative luminance of the liquid crystal display device provided in FIG.

  As shown in FIG. 10A, by using the AGLR film 79 as the optical functional film 29 on the liquid crystal panel surface, the relative luminance of the surface reflection component of the reflected light intensity can be suppressed to 40 or less at the maximum. Further, as shown in FIG. 10B, the AGLR film is used, and the conductive film for forming the gate signal line 37 and the source signal line 39, and the gate electrode 41, the source electrode 43, and the drain electrode 49 described above are used. By providing the antireflection film 53, the internal reflection component is reduced to about 1/3. As a result, the substantial reflection intensity obtained by adding the surface reflection component and the internal reflection component is reduced to about 2/3.

  Thus, in order to suppress reflection beyond a certain level, it is important not only to suppress the reflectance of the optical functional film 29 but also to suppress reflection from the inside of the liquid crystal panel.

  That is, an optical functional film 29 that suppresses reflection of external light is provided on at least one side of the liquid crystal panel 10, and the antireflection film 53 is formed on the conductive film that forms the gate signal line 37 and the source signal line 39 of the switching element 35. Even if it is a liquid crystal display device using the optical functional film 29 having particularly excellent antireflection and antiglare properties and reducing the reflection on the surface of the liquid crystal panel, the reflected light from the inside of the liquid crystal panel becomes apparent. Ingredients can be reduced. Thereby, reflection of external light can be reduced and good display characteristics can be obtained.

Hereinafter, the detailed composition of the optical functional film will be described. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . Moreover, in this specification, description with "(meth) acrylate" represents the meaning of "at least one of an acrylate and a methacrylate." The same applies to “(meth) acrylic acid” and the like. Furthermore, the term “on the support” as used in the present specification includes both the case where the surface directly refers to the support and the case where the surface includes a layer (film) provided on the support. It is.
(1) AR film The antireflection film as the optical functional film 29 shown in FIG. 1 has the layer structure shown in FIG. In particular, in this antireflection film, the intermediate refractive index layer is represented by the following formula (I) and the high refractive index layer is represented by the following formula (designated wavelength λ (representative of the wavelength region having the highest visibility): II), and the low refractive index layer satisfies the following formula (III).
Formula (I) λ / 4 × 0.68 <n ¹ d ¹ <λ / 4 × 0.74
Formula (II) λ / 2 × 0.66 <n ² d ² <λ / 2 × 0.72
Formula (III) λ / 4 × 0.84 <n ³ d ³ <λ / 4 × 0.92
(Where n ¹ is the refractive index of the medium refractive index layer, d ¹ is the layer thickness (nm) of the medium refractive index layer, and n ² is the refractive index of the high refractive index layer; D ² is the thickness (nm) of the high refractive index layer, n ³ is the refractive index of the low refractive index layer, and d ³ is the thickness (nm) of the low refractive index layer, n ³ <n ¹ <n ²

  When the above formula (I), formula (II), and formula (III) are not satisfied, the reflectance cannot be lowered and the change in reflected color cannot be suppressed.

Further, the medium refractive index layer, the high refractive index layer, and the low refractive index layer,
The medium refractive index layer is (A) a medium refractive index layer having a refractive index of 1.60 to 1.64 and a thickness of 58.5 to 61.5 nm at a wavelength of 550 nm,
The high refractive index layer is (B) a high refractive index layer having a refractive index of 1.70 to 1.74 at a wavelength of 550 nm and a thickness of 107.5 nm to 112.5 nm,
The low refractive index layer is preferably (C) a low refractive index layer having a refractive index of 1.32 to 1.37 at a wavelength of 550 nm and a thickness of 88.0 nm to 92.0 nm.
By making the refractive index and thickness of each layer within the above ranges, it is possible to reduce the variation in the reflected color, which is preferable.

  The low refractive index layer preferably contains at least one kind of inorganic fine particles. Although this point will be described later, by satisfying all of the above relational expression, the refractive index and the layer thickness, and the inclusion of the inorganic fine particles in the low refractive index layer, the effect of excellent scratch resistance is achieved. Useful.

  In this configuration, it is not necessary to provide a hard coat layer, but it is preferable to provide a hard coat layer because the scratch resistance surface such as a pencil scratch test becomes strong. Further, a conductive layer may be provided separately from the medium refractive index layer or the high refractive index layer between the transparent support and the hard coat layer, and the medium refractive index layer or the high refractive index layer has conductivity. It is good also as a conductive layer.

The CIE standard light source D65 in the wavelength region of 380 nm to 780 nm has a specular reflected light color of 5 ° incident light, and the a ^* and b ^* values of the CIE 1976 L ^* a ^* b ^* color space are 0 ≦ a ^* ≦ 8, respectively. , -10 ≦ b ^* ≦ 0, and further within the above-described color fluctuation range, the color difference ΔE when the layer thickness of any layer among the layers fluctuates by 2.5% is expressed by the following formula ( The range of 1) is preferable because the neutrality of the reflected color is good, there is no difference in the reflected color for each product, and coating stripes and unevenness are not noticeable.

Formula (1): ΔE = | (L ^{* 2} + a ^{* 2} + b ^{* 2} ) ^1/2 − (L ^* ′ ² + a ^* ′ ² + b ^* ′ ² ) ^1/2 | ≦ 3
(L ^* ', a ^* ', b ^* 'are the colors of reflected light at the design film thickness)

  Further, when it is installed on the surface of the image display device, it can be remarkably reduced by setting the average value of the specular reflectance to 0.5% or less, which is preferable.

  In addition, when controlling the refractive index of the high refractive index layer, it is preferable to use inorganic fine particles as described later. However, titanium dioxide particles often used in this industry deteriorate in light resistance due to photocatalytic action. Problems may arise in terms of manufacturing suitability, durability, and the like. Therefore, by making the refractive index of the high refractive index layer within the above-mentioned range, it is possible to use inorganic fine particles having a refractive index lower than that of the titanium dioxide particles, for example, zirconium oxide particles. It came to the knowledge that the problem in this aspect does not occur either.

The specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” (manufactured by JASCO Corporation), and in the wavelength region of 380 to 780 nm, the incident angle θ ( The antireflection property can be evaluated by measuring the specular reflectivity at the exit angle −θ at θ = 5 to 45 °, 5 ° interval, and calculating the average reflectivity of 450 to 650 nm. Furthermore, from the measured reflectance spectra, L ^* value of the CIE1976L ^* a ^* b ^* color space representing the color of specular reflection light with respect to incident light of each angle of incidence of the CIE standard illuminant D _65, a ^* value, b ^* value And the color of the reflected light can be evaluated.

The refractive index of each layer can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.) by applying the coating solution of each layer to a glass plate so as to have a thickness of 3 to 5 μm.
The film thickness of each layer can be measured by cross-sectional observation using a reflection spectral film thickness meter “FE-3000” (manufactured by Otsuka Electronics Co., Ltd.) utilizing light interference or a TEM (transmission electron microscope). Although the reflection spectral film thickness meter can measure the refractive index simultaneously with the film thickness, it is desirable to use the refractive index of each layer measured by another means in order to increase the measurement accuracy of the film thickness. When the refractive index of each layer cannot be measured, film thickness measurement by TEM is desirable. In that case, it is desirable to measure 10 points or more and use the average value.

It is preferable that the antireflection film has a form in which the film is rolled up in the form during production. In that case, in order to obtain the neutrality of the color of the reflected color, the average value d (average value), minimum value d (minimum value), and maximum value d (maximum value) of the layer thickness in an arbitrary 1000 m long range The value of the layer thickness distribution calculated by the following formula (2) using the value) as a parameter is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less for each layer of the thin film layer. More preferably, it is particularly preferably 2.5% or less and 2% or less.
Formula (2): (maximum value d−minimum value d) × 100 / average value d

Next, each layer constituting the antireflection film will be described in detail.
[Transparent substrate film]
The transparent substrate film used as the transparent support of the antireflection film is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film polyolefin, alicyclic structure Polymer (Norbornene resin (Arton: trade name, manufactured by JSR Corporation, amorphous polyolefin (ZEONEX: Name, Nippon Zeon Co., Ltd.)), and the like. Among these, triacetyl cellulose, polyethylene terephthalate, is preferably a polymer having an alicyclic structure, particularly triacetyl cellulose.
Although the thickness of a transparent support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.
Although the arbitrary width | variety of a transparent support body can be used, the thing of 100-5000 mm is normally used from the point of handling, a yield, and productivity, and it is preferable that it is 800-3000 mm, 1000-2000 mm More preferably it is. The transparent support can be handled in the form of a roll, and is usually 100 m to 5000 m, preferably 500 m to 3000 m.
The surface of the transparent support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. More preferably.

<Cellulose acylate film>
Among the various films described above, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for polarizing plates is preferable.
For the cellulose acylate film, various improvement techniques are known for the purpose of improving mechanical properties, transparency, flatness, etc., and the technique described in the published technical report 2001-1745 is known as this film. Applicable to.

Here, a cellulose triacetate film is particularly preferable among the cellulose acylate films, and it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used has a value of Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) by gel permeation chromatography close to 1.0, in other words, the molecular weight distribution is narrow. preferable. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. Here, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with 32% or more of an acyl group, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
Here, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], and paragraph “0051” of JP-A No. 11-5851 are disclosed. To “0052” [Synthesis Example 3] can be used.

<Manufacture of cellulose acylate film>
The cellulose acylate film used here can be produced by a solution casting method (solvent casting method). In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

  The organic solvent is a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to contain. Two or more organic solvents may be mixed and used.

  The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the preferred number of carbon atoms may be within the range of the preferred number of carbon atoms specified above for the compound having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

  Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.

The cellulose acylate solution (dope) can be adjusted by a general method. A general method means processing at a temperature of 0 ° C. or higher (room temperature or high temperature). The solution can be prepared using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent. Non-chlorinated solvents can also be used, and examples thereof include those described in JIII Journal of Technical Disclosure No. 2001-1745.
The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).
The solution can be prepared by stirring the cellulose acylate and the organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while heating to a temperature not lower than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially.
The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.
When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.
It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.
Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acetate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.
In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring.
The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture at 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this way, the mixture of cellulose acetate and organic solvent solidifies.
The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acetate is dissolved in the organic solvent. The temperature can be raised by simply leaving it at room temperature or in a warm bath.
The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .
A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
A 20% by mass solution of cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) dissolved in methyl acetate by the cooling dissolution method was 33 according to differential scanning calorimetry (DSC). There exists a quasi-phase transition point between a sol state and a gel state in the vicinity of ° C., and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature plus about 10 ° C. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method.
The dope is cast on a drum or band, and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%.
The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. No. 7,736892, JP-B Nos. 45-4554, 49-5614, and 62-1115035.
The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  A film can also be produced by casting two or more layers by a solvent casting method using a plurality of prepared cellulose acylate solutions (dope). In this case, the dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 10 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state.

  When casting a plurality of cellulose acylate solutions of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, from a plurality of casting openings provided at intervals in the direction of travel of the transparent support. A film may be produced while casting and laminating a solution containing cellulose acylate. For example, JP-A 61-158414, JP-A 1-122419, JP-A 11-198285, etc. Can be applied. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-104813, It can be carried out by the methods described in JP-A Nos. 61-158413 and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A casting method may be used.

  Alternatively, by using two casting ports, the film cast on the transparent support is peeled off by the first casting port, and the second casting is performed on the side that is in contact with the transparent support surface. Alternatively, a film may be prepared, for example, a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port.

  Furthermore, the cellulose acylate solution is cast simultaneously with a solution for forming other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer), and the functional layer and film Co-formation can also be performed.

  In a single-layer solution, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution to obtain the required film thickness. In this case, the stability of the cellulose acylate solution is poor and solids are generated. In many cases, however, it becomes a problem due to a failure or poor flatness. As this solution, a plurality of cellulose acylate solutions are cast from a casting port. This makes it possible to extrude a highly viscous solution onto a transparent support at the same time, to improve the flatness and to produce an excellent planar film, as well as to dry load by using a concentrated cellulose acylate solution. Can be achieved, and the film production speed can be increased.

A plasticizer can be added to the cellulose acylate film in order to improve the mechanical properties or to improve the drying rate after casting during film production. As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP), diphenyl biphenyl phosphate, and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP), dicyclohexyl phthalate (DCyP) and diethyl hexyl phthalate (DEHP) Is included. Examples of citrate esters include triethyl O-acetylcitrate (OACTE), tributyl O-acetylcitrate (OACTB), and tricyclohexyl O-acetylcitrate (OACTCy). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Of these, phthalate ester plasticizers and citrate ester plasticizers are preferably used. DEP, DPP and OACTCy are particularly preferred.
The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose acylate, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass.

  A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. The deterioration inhibitors are described in JP-A-3-199201, JP-A-597073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared in consideration of the effect of the deterioration preventing agent and bleeding out (bleeding out) to the film surface. More preferably, the content is 0.01 to 0.2% by mass. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

In the cellulose acylate film, a retardation increasing agent can be used as necessary in order to adjust the retardation of the film. The retardation of the film is preferably 0 to 300 nm in the film thickness direction and 0 to 1000 nm in the in-plane direction.
An aromatic compound having at least two aromatic rings is preferable as the retardation increasing agent, and the aromatic compound is used in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more aromatic compounds may be used in combination.
Details are described in Japanese Patent Application Laid-Open Nos. 2000-1111914, 2000-275434, 2002-236215, and International Publication No. 00/065384.

<Stretching treatment of cellulose acylate film>
The produced cellulose acylate film can further improve drying unevenness, uneven film thickness caused by drying shrinkage, and surface unevenness by stretching treatment. The stretching treatment is also used for adjusting the retardation.
Although there is no limitation in particular in the method of the width direction extending | stretching process, the extending | stretching method by a tenter is mentioned as the example.
More preferably, the longitudinal stretching is performed in the longitudinal direction of the roll, and the longitudinal stretching is performed by adjusting the draw ratio of each pass roll (rotational ratio between the pass rolls) between the pass rolls that convey the roll film. Is possible.

<Polyethylene terephthalate film>
Here, the polyethylene terephthalate film is also excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is preferably used because it is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the hard coat layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Cosmo Shine A4100 and A4300 manufactured by Toyobo Co., Ltd.

Moreover, as a transparent support used, what consists of a polymer which has an alicyclic structure can also be used preferably. A polymer containing an alicyclic structure has an alicyclic structure in the repeating unit of the polymer, a polymer containing an alicyclic structure in the main chain, and an alicyclic structure in the measurement chain. Any of the polymers containing can be used.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability. Although carbon number which comprises an alicyclic structure does not have a restriction | limiting in particular, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. When the number of carbon atoms constituting the alicyclic structure is in this range, a transparent plastic film excellent in heat resistance and flexibility can be obtained.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably 90%. % By weight or more. If the number of repeating units having an alicyclic structure is too small, the heat resistance is undesirably lowered. In addition, repeating units other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer are suitably selected according to the intended purpose.

  Specific examples of the alicyclic structure-containing polymer include (i) a norbornene polymer, (ii) a monocyclic olefin polymer, (iii) a cyclic conjugated diene polymer, and (iv) a vinyl alicyclic polymer. Examples include hydrocarbon polymers and their hydrides. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

Specific examples of the norbornene-based polymer include ring-opening polymers of norbornene-based monomers, ring-opening copolymers of norbornene-based monomers and other monomers capable of ring-opening polymerization, and these Examples thereof include hydrides, addition polymers of norbornene monomers, addition polymers with other monomers copolymerizable with norbornene monomers, and the like. Among these, from the viewpoint of transparency, a hydride of a ring-opening (co) polymer of a norbornene-based monomer is particularly preferable.
Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ^2.5 ] deca-3,7-diene (conventional Name: cyclopentadiene), 7,8-benzotricyclo [4,3.0.1 ^2.5 ] dec-3-ene (common name: methanotetrahydrofluorene), tetracyclo [4.4.0.1 ^2.5 . 1 ^7.10 ] dodec-3-ene (common name: tetracyclododecene), and derivatives of these compounds, for example, those in which a substituent is introduced into the ring. Examples of the substituent include an alkyl group, an alkenyl group, an alkoxycarbonyl group, and a carboxyl group. In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers can be used alone or in combination of two or more.

  Other monomers capable of ring-opening polymerization with norbornene monomers include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene and the like. Derivatives; and the like.

Ring-opening polymers of norbornene-based monomers and ring-opening copolymers of norbornene-based monomers and other monomers copolymerizable therewith are polymerized in the presence of a ring-opening polymerization catalyst. Can be obtained.
Known ring-opening polymerization catalysts can be used.

  Other monomers that can be addition copolymerized with norbornene monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene and propylene, and derivatives thereof; cycloolefins such as cyclobutene and cyclopentene, and derivatives thereof. A non-conjugated diene such as 1,4-hexadiene; These monomers can be used alone or in combination of two or more. Among these, α-olefin is preferable, and ethylene is more preferable.

  The addition polymer of norbornene monomer and the addition copolymer of norbornene monomer and other monomer copolymerizable with it must be polymerized in the presence of an addition polymerization catalyst. Can be obtained. As the addition polymerization catalyst, a known catalyst can be used.

  A ring-opening polymer of a norbornene-based monomer, a hydride of a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening polymerization, carbon-carbon using a known hydrogenation catalyst It is obtained by hydrogenating unsaturated bonds, preferably 90% or more.

  Examples of the norbornene-based resin include those manufactured by ZEON Corporation, trade names “ZEONOR” and “ZEONEX”; manufactured by JSR Corporation, trade names “ARTON”; manufactured by Hitachi Chemical Co., Ltd., and trade names “OPTOREZ”; manufactured by Mitsui Chemicals, Inc. The trade name “APEL” is commercially available.

Examples of the monocyclic olefin polymer include addition polymer polymers such as cyclohexene, cycloheptene, and cyclooctene.
Examples of the cyclic conjugated diene polymer include a polymer obtained by 1,2-addition polymerization or 1,4-addition polymerization of a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene. .

The vinyl alicyclic hydrocarbon polymer is a polymer having a repeating unit derived from vinylcycloalkane or vinylcycloalkene. Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon compounds such as vinyl cyclohexane and hydrides thereof; polymers of vinyl aromatic hydrocarbon compounds such as styrene and α-methyl styrene. And hydrides of the aromatic ring moiety.
The vinyl alicyclic hydrocarbon polymer is a random copolymer of a vinyl alicyclic hydrocarbon compound or a vinyl aromatic hydrocarbon compound and another monomer copolymerizable with these monomers, It may be a copolymer such as a block copolymer and a hydride thereof.

  The molecular weight of the polymer having an alicyclic structure is a polyisoprene or polystyrene equivalent weight average molecular weight measured by gel permeation chromatography using cyclohexane (toluene when the polymer resin is not dissolved) as a solvent. Usually in the range of 10,000 to 300,000, preferably 20,000 to 200,000. When the molecular weight is in such a range, the mechanical strength and molding processability of the transparent plastic film are highly balanced and suitable.

  Although the glass transition temperature of the polymer which has an alicyclic structure should just be selected suitably according to a use purpose, Preferably it is 80 degreeC or more, More preferably, it is the range of 100 to 250 degreeC. When the glass transition temperature is in such a range, the transparent plastic film is excellent in durability without causing deformation or stress in use at high temperatures.

A transparent support composed of a polymer having an alicyclic structure can be obtained by molding the polymer into a film by a known molding method.
Examples of the method for forming into a film include a solution casting method and a melt extrusion method. Among these, the melt extrusion molding method is preferable from the viewpoint of reducing the content of volatile components and the thickness unevenness in the film and productivity. Further, examples of the melt extrusion molding method include a method using a die such as a T die and an inflation method, but a method using a T die is preferable in terms of excellent thickness accuracy.
When a method using a T die is employed as a method for forming a film, the melting temperature in an extruder having a T die is preferably 80 ° C. to 180 ° C. higher than the glass transition temperature of the polymer used. It is more preferable to set the temperature to be higher by 150 ° C. If the melting temperature in the extruder is excessively low, the fluidity of the polymer is lowered. Conversely, if the melting temperature is excessively high, the polymer may be deteriorated.

  Furthermore, it is preferable to pre-dry the polymer to be used before forming into a film. For example, the preliminary drying is performed using a hot air dryer in the form of pellets. The drying temperature is preferably 100 ° C. or more, and the drying time is preferably 2 hours or more. By performing preliminary drying, the amount of volatile components in the film can be reduced. Furthermore, foaming of the extruded polymer can be prevented.

  The polymer to be used preferably has a saturated water absorption of less than 0.05%. By using a material having a saturated water absorption rate of less than 0.05%, moisture is released when forming a laminate on the film, so that quality is not deteriorated and productivity is not lowered. Further, the film does not expand and contract due to moisture absorption, and the laminated layer does not peel from the transparent plastic film. In particular, when used in a large-screen liquid crystal display device, it is possible to eliminate image quality deterioration caused by dimensional changes due to moisture absorption.

[High refractive index layer and medium refractive index layer]
As described above, the refractive index of the high refractive index layer, which is a thin film layer, is preferably 1.70 to 1.74, and more preferably 1.71 to 1.73. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. As described above, the refractive index of the medium refractive index layer is preferably 1.60 to 1.64, and more preferably 1.61 to 1.63.
The formation method of the high refractive index layer and the medium refractive index layer is a chemical vapor deposition (CVD) method or physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or sputtering method, which is a kind of physical vapor deposition method, to form a transparent thin film of inorganic oxide. Although it can be used, an all wet coating method is preferred.

The medium refractive index layer can be similarly adjusted using the same material except that the refractive index is different from that of the high refractive index layer. Therefore, the high refractive index layer will be particularly described below.
The medium refractive index layer and the high refractive index layer are inorganic fine particles containing at least one metal oxide selected from Ti, Zr, In, Zn, Sn, Al, and Sb, and have at least three functional groups. After applying a coating composition containing a curable compound having a polymerizable group (curable material) (hereinafter sometimes referred to as “binder precursor”), a solvent and a polymerization initiator, and drying the solvent, It is preferably formed by being cured by heating, ionizing radiation irradiation or a combination of both means. When a curable resin or initiator is used, a medium refractive index layer or a high refractive index layer excellent in scratch resistance and adhesion is formed by curing the curable resin by a polymerization reaction by heat and / or ionizing radiation after coating. it can.

(Inorganic fine particles)
As the inorganic fine particles, metal (eg, Ti, Zr, In, Zn, Sn, Sb, Al) oxides are preferable, and zirconium oxide fine particles are most preferable from the viewpoint of refractive index. However, from the viewpoint of conductivity, it is preferable to use inorganic fine particles whose main component is an oxide of at least one kind of metal of Sb, In, and Sn. The refractive index can be adjusted to a predetermined refractive index by changing the amount of the inorganic fine particles. The average particle size of the inorganic fine particles in the layer is preferably 10 to 120 nm, more preferably 15 to 100 nm, and further preferably 20 to 90 nm when zirconium oxide is used as a main component. Within this range, haze is suppressed, dispersion stability, and adhesion with the upper layer due to moderate irregularities on the surface become favorable, which is preferable.

The inorganic fine particles mainly composed of zirconium oxide preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferred.
The mass average diameter of primary particles of inorganic fine particles mainly composed of zirconium oxide is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.
The addition amount of the inorganic fine particles varies depending on the layer to be added. In the medium refractive index layer, it is 10 to 50% by mass, preferably 15 to 40% by mass, and preferably 20 to 30% by mass with respect to the solid content of the entire medium refractive index layer. Is more preferable. In a high refractive index layer, it is 40-90 mass% with respect to solid content of the whole high refractive index layer, 50-85 mass% is preferable, and 60-80 mass% is still more preferable.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph.
The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, treatment with a silane coupling agent having an acryloyl group or a methacryloyl group is particularly effective. Chemical surface treatment agents for inorganic fine particles, solvents, catalysts, and dispersion stabilizers are described in JP-A-2006-17870, [0058] to [0083].

(Curable compound)
As the curable compound, a polymerizable compound is preferable, and as the polymerizable compound, an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably used. The functional group in these compounds is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2-2-2bis {4- (acryloxy-polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Is mentioned. Two or more polyfunctional monomers may be used in combination.
The usage-amount of a sclerosing | hardenable compound can be adjusted in the range with which the refractive index of each above-mentioned layer is satisfy | filled.

(Polymerization initiator)
As the polymerization initiator, it is preferable to use a photopolymerization initiator. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  Commercially available radical photopolymerization initiators include Kayacure (DETX-S, BP-100, BDMK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 907, 369, 1173, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals Co., Ltd., Esacure (KIP100F, KB1, EB3, BP, manufactured by Sartomer) X33, KT046, KT37, KIP150, TZT) and the like.

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.

It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of curable compounds, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Examples of commercially available photosensitizers include Kayacure (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably performed by ultraviolet irradiation after the high refractive index layer is applied and dried.

  In addition to the above-mentioned components (inorganic fine particles, curable resins, polymerization initiators, photosensitizers, etc.), the high refractive index layer includes a surfactant, an antistatic agent, a coupling agent, a thickener, and an anti-coloring agent. , Colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductive metal particles, Etc. can also be added.

(solvent)
As said solvent, it is preferable to use the liquid whose boiling point is 60-170 degreeC. Specifically, water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, propyl acetate) , Butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (Eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy) 2-propanol) and the like. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are preferred, and particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
The amount of the solvent used is preferably such that the solid content concentration of the high refractive index layer coating composition is 2 to 30% by mass, and more preferably 3 to 20% by mass. The medium refractive index layer is preferably used so that the solid content concentration of the coating composition is 1 to 20% by mass, and more preferably 2 to 15% by mass.

(Method of forming high (medium) refractive index layer)
The inorganic fine particles mainly composed of zirconium oxide used for the high refractive index layer and the medium refractive index layer are preferably used for forming the high refractive index layer and the medium refractive index layer in a dispersion state.

The inorganic fine particles can be dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
The inorganic fine particles are preferably made as fine as possible in the dispersion medium, and the mass average diameter is 10 to 120 nm. Preferably it is 20-100 nm, More preferably, it is 30-90 nm, Most preferably, it is 30-80 nm.
By refining the inorganic fine particles to 200 nm or less, a high refractive index layer and a medium refractive index layer that do not impair transparency can be formed.

  The high refractive index layer and medium refractive index layer used here are curable compounds (for example, the above-mentioned binder precursors necessary for matrix formation) in the dispersion liquid in which the inorganic fine particles are dispersed in the dispersion medium as described above. Ionizing radiation curable polyfunctional monomers and polyfunctional oligomers), photopolymerization initiators, and the like to obtain a coating composition for forming a high refractive index layer and a middle refractive index layer, and a high refractive index layer on a transparent support. In addition, it is preferable to form by applying a coating composition for forming a medium refractive index layer and curing it by a crosslinking reaction or a polymerization reaction of a curable compound.

Furthermore, it is preferable to cause the binder of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant simultaneously with or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic fine particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains the inorganic fine particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

In the formation of the high refractive index layer, the crosslinking reaction or polymerization reaction of the curable compound is preferably carried out in an atmosphere having an oxygen concentration of 10% by volume or less.
By forming the high refractive index layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, and weather resistance of the high refractive index layer, and further, the high refractive index layer and the high refractive index layer are adjacent to each other. Adhesion with the layer can be improved.
Preferably, it is formed by a crosslinking reaction or a polymerization reaction of a curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2% by volume. Hereinafter, it is most preferably 1% by volume or less.
The thickness of the high refractive index layer is preferably 107.5 to 112.5 nm, and more preferably 109 to 111 nm. The thickness of the medium refractive index layer is preferably 58.5 to 61.5 nm, and more preferably 59 to 61 nm.

As described above, the medium refractive index layer can be obtained in the same manner using the same material as that of the high refractive index layer.
Specifically, the type of fine particles and the type of resin are selected so that the middle refractive index layer and the high refractive index layer satisfy the film thickness and refractive index of the formulas (I) and (II), and the blending ratio is set. Decide and determine the main composition.

[Low refractive index layer]
The low refractive index layer suitably used preferably has a refractive index of 1.32 to 1.37, more preferably 1.35 to 1.37. Within the above range, the reflectance can be suppressed and the film strength can be maintained, which is preferable. The low refractive index layer can be formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method, which is a kind of physical vapor deposition method. It is preferable to use a method by all wet coating using a composition for low refractive index layer forming solution coating described later. The low refractive index layer preferably contains inorganic fine particles. At least one of the inorganic fine particles is preferably a hollow particle, and hollow particles mainly composed of silica (hereinafter referred to as hollow silica particles) Particularly preferred.
The thickness of the low refractive index layer is preferably 88.0 to 92.0 nm, and more preferably 89.0 to 91.0 nm.
The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less.
The strength of the antireflection film formed up to the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test under a 500 g load.
Further, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 ° or more. More preferably, it is 95 ° or more, and particularly preferably 100 ° or more.

(Inorganic fine particles)
The inorganic fine particles that can be used in the low refractive index layer are preferably hollow particles.
The hollow particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.33. As the hollow particles, hollow silica particles are preferable, and the hollow silica particles will be described below as an example. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the void in the particle is a and the radius of the particle outer shell is b, the porosity x represented by the following formula (3) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.
Equation (3): x = (4πa 3/3) / (4πb 3/3) × 100
If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Particles are preferred.
The refractive index of these hollow silica particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).
A method for producing hollow silica particles is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616.
A commercial item can also be used as a hollow silica particle.

The coating amount of the hollow silica particles is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . Within this range, the effect of lowering the refractive index and improving the scratch resistance is good, prevents the formation of fine irregularities on the surface of the low refractive index layer, and maintains the appearance and integrated reflectance such as black tightening. can do.
The average particle diameter of the hollow silica particles is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, and still more preferably 40% or more and 60% or less of the thickness of the low refractive index layer. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
By setting the particle size within the above range, the ratio of the cavity portion is kept sufficiently, the refractive index is sufficiently lowered, the fine refractive surface is prevented from being formed on the surface of the low refractive index layer, the appearance and integration such as black tightening. The reflectance can be maintained well. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the hollow silica particles can be determined from an electron micrograph.

Here, silica particles having no voids can be used in combination with hollow silica particles. The preferred particle size of silica without voids is 5 nm to 150 nm, more preferably 10 nm to 80 nm, and most preferably 15 nm to 60 nm.
Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It is preferably used in combination with “silica fine particles having a diameter”.
Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.
The average particle size of the silica fine particles having a small size is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

  Hollow particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, treatment with a silane coupling agent having an acryloyl group or a methacryloyl group is particularly effective. Hollow particle chemical surface treatment agents, solvents, catalysts, and dispersion stabilizers are described in JP-A-2006-17870, [0058] to [0083].

The low refractive index layer is formed by applying a coating composition containing a film-forming solute and one or more solvents, drying the solvent, and then curing by heating, ionizing radiation irradiation, or a combination of both means. It is preferred that
The solute is preferably either a composition containing a heat- or ionizing radiation-curable fluorine-containing curable resin, or a hydrolyzate of an organic silyl compound and a partial condensate thereof.
It is more preferable to use a composition containing a fluorine-containing curable resin, and an embodiment in which a hydrolyzate of an organic silyl compound and a partial condensate thereof are used supplementarily is more preferable. The addition amount of the hydrolyzate of the organic silyl compound and the partial condensate thereof used in an auxiliary amount is 10 to 40% by mass of the fluorinated curable resin.

(Fluorine-containing curable resin)
Examples of the fluorine-containing curable resin (hereinafter also referred to as “fluorinated polymer”) include perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). In addition to hydrolysis and dehydration condensates, there may be mentioned fluorine-containing copolymers having a fluorine-containing monomer unit and a constituent unit for imparting crosslinking reactivity as constituent components. In particular, the low refractive index layer is preferably formed by a cured film of a copolymer having a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as essential constituent components. . It is also preferable to use a curing agent such as polyfunctional (meth) acrylate in combination from the viewpoint of achieving both low refractive index and film hardness. Although there is no restriction | limiting in particular in the mixing ratio of this fluoropolymer and this polyfunctional (meth) acrylate, It is desirable to set it as the mixing ratio which does not raise | generate phase separation with the film after drying. Of course, only one of them can be used. Specific examples of the polyfunctional (meth) acrylate include a photopolymerizable polyfunctional monomer described in a high refractive index layer.

Below, the example of the preferable fluorine-containing curable resin used for a low refractive index layer is demonstrated.
Fluorinated vinyl monomers include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (trade name) , Osaka Organic Chemical Co., Ltd.) and M-2020 (trade name, manufactured by Daikin Co., Ltd.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, and transparency. From the viewpoint of availability, hexafluoropropylene is particularly preferable. Here, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. %. By setting the composition ratio of the fluorinated vinyl monomer within the above range, the refractive index can be sufficiently lowered and the film strength can be maintained.

  The fluorine-containing curable resin used for the low refractive index layer preferably has a crosslinking reactive group. As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxy group, hydroxy group, amino group , Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) But It is below. The copolymer as the fluorine-containing polymer used in the low refractive index layer preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential constituent component. Generally, the (meth) acryloyl group-containing repeating unit preferably accounts for 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight. Increasing the composition ratio of these (meth) acryloyl group-containing repeating units improves the film strength but also increases the refractive index, which is preferable.

  In the copolymer useful here, in addition to the repeating unit derived from the fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the transparent support and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and more preferably in the range of 0 to 40 mol%. The range of 0 to 30 mol% is particularly preferable.

  The vinyl monomer that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2) -Ethylhexyl, 2-hydroxyethyl acrylate), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p- Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate, Vinyl pionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tertbutylacrylamide, N- Cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the above polymer.

  As a preferred form of the fluorine-containing curable resin used here, one having the following general formula III may be mentioned.

Formula III

In the general formula III, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, * - (} CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * - CH 2 CH (OH ) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents a connecting site on the polymer main chain side, and ** represents a connection on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In general formula III, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula III, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Adhesiveness to a transparent support, polymer Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc., can be selected as appropriate, depending on the purpose, single or multiple vinyl monomers It may be constituted by.

  Examples of preferred vinyl monomers include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, propionic acid Vinyl esters such as vinyl and vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, etc. (Meth) acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, male Acid, can be mentioned and unsaturated carboxylic acids and derivatives thereof such as itaconic acid, more preferably a vinyl ether derivative, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. However, x + y + z = 100. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  A particularly preferred form of the copolymer used here is general formula IV.

Formula IV

In the above general formula IV, X, x and y have the same meaning as in general formula III, and the preferred ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. However, x + y + z1 + z2 = 100. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  For the copolymer represented by the general formula III or IV, for example, a (meth) acryloyl group is introduced into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any one of the methods described above. Can be synthesized.

  Although the preferable example of a useful copolymer is shown below, it is not limited to these.

  The copolymer as the fluorine-containing curable resin used here is synthesized by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization to synthesize precursors such as hydroxyl group-containing polymers. Then, it can be carried out by introducing a (meth) acryloyl group by the polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like, and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to perform the polymerization in the range of 50 to 100 ° C.

The reaction pressure can be selected as appropriate, but it is usually preferably about 0.098 to 9.8 MPa (1 to 100 kg / cm ² ), particularly about 0.098 to 2.94 MPa (1 to 30 kg / cm ² ). . The reaction time is about 5 to 30 hours.

As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.
A commercial item can also be used as a fluorine-containing curable resin.
The amount of the fluorine-containing curable resin thus obtained is preferably 10 to 98% by mass, more preferably 30 to 95% by mass in the total solid content of the low refractive index layer coating composition. . In particular, when inorganic fine particles are used in combination, it is preferably 30 to 80% by mass, and more preferably 40 to 75% by mass.

(Coating composition for forming a low refractive index layer)
The coating composition for forming a low refractive index layer usually takes the form of a liquid, and preferably contains the inorganic fine particles and the fluorinated curable resin, and if necessary, various additives and radical polymerization initiators in an appropriate solvent. It is prepared by dissolving in At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1 to 20% by mass. Degree.

  The radical polymerization initiator may be in any form of generating radicals by the action of heat or generating radicals by the action of light.

As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with ionizing radiation.
Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photoradical polymerization initiators.

  The amount of the compound that initiates radical polymerization by the action of heat or light may be an amount that can initiate polymerization of the carbon-carbon double bond, and is based on the total solid content in the low refractive index layer forming composition. 0.1-15 mass% is preferable, More preferably, it is 0.5-10 mass%, Especially preferably, it is the case of 2-5 mass%.

(solvent)
The solvent contained in the coating composition for the low refractive index layer is not particularly limited as long as the fluorine-containing curable resin is uniformly dissolved or dispersed without causing precipitation, and two or more kinds of solvents are used in combination. You can also Preferred examples include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), ethers (tetrahydrofuran, 1,4-dioxane, etc.), alcohols (methanol, ethanol, isopropyl). Alcohol, butanol, ethylene glycol, etc.), aromatic hydrocarbons (toluene, xylene, etc.), water and the like.

(Other compounds suitably contained in the coating composition for forming a low refractive index layer)
In addition, for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipping property, a known silicone-based or fluorine-based antifouling agent, slipping agent, and the like can be appropriately added. In the case of adding these additives, it is preferably added in the range of 0 to 20% by mass, more preferably in the range of 0 to 10% by mass of the total solid content of the low refractive index layer. Particularly preferred is 0 to 5% by mass.

  The low refractive index layer can contain an inorganic filler, a silane coupling agent, a slip agent, a surfactant and the like. In particular, it is preferable to contain inorganic fine particles, a silane coupling agent, and a slip agent.

  As the silane coupling agent, a compound represented by the following general formula (I) and / or a derivative compound thereof can be used. Preferred are silane coupling agents containing a hydroxyl group, a mercapto group, a carboxy group, an epoxy group, an alkyl group, an alkoxysilyl group, an acyloxy group, and an acylamino group, and particularly preferred are an epoxy group and a polymerizable acyloxy group ( (Meth) acryloyl), a silane coupling agent containing a polymerizable acylamino group (acrylamino, methacrylamino).

  Particularly preferred among the compounds represented by the following general formula (I) are compounds having a (meth) acryloyl group as a crosslinking or polymerizable functional group, such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxy And propyltrimethoxysilane.

  As the slip agent, a silicone compound such as dimethyl silicone, and a fluorine-containing compound into which a polysiloxane segment is introduced are preferable.

[Organic silyl compounds]
The organic silyl compound becomes a hydrolyzate and / or a partial condensate obtained by hydrolysis and condensation in the coating composition for forming a low refractive index layer, and acts as a binder in the composition. To improve the alkali resistance.

  As an organic silyl compound used for the coating composition for low refractive index layer formation, the compound represented by following General formula (1) is mentioned preferably.

Formula (1): R ¹¹ _m Si (X ¹¹ ) _n

(In the formula, X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹¹ represents an alkyl group, an alkenyl group, or an aryl group, and R ¹² represents an alkyl group. M + n represents 4 and m and n are each a positive integer.)

Specifically, R ¹¹ is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, i-propyl group, butyl group, hexyl group, octyl group), carbon number 2 -10 substituted or unsubstituted alkenyl group (for example, vinyl group, allyl group, 2-buten-1-yl group), or substituted or unsubstituted aryl group having 6 to 10 carbon atoms (for example, phenyl group) R ¹² represents a group having the same meaning as the alkyl group represented by R ¹¹ . When the group represented by R ¹¹ or R ¹² has a substituent, preferred substituents are halogen (for example, fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (for example, Methyl group, ethyl group, i-propyl group, propyl group, t-butyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), aromatic heterocyclic group (for example, furyl group, pyrazolyl group, pyridyl group) Etc.), alkoxy groups (eg methoxy group, ethoxy group, i-propoxy group, hexyloxy group etc.), aryloxy groups (eg phenoxy group etc.), alkylthio groups (eg methylthio group, ethylthio group etc.), arylthio Group (for example, phenylthio group), alkenyl group (for example, vinyl group, allyl group, etc.), acyloxy group (for example, acetoxy group) , Acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), carbamoyl group (eg, carbamoyl group, N- Methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group, etc.), acylamino group (for example, acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like. .

  The compound of the general formula (1) forms a matrix by a so-called sol-gel method in which it is hydrolyzed and condensed with each other. The compound of general formula (1) is represented by the following four general formulas.

General formula (1a): Si (X ¹¹ ) ₄
Formula (1b): R ¹¹ Si (X ¹¹ ) ₃
General formula (1c): R ¹¹ ₂ Si (X ¹¹ ) ₂
Formula (1d): R ¹¹ ₃ SiX ¹¹

First, the component of General formula (1a) is demonstrated concretely.
Specific examples of the compound represented by the general formula (1a) include tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, and tetra-s-. Examples include butoxysilane and tetra-t-butoxysilane. Tetramethoxysilane or tetraethoxysilane is particularly preferable.

Next, the component of general formula (1b) is demonstrated. In the component of the general formula (1b), R ¹¹ represents a group having the same meaning as R ¹¹ in the general formula (1). In addition, γ-chloropropyl group, vinyl group, CF ₃ CH ₂ CH ₂ CH ₂ —, C ₂ F ₅ CH ₂ CH ₂ CH ₂ —, C ₃ F ₇ CH ₂ CH ₂ CH ₂ —, C ₂ F ₅ CH _{2 CH 2 -, CF 3 OCH 2} CH 2 CH 2 -, C 2 F 5 OCH 2 CH 2 CH 2 -, C 3 F 7 OCH 2 CH 2 CH 2 -, (CF 3) 2 CHOCH 2 CH 2 CH 2 - , C ₄ F ₉ CH ₂ OCH ₂ CH ₂ CH ₂ —, 3- (perfluorocyclohexyloxy) propyl group, H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ —, H (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ -, 3-glycidoxypropyl group, 3-acryloxy propyl Group, 3-methacryloxypropyl group, 3-mercaptopropyl group, a phenyl group, a 3,4-epoxycyclohexylethyl group.

X ¹¹ represents —OH, a halogen atom, —OR ¹² group, or —OCOR ¹² group. R ¹² represents a group having the same meaning as R ¹² in the general formula (1). Preferably, it is a C1-C5 alkoxy group or a C1-C4 acyloxy group, for example, a chlorine atom, a methoxy group, an ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group , S-butyloxy group, t-butyloxy group, acetyloxy group and the like.

Specific examples of these components of the general formula (1b) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i -Propyltrimethoxysilane, i-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Toxisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, _{CF 3 CH 2 CH 2 CH 2} Si (OCH 3) 3 -, C 2 H 5 CH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 2 F 5 CH 2 CH 2 Si (OCH 3) 3 -, _{C 3 F 7 CH 2 CH 2} CH 2 Si (OCH 3) 3 -, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 3 F 7 OCH 2 CH 2 CH 2 Si (OC 2 _{H 5) 3 -, (CF} 3) 2 CHOCH 2 CH 2 CH 2 Si (OCH 3) 3 -, C 4 F 9 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3) 3 - _{H (CF 2) 4 CH 2} OCH 2 CH 2 CH 2 Si (OCH 3) 3 -, 3- can be mentioned (perfluorocyclohexyl) propyl silane.

Among these, an organic silyl compound having a fluorine atom is preferable. In the case of using an organic silyl compound having no fluorine atom as R ^11, it is preferable to use methyltrimethoxysilane or methyltriethoxysilane. Said organic silyl compound may be used individually by 1 type, and can also use 2 or more types together.

Next, the component of general formula (1c) is demonstrated. The component of the general formula (1c) has the general formula R ¹¹ ₂ Si (X ¹¹ ) ₂ {wherein R ¹¹ and X ¹¹ are defined as the organic silyl compound used for the component of the general formula (1b), It is the same as R ¹¹ and X ¹¹ }. However, the plurality of R ¹¹ may not be the same group.

Specific examples of these organic silyl compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyl. dimethoxysilane, di -i- propyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, (CF 3 CH 2 CH 2 CH 2) 2 Si ( _{OCH 3) 2, (C 3} F 7 OCH 2 CH 2 CH 2) 2 Si (OCH 3) 2, [H (CF 2) 6 CH 2 OCH 2 CH 2 CH 2] 2 Si (OCH 3) 2, ( C ₂ F ₅ OCH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like can be mentioned, and an organic silyl compound having a fluorine atom is preferred. In the case of using an organic silyl compound having no fluorine atom as R ¹¹ is, dimethyldimethoxysilane, dimethyldiethoxysilane are preferred. Moreover, the organic silyl compound represented by the component of general formula (1c) may be used individually by 1 type, or can also use 2 or more types together.

Next, the component of general formula (1d) is demonstrated. The components of the general formula (1d), the general formula R ¹¹ ₃ SiX ¹¹ {wherein, R ¹¹ and X ¹¹ R ¹¹ as defined in the organosilyl compound used in component of the general formula (1b) is and X ¹¹ It is an organic silyl compound represented by However, the plurality of R ¹¹ may not be the same group.

  Specific examples of these organic silyl compounds are trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-i-propylmethoxysilane. , Tri-i-propylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane and the like.

  Each component of the general formulas (1a) to (1d) can be used alone, but may be used as a mixture, and the mixing ratio at that time is when the component (1a) is 100 parts by mass. The component (1b) is 0 to 100 parts by mass, preferably 1 to 60 parts by mass, and more preferably 1 to 40 parts by mass. The component (1c) is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass when the component (1a) is 100 parts by mass. The component (1d) is preferably 0 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass when the component (1a) is 100 parts by mass. Among the components (1a) to (1d), the proportion of the component (1a) is preferably 30% by mass or more in 100% by mass of the total organic silyl compound. If the ratio of the component (1a) is 30% by mass or more, it is preferable because problems such as a decrease in adhesion and curability of the obtained coating film do not occur. In addition to the components of the general formulas (1a) to (1d), compounds described in JP-A-2006-30740, [0039] and [0052] to [0067] are added, or a coating composition for forming a low refractive index layer It is desirable to prepare

(Formation of a low refractive index layer)
The low refractive index layer is irradiated with ionizing radiation simultaneously with application or after application / drying of a coating composition in which hollow particles, fluorine-containing curable resin, organic silyl compound and other optional components contained therein are dissolved or dispersed (for example, And light irradiation, electron beam irradiation, etc.) and are preferably cured by a crosslinking reaction by heating or a polymerization reaction.
In particular, when the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, an outermost layer having excellent physical strength and chemical resistance can be obtained.
The oxygen concentration is preferably 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume or less, and most preferably 1% by volume or less.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

[Conductive layer]
The antireflection film preferably has a conductive layer in terms of preventing static electricity on the film surface. The conductive layer may be provided separately from the thin film layer described so far, and the thin film layer may have conductivity.
When the conductive layer is a thin film layer, that is, a layer different from the film thickness and refractive index satisfying the formulas (I) to (III), the conductive layer is positioned between the thin film layers. Or a layer positioned between the thin film layer closest to the transparent support or an upper layer of the thin film layer close to the film surface. The thickness of the conductive layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The materials used for the conductive layer and the performance of the conductive layer will be described in detail below.
At least one of the thin film layers of the antireflection film can be a conductive layer. That is, a conductive layer may be formed by imparting conductivity to at least one of the low refractive index layer, the middle refractive index layer, and the high refractive index layer which is a thin film layer. In this case, it is necessary to select a material for the conductive layer so that the layer thickness and refractive index satisfy the conditions of the corresponding layer in the formulas (I) to (III). Since the low refractive index layer is a surface layer of the antireflection film or a layer near the surface, it is most preferable to impart conductivity to prevent static electricity on the film surface. However, conductive particles and compounds are often high refractive index materials, and there is a problem that it is difficult to obtain a desired low refractive index. Since the conductive particles and compounds are high refractive index materials, it is easy to impart conductivity to the medium refractive index layer and the high refractive index layer. The low refractive index layer, medium refractive index layer, and high refractive index layer imparted with conductivity preferably have a surface resistance value of the following formula (4).
The materials used for the conductive layer and the performance of the conductive layer will be described in detail below.

  The method for forming the conductive layer is, for example, a method of applying a conductive coating liquid containing conductive fine particles and a reactive curable resin, a method of applying a transparent conductive material made of a transparent and conductive polymer, or transparent. A conventionally known method such as a method of forming a conductive thin film by vapor deposition or sputtering of a metal or metal oxide that forms a film can be used. The conductive layer can be formed on the transparent support directly or via a primer layer that strengthens adhesion to the transparent support. When a conductive layer is provided as a layer close to the outermost surface layer of the antireflection film, it is preferable because sufficient antistatic properties can be obtained even if the layer is thin. Moreover, it is preferable to have as an electroconductive layer the layer located between at least 1 layer of a thin film layer or a transparent support body, and the thin film layer located in the nearest vicinity of a transparent support body among this thin film layer. The coating method is not particularly limited, and an optimal method may be selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics of the coating solution and the coating amount. .

  The surface resistance of the conductive layer preferably has a resistance value (SR) that satisfies the following formula (4).

    Formula (4): LogSR ≦ 12

The Log SR is more preferably 5 to 12, further preferably 5 to 9, and most preferably 5 to 8. The surface resistance (SR) of the conductive layer can be measured by a four-probe method or a circular electrode method.
It is preferable that the conductive layer is substantially transparent. Specifically, the haze of the conductive layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

1. Transparent and conductive transparent conductive material A transparent conductive material is a transparent and conductive substance made of a polymer, and is a single material or a composite of a plurality of materials.
As the transparent conductive material, a cationic or anionic polymer exhibiting ionic conductivity, or a complex of a π-conjugated conductive polymer exhibiting electronic conductivity and an accompanying dopant is preferably used. In particular, a complex of a π-conjugated conductive polymer and an accompanying dopant is preferable.

1- (1) π-conjugated system conductive polymer The π-conjugated system conductive polymer can be used as long as the main chain is an organic polymer composed of a π-conjugated system. Examples thereof include polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacenes, polythiophene vinylenes, and copolymers thereof. From the viewpoint of easy polymerization and stability in air, polypyrroles, polythiophenes and polyanilines are preferred. Even if the π-conjugated conductive polymer remains unsubstituted, sufficient conductivity and compatibility with the binder resin can be obtained, but in order to further improve conductivity and dispersibility or solubility in the binder resin. It is preferable to introduce a functional group such as an alkyl group, a carboxy group, a sulfo group, an alkoxy group, a hydroxy group, or a cyano group into the π-conjugated conductive polymer.

  Specific examples of such a π-conjugated conductive polymer include poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), polypyrrole examples. (3-butylpyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole) , Poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3 -Hydroxypyrrole), poly (3-methoxypyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-hexyloxy) Pyrrole), poly (3-methyl-4-hexyloxy-pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.

  Examples of polythiophenes include poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly (3 -Heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3-chloro Thiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly (3 -Hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythiophene), poly (3-butoxythiophene), poly (3-hexyloxythiophene), poly (3-heptyloxythiophene), poly (3-octyloxythiophene), poly (3-decyloxythiophene), poly (3-dodecyloxythiophene) ), Poly (3-octadecyloxythiophene), poly (3,4-dihydroxythiophene), poly (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly (3,4-dipropoxy) Thiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyloxythiophene), poly ( 3,4-didecyloxythiophene), poly (3,4-didodecyloxythiophene) ), Poly (3,4-ethylenedioxythiophene), poly (3,4-propylenedioxythiophene), poly (3,4-butenedioxythiophene), poly (3-methyl-4-methoxythiophene), Poly (3-methyl-4-ethoxythiophene), poly (3-carboxythiophene), poly (3-methyl-4-carboxythiophene), poly (3-methyl-4-carboxyethylthiophene), poly (3-methyl -4-carboxybutylthiophene) and the like.

  Examples of polyanilines include poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like.

Among them, from one or two kinds selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), and poly (3,4-ethylenedioxythiophene). The (co) polymer is preferably used from the viewpoints of resistance and reactivity. Furthermore, polypyrrole and poly (3,4-ethylenedioxythiophene) are more preferable because they have higher conductivity and improved heat resistance.
In addition, alkyl-substituted compounds such as poly (N-methylpyrrole) and poly (3-methylthiophene) are more preferable because they improve solvent solubility, compatibility with a binder resin, and dispersibility. Among the alkyl groups, a methyl group is preferred because it does not adversely affect the conductivity.

1- (2) Dopant The transparent conductive material is preferably a composite of the π-conjugated conductive polymer and a dopant.
The dopant is preferably a polymer dopant, and particularly preferably a polyanion having an anionic group in the molecule.
Hereinafter, a dopant composed of a polyanion is referred to as a polyanion dopant. This polyanion dopant forms a complex by chemically oxidizing and doping a conductive polymer to form a salt.

  The anion group of the polyanion dopant is preferably a functional group that undergoes chemical oxidation doping to the conductive polymer, and that the protonic acid of the anion group can be bonded to any of a vinyl group, a glycidyl group, and a hydroxy group. Specifically, a sulfuric acid group, a phosphoric acid group, a sulfo group, a carboxy group, a phospho group, and the like are preferable, and a sulfo group and a carboxy group are more preferable from the viewpoint of chemical oxidation doping.

  Examples of the polyanion dopant having a sulfo group include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, and polyisoprene sulfone. An acid etc. are mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  Examples of the polyanion dopant having a carboxy group include polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid. An acid, polyacrylic acid, etc. are mentioned. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.

  The transparent conductive material is a chemical oxidative polymerization of a precursor monomer that forms the π-conjugated conductive polymer in a solvent in the presence of an appropriate oxidizing agent, an oxidation catalyst, and the polymer dopant (preferably a polyanion). Can be manufactured easily.

  The conductive material may contain a dopant other than the polyanion dopant in order to further improve electrical conductivity and thermal stability. Examples of the dopant include halogen compounds, Lewis acids, proton acids, and the like. Specific examples include organic acids such as organic carboxylic acids and organic sulfonic acids, organic cyano compounds, and fullerene compounds.

  Examples of the halogen compound include chlorine, bromine, iodine, iodine chloride, iodine bromide, iodine fluoride, and the like.

  Examples of the protic acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, borofluoric acid, hydrofluoric acid, and perchloric acid, organic carboxylic acids, phenols, and organic sulfonic acids.

  Furthermore, examples of organic carboxylic acids include formic acid, acetic acid, succinic acid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonic acid, tartaric acid, citric acid, lactic acid, succinic acid, monochloroacetic acid, dichloroacetic acid, and trichloroacetic acid. Trifluoroacetic acid, nitroacetic acid, triphenylacetic acid and the like.

  Examples of the organic sulfonic acid include alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl naphthalene disulfonic acid, naphthalene sulfonic acid formalin polycondensate, melamine sulfonic acid formalin polycondensate, naphthalene disulfonic acid, naphthalene trisulfonic acid, dinaphthylmethane. Examples include disulfonic acid, anthraquinone sulfonic acid, anthraquinone disulfonic acid, anthracene sulfonic acid, and pyrene sulfonic acid. These metal salts can also be used.

  Examples of the organic cyano compound include dichlorodicyanobenzoquinone (DDQ) and tetracyanoquinodimethanetetracyanoazanaphthalene.

  Examples of the fullerene compound include hydrogenated fullerene, hydroxylated fullerene, carboxylated fullerene, and sulfonated fullerene.

The polymer dopant is preferably crosslinked with a crosslinking point forming compound described later. Thereby, the adhesiveness of an electroconductive layer can be improved and the outstanding scratch resistance can be implement | achieved.
The polymer dopant preferably has at least two types of functional groups, at least one type being an anionic group, and at least the other type being a group that is not an anionic group.
Of the functional groups possessed by the polymer dopant, the residual anionic group that did not form a salt with the π-conjugated conductive polymer, or the group that is not an anionic group is preferably crosslinked with a crosslinking point forming compound described later. .
The functional group that is not an anionic group of the polymer dopant is not particularly limited as long as it is a group that crosslinks with a crosslinking point forming compound described later, and examples thereof include a hydroxy group, an amino group, a mercapto group, and the like. By copolymerizing ethanol, (hydroxymethyl) vinyl ketone, (2-hydroxyethyl) vinyl ketone, allylamine, 2-aminoethyl vinyl ether, 3-vinyloxy-1-propanamine, 2-allylaminoethanethiol and the like with a polymer dopant. be introduced. The copolymerization ratio of the monomer having a functional group that is not an anionic group is preferably 1 to 50 mol%, particularly preferably 5 to 30 mol%, and if it is less than 1 mol%, the number of crosslinking points becomes insufficient, and 50 mol% If it exceeds 1, it will not function sufficiently as an anionic dopant.

1- (3) Composite Composed of π-Conjugated Conductive Polymer and Polymeric Dopant Hereinafter, a polyanion dopant in the complex of π-conjugated conductive polymer and polymer dopant will be described as an example.

  During the formation of the composite, the main chain of the conductive polymer grows along the polyanion dopant because the anionic group of the polyanion dopant forms a salt with the conductive polymer along with the growth of the main chain of the conductive polymer. To do. Therefore, the obtained conductive polymer and polyanion dopant become a complex in which an infinite number of salts are formed. In this composite, one unit of anionic group forms a salt with respect to three units of the conductive polymer monomer, and several shortly grown conductive polymers form a salt along a long polyanion dopant. It is estimated that

  Examples of a method for forming a complex in which a conductive polymer and a polyanion dopant are combined include a method in which a monomer that forms a conductive polymer is chemically oxidatively polymerized in the presence of a polyanion dopant.

  The oxidizing agent and oxidation catalyst used for polymerizing the monomer in chemical oxidative polymerization may be any one that can oxidize the precursor monomer to obtain a π-conjugated conductive polymer. Peroxodisulfates such as ammonium oxodisulfate, sodium peroxodisulfate, and potassium peroxodisulfate; transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride; Examples thereof include metal halides such as boron fluoride and aluminum chloride, metal oxides such as silver oxide and cesium oxide, peroxides such as hydrogen peroxide and ozone, organic peroxides such as benzoyl peroxide, oxygen, and the like.

  Chemical oxidative polymerization may be performed in a solvent. The solvent used in that case is not particularly limited as long as it dissolves the polyanion dopant and the conductive polymer. For example, water, methanol, ethanol, propylene carbonate, cresol, phenol, xylenol, acetone, methyl ethyl ketone, Hexane, benzene, toluene, dioxane, diethyl ether, acetonitrile, benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl Examples include 2-imidazolidine, dimethylimidazoline, ethyl acetate, 2-methyltetrahydrofuran, dioxane, dimethyl sulfoxide, sulfolane, and diphenyl sulfone. These solvents can be used as a single solvent or a mixture of two or more solvents as required.

The application amount of the transparent conductive material is preferably 0.01 g to 5.0 g, more preferably 0.05 to 2.0 g, and most preferably 0.10 g to 1.0 g per square meter.
Further, when the transparent conductive material is a composite of the above-described π-conjugated conductive polymer and polymer dopant, the molecular weight per unit of the π-conjugated conductive polymer and the molecular weight per unit of the polymer dopant The ratio is preferably 1: 1 to 1: 5, more preferably 1: 1 to 1: 2.

2. Conductive inorganic fine particles of conductive layer The conductive layer can be formed using a coating composition obtained by dissolving conductive inorganic fine particles and a reactive curable resin in a solvent. In this case, the conductive inorganic fine particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic fine particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add at least one selected from Sb, P, B, Nb, In, V, and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

  The average particle diameter of the primary particles of the conductive inorganic fine particles used for the conductive layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic fine particles in the formed conductive layer is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic fine particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.

The conductive inorganic fine particles may be surface-treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.
Two or more kinds of conductive inorganic fine particles may be used in combination in the conductive layer.

  The ratio of the conductive inorganic fine particles in the conductive layer is preferably 20 to 90% by mass, more preferably 25 to 85% by mass, and most preferably 30 to 80% by mass in the total solid content. preferable.

  The conductive inorganic fine particles are used for forming a conductive layer in a dispersion state. As the dispersion medium for the conductive inorganic fine particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred. The conductive inorganic fine particles can be dispersed in the medium using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

(Binder precursor of conductive layer)
As the binder precursor of the conductive layer, a curable compound used in the high refractive index layer, particularly an ionizing radiation curable polyfunctional monomer or a polyfunctional oligomer is preferably used, and is formed by reacting a reactive curable resin. Crosslinked polymers can also be used as binders. The crosslinked polymer preferably has an anionic group.
The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersion state of the conductive inorganic fine particles. The crosslinked structure has a function of reinforcing the conductive layer by imparting a film forming ability to the polymer.

Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.
The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxy group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxy group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that connects the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure chemically bonds (preferably covalently bonds) two or more main chains. The cross-linked structure is preferably covalently bonded to three or more main chains. The crosslinked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. In addition, even if the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, the same effect can be obtained.
In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the proportion is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. % Is more preferable, and 0.1 to 28% by mass is most preferable.

  The binder can be used in combination with the following reactive organosilicon compound described in, for example, JP-A No. 2003-39586. The reactive organosilicon compound is used in the range of 10 to 70% by mass with respect to the ionizing radiation curable resin as the binder. The reactive organosilicon compound is preferably an organosilane compound, and it is possible to form a conductive layer using only this as a resin component.

[Hard coat layer]
In order to impart physical strength to the antireflection film, it is preferable to provide a hard coat layer between the transparent support and the thin film layer (between the thin film layers and the layer closest to the transparent support). In particular, it is preferably provided between the transparent support and the high refractive index layer (or medium refractive index layer). Moreover, it is preferable that the layer thickness of a hard-coat layer exists in the range of 1-30 micrometers.
The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Moreover, inorganic fine particles can also be contained.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those exemplified for the high refractive index layer, and it is preferable to polymerize using a photopolymerization initiator and a photosensitizer. The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried.
In order to impart brittleness, the hard coat layer may contain an oligomer or polymer having a mass average molecular weight of 500 or more, or both.
Examples of the oligomer and polymer include (meth) acrylate-based, cellulose-based, and styrene-based polymers, urethane acrylate, and polyester acrylate. Preferable examples include poly (glycidyl (meth) acrylate) and poly (allyl (meth) acrylate) having a functional group in the side chain.

  The total amount of oligomer and polymer in the hard coat layer is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 35 to 65% by mass with respect to the total mass of the hard coat layer. is there.

The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
In the formation of the hard coat layer, when the ionizing radiation curable compound is formed by a crosslinking reaction or a polymerization reaction, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. By forming in an atmosphere having an oxygen concentration of 10% by volume or less, a hard coat layer excellent in physical strength and chemical resistance can be formed, which is preferable.
Preferably, it is formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2 Volume% or less, most preferably 1 volume% or less.

As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.
The hard coat layer is preferably constructed by applying a coating composition for forming a hard coat layer on the surface of the transparent support.

The coating solvent is preferably a ketone solvent exemplified in the high refractive index layer. By using the ketone solvent, the adhesion between the surface of the transparent support (particularly, the triacetyl cellulose transparent support) and the hard coat layer is further improved.
Particularly preferred coating solvents are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
The coating solvent may contain a solvent other than the ketone solvent exemplified for the high refractive index layer.
In the coating solvent, the content of the ketone solvent is preferably 10% by mass or more of the total solvent contained in the coating composition. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

[Other layers of antireflection film]
The antireflection film may be provided with layers other than those described above. For example, an adhesive layer, a shield layer, a sliding layer, a light diffusing layer, or an antiglare layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.

  In addition, when the antireflection film is applied to a liquid crystal display device, it may have an undercoat layer to which particles having an average particle size of 0.1 to 10 μm are added, but the particles are added to the hard coat layer. It is also useful to make a light-scattering hard coat layer and eliminate ripples in the reflectance curve due to light interference. By providing such a layer, viewing angle characteristics can be improved, which is preferable. The average particle size of the particles is preferably 0.2 to 5.0 μm, more preferably 0.3 to 4.0 μm, and particularly preferably 0.5 to 3.5 μm.

  The refractive index of the particles is preferably 1.35 to 1.80, more preferably 1.40 to 1.75, and still more preferably 1.45 to 1.75.

Further, the difference in refractive index between the refractive index of the particles and the refractive index of the binder component other than the particles of the undercoat layer is preferably 0.02 or more. More preferably, the difference in refractive index is 0.03 to 0.5, more preferably the difference in refractive index is 0.05 to 0.4, and particularly preferably the difference in refractive index is 0.07 to 0.3. .
Examples of the particles added to the undercoat layer include inorganic particles and organic particles as matte particles added to the antiglare layer when the antiglare layer is provided. Preferably, particles described in JP-A-2002-55205, [0018] can be used.
The undercoat layer is preferably constructed between the hard coat layer and the transparent support. Moreover, it can also serve as an undercoat layer and a hard coat layer.
When particles having an average particle size of 0.1 to 10 μm are added to the undercoat layer, the haze of the undercoat layer is preferably 3 to 90%. More preferably, it is 5 to 80%, further preferably 7 to 45%, particularly preferably 10 to 40%.

[Antireflection film formation method, etc.]
Each layer of the antireflection film should be coated on the transparent support by the dip coating method, air knife coating method, curtain coating method, roller coating method, die coating method, wire bar coating method, and gravure coating method. Can be formed.
In order to increase the uniformity of the coating film among these coating methods, it is preferable to use a gravure coating method or a die coating method.
Among the gravure coating methods, the micro gravure method is more preferable. The die coating method is particularly preferable because the film thickness control is relatively easy because the die coating method is a total metering method, and further, there is little evaporation of the solvent in the coating part. A tandem method can be employed when forming multiple layers continuously.
In the die coating method, two or more layers can be applied simultaneously. The method of simultaneous application by the die coating method is described in the specifications of US Pat. These can be used.
In the die coating method, an extrusion type or slide type die can be used alone or in combination. Of these, an extrusion die (also referred to as a slot die) is preferable. For the die design, it is preferable to use the overbiting method described in detail in paragraph numbers 0344 to 0427 of JP2003-211052A and JP2006-122889A.

[Protective film for polarizing plate]
When the antireflection film is used as a surface protective film for a polarizing film (protective film for polarizing plate), the surface of the transparent support opposite to the side having the thin film layer, that is, the surface to be bonded to the polarizing film is hydrophilized. Thereby, adhesiveness with the polarizing film which has polyvinyl alcohol as a main component can be improved.
Of the two protective films of the polarizer, the film other than the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

When the antireflection film is used as a surface protective film for a polarizing film (protective film for polarizing plate), it is particularly preferable to use a triacetyl cellulose film as the transparent support.
As a method for producing a protective film for polarizing plate, (1) each layer constituting the antireflection film on one side of a transparent support previously saponified (eg, high refractive index layer, low refractive index layer, suitable) (2) A method of applying a hard coat layer or the like, that is, a layer of the antireflection film excluding the transparent support (hereinafter also referred to as “antireflection layer”), and (2) reflection on one surface of the transparent support. A method of saponifying the side or both sides to be bonded to the polarizing film after coating the anti-reflection layer, (3) A part of the anti-reflection layer is coated on one surface of the transparent support, and then bonded to the polarizing film There are three methods: a method of applying the remaining layer after saponifying the side or both sides, and (1) is hydrophilicized to the surface on which the antireflection layer is to be applied, and the transparent support and the antireflection layer It is difficult to ensure the adhesion with the Masui.

(Saponification treatment)
Examples of the saponification treatment method include the following two methods.
(1) Immersion method An antireflection film is immersed in an alkaline solution under appropriate conditions to saponify all surfaces that are reactive with alkali on the entire surface of the film, requiring no special equipment. Therefore, it is preferable from the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / l, particularly preferably 1 to 2 mol / l. The liquid temperature of a preferable alkali liquid is 30-70 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the above saponification conditions is preferably a combination of relatively mild conditions, but can be set according to the material and configuration of the antireflection film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface of the transparent support opposite to the surface having the antireflection layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle of water on the surface of the transparent support opposite to the side having the high refractive index layer, the better from the viewpoint of adhesiveness to the polarizing film. Since the surface having the rate layer is damaged by the alkali, it is important to set the necessary minimum reaction conditions. As an index of damage received by the antireflection layer due to alkali, the surface of the transparent support opposite to the side having the antireflection layer, that is, the bonding angle of the antireflection film, particularly when using the contact angle with water, is transparent. If the support is triacetyl cellulose, it is preferably 20 to 50 degrees, preferably 30 to 50 degrees, more preferably 40 to 50 degrees. By setting it as this range, the adhesiveness with a polarizing film is fully maintained, there is little damage to an antireflection film, and physical strength and light resistance can fully be maintained, which is preferable. Further, in order to prevent various adverse effects such as corrosion, dissolution, peeling, etc. on the antireflection layer due to the alkali solution, a saponification method is preferably used in which the antireflection layer side is protected with a laminate film to prevent damage. Although there is no limitation in particular in the kind of antireflection layer which uses this system, this form is especially preferable when an antireflection layer is formed with a vapor deposition film or a sol-gel film.

(2) Alkaline liquid application method As a means for avoiding damage to the antireflection film in the above-mentioned immersion method, the alkaline liquid is applied only to the surface opposite to the surface having the antireflection film under appropriate conditions, heated, washed with water, A drying alkaline solution coating method is preferably used. The application in this case means that an alkali solution or the like is brought into contact only with the surface to be saponified, and at this time, the contact angle with respect to water of the bonded surface of the antireflection film is 10 to 50 degrees. It is preferable to perform a saponification treatment. In addition to the application, it may include spraying, contact with a belt containing liquid, or the like. Since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material weak to the alkali solution. There are no particular restrictions on the type of antireflection layer using this method, but when it is formed with a vapor-deposited film or sol-gel film, various adverse effects such as corrosion, dissolution, and peeling occur due to the alkali solution. Is particularly preferable.

  In any of the above methods (1) and (2), since the antireflection layer can be formed by unwinding from the roll-shaped transparent support, a series of processes are added in addition to the above-described antireflection film manufacturing process. It may be done by operation. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate comprising the transparent support that has been unwound in the same manner.

(2) AGLR film The optical function film 29 shown in FIG. 1 can be configured to include an antiglare film. This anti-glare film (hereinafter, a film including an anti-glare function layer is referred to as a light scattering film, and an anti-reflection function layer is referred to as an optical film) has the layer structure shown in FIG.
The optical film is an optical film having a light diffusion layer containing translucent particles and a binder on a transparent support. The optical film shown here is also an antireflection film having a low refractive index layer on the light diffusion layer of the optical film. In the present specification, a layer having a physical and optical function formed on a transparent support is referred to as a functional layer. Here, the said optical film can have another functional layer as needed other than functional layers, such as a light-diffusion layer and a low-refractive-index layer.

1. Constituents First, various compounds that can be used in the present optical film (light scattering film or antireflection film) will be described.

  First, components used for forming a binder such as an ionizing radiation compound, an organosilane compound used as necessary, and an initiator will be described.

1- (1) Multifunctional monomer, polyfunctional oligomer The functional layer of the film can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer as a component for forming a binder is coated on a transparent support, and the polyfunctional monomer or polyfunctional oligomer is subjected to a crosslinking reaction or a polymerization reaction. Can be formed.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

  Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

  Among these, esters of polyhydric alcohol and (meth) acrylic acid are preferable. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like.

As the monomer binder, monomers having different refractive indexes can be used to control the refractive index of each layer. Examples of particularly high refractive index monomers include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like.
Further, for example, dendrimers described in JP-A-2005-76005 and JP-A-2005-36105, and norbornene ring-containing monomers as described in JP-A-2005-60425 can also be used.

Two or more polyfunctional monomers may be used in combination.
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

1- (2) Polymer Binder For the optical film, an uncrosslinked polymer or a crosslinked polymer can be applied to the binder component. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.
The polyolefin main chain consists of saturated hydrocarbons. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. In the polyurethane main chain, repeating units are bonded by a urethane bond (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group. The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group). The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that connects the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure is a structure in which two or more main chains are chemically bonded (preferably covalent bonds), but it is preferable to covalently bond three or more main chains. The crosslinked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles, like the anionic group. The same effect can be obtained even when the amino group, quaternary ammonium group and benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.
In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. It is more preferable that it is 0.1 to 28% by mass.

1- (3) Fluorine-containing polymer binder In the present optical film, a fluorine-containing polymer can be preferably used as a binder component, particularly in the low refractive index layer of the antireflection film.
Fluorinated vinyl monomers for forming a fluorinated polymer include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (For example, Biscoat 6FM (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Industries, Ltd.)), complete or partially fluorinated vinyl ethers, and the like are preferable. Is a perfluoroolefin, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like. Increasing the composition ratio of these fluorine-containing vinyl monomers can lower the refractive index but lowers the film strength. Here, it is preferable to introduce the fluorine-containing vinyl monomer so that the fluorine content of the fluorine-containing polymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. %.

Examples of the structural unit for imparting crosslinking reactivity to the fluoropolymer include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether,
(B): Monomer having a carboxyl group, hydroxy group, amino group, sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): reacting a compound having a crosslinkable functional group separately from the group that reacts with the functional group of (A) or (B) in the molecule with the structural unit of (A) or (B). Examples of the structural unit to be obtained (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

  As the structural unit (C), a crosslinkable functional group different from the group that reacts with the functional group (A) or (B) is preferably a photopolymerizable group. Examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide group, carbonyl Azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclopropene group, An azadioxabicyclo group etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting a (meth) acrylic acid ester containing an isocyanate group with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.
The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and the carboxyl group, hydroxyl group, etc. can be controlled from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. It is also preferable to leave a certain amount.

  Here, in the useful fluorine-containing polymer, the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the structural unit for imparting crosslinking reactivity such as a repeating unit having a (meth) acryloyl group in the side chain, as necessary, Copolymerize other vinyl monomers as appropriate from various viewpoints such as adhesion to substrates, polymer Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc. You can also. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the total in the fluoropolymer, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.

  Other vinyl monomer units that can be used in combination are not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene) , P-methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinegar) Vinyl, vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide) N-cyclohexylacrylamide), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.

  Particularly useful fluorine-containing polymers are random copolymers of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

  Moreover, it is preferable that a polysiloxane structure is introduced into the fluorine-containing polymer preferably used for the purpose of imparting antifouling properties. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable. Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.

  The preferred molecular weight of the fluorine-containing polymer that can be preferably used is a mass average molecular weight of 5000 or more, preferably 10,000 to 500,000, and most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

  As described in JP-A-10-25388 and JP-A-2000-17028, a curing agent having a polymerizable unsaturated group may be used in combination with the above polymer. Moreover, combined use with the compound which has a fluorine-containing polyfunctional polymerizable unsaturated group as described in Unexamined-Japanese-Patent No. 2002-145952 is also preferable. Examples of the compound having a polyfunctional polymerizable unsaturated group include the polyfunctional monomer. These compounds are particularly preferred because they have a large combined effect for improving scratch resistance, particularly when a compound having a polymerizable unsaturated group is used in the polymer body.

1- (4) Organosilane compound At least one of the layers constituting the optical film is at least one of a hydrolyzate of organosilane compound and / or a partial condensate thereof in the coating solution forming the layer. It is preferable from the viewpoint of scratch resistance that it contains a so-called sol component (hereinafter sometimes referred to as such).
In particular, in the antireflection film, it is particularly preferable that both the low refractive index layer and the light diffusion layer contain a sol component in order to achieve both antireflection ability and scratch resistance. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product and becomes a part of the binder of these layers. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

As the organosilane compound, those represented by the following general formula 1 can be preferably used.
Formula _{^{1: (R 1) m -Si}} (X) 4-m
In the general formula 1, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As an alkyl group, a C1-C30 alkyl group is preferable, More preferably, it is C1-C16, Most preferably, it is a C1-C6 thing. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ) And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, and is preferably 1 or 2.
When there are a plurality of Xs, the plurality of Xs may be the same or different.

There are no particular limitations on the substituents contained in R ^1, a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group (methyl, ethyl, i- propyl, n- Propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy ( Phenoxy, etc.), alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl) , Ethoxycarbonyl, etc.), aryl Xyloxycarbonyl group (phenoxycarbonyl, etc.), carbamoyl group (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino group (acetylamino, benzoylamino, acrylamino, methacryl) Amino) and the like, and these substituents may be further substituted.
R ¹ is preferably a substituted alkyl group or a substituted aryl group. When R ¹ there are a plurality, it may be different even multiple R ¹ is the same, respectively.
Two or more compounds of the general formula 1 may be used in combination.

As the organosilane compound used here, an organosilane compound having a vinyl polymerizable substituent represented by the following general formula 2 is also preferably used. In addition, the compound of the general formula 2 can be synthesized using two kinds of the compounds of the general formula 1 as starting materials.
General formula 2

In the general formula 2, R ₂ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ₂ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

l and m represent the respective mol% of the two components. l represents a number satisfying the mathematical formula of l = 100−m, and m represents a number from 0 to 50. As for m, the number of 0-40 is more preferable, and the number of 0-30 is especially preferable.
R _{3 to} R ₆ are preferably a halogen atom, a hydroxyl group, an unsubstituted alkoxy group, or an unsubstituted alkyl group. R _{3 to} R ₅ are more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methoxy group.
R ₆ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an alkoxycarbonyl group as a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
R ₇ has the same meaning as R ^{1 in} formula 1 above, more preferably a hydroxyl group or an unsubstituted alkyl group, still more preferably a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methyl group.

  Although the specific example of the starting material of the compound represented by the compound of General formula 1 below is shown, it is not limited. As described above, the compound of the general formula 2 can be synthesized using two kinds of the compounds of the general formula 1 as starting materials.

    M-48 Methyltrimethoxysilane

Among these, (M-1), (M-2), and (M-25) are particularly preferable as the organosilane containing a polymerizable group.
In order to obtain the effect of the present optical film, the content of the organosilane containing the vinyl polymerizable group in the hydrolyzate of organosilane and / or its partial condensate is preferably 30% by mass to 100% by mass, 50 mass%-100 mass% are more preferable, and 70 mass%-95 mass% are still more preferable. If the content of the organosilane containing the vinyl polymerizable group is 30% by mass or more, solids are produced, the liquid is turbid, the pot life is deteriorated, and the molecular weight is difficult to control (increase in molecular weight). Or problems such as difficulty in obtaining improved performance after polymerization (for example, scratch resistance of the antireflection film) due to a low content of the polymerizable group. When synthesizing the compound represented by the general formula 2, (M-1) and (M-2) as organosilanes containing the vinyl polymerizable group, and organosilanes having no vinyl polymerizable group ( It is preferable to use one of each of M-19) to (M-21) and (M-48) in combination in the above amounts.

  It is preferable to suppress volatility of at least one of the hydrolyzate of organosilane and the partial condensate thereof preferably used for stabilizing the performance of the coated product, specifically, volatilization per hour at 105 ° C. The amount is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The sol component used here is prepared by hydrolysis and / or partial condensation of the organosilane.
In the hydrolysis condensation reaction, 0.05 to 2.0 mol, preferably 0.1 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X), and the presence of the catalyst used in this configuration is present. Under stirring at 25-100 ° C.

In at least one of the hydrolyzate of organosilane and the partial condensate thereof used here, the mass average molecular weight of either the hydrolyzate of organosilane containing a vinyl polymerizable group or the partial condensate thereof has a molecular weight of 300. When excluding less than components, 450-20000 is preferable, 500-10000 is more preferable, 550-5000 is further preferable, and 600-3000 is more preferable.
Of the components having a molecular weight of 300 or more in the hydrolyzate of organosilane and / or its partial condensate, the component having a molecular weight of more than 20000 is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 3 mass% or less. If the component having a molecular weight greater than 20000 is 10% by mass or less, a cured film obtained by curing such a curable composition containing a hydrolyzate of organosilane and / or a partial condensate thereof is transparent. And adhesion to the substrate are sufficient.

Here, the mass average molecular weight and the molecular weight were measured using a TPCgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) with a solvent tetrahydrofuran (THF) and a differential refractometer detection. The molecular weight expressed in terms of polystyrene is based on the molecular weight, and the content of each molecular weight component is the area% of the peak in the molecular weight range when the peak area of the component having a molecular weight of 300 or more is defined as 100%.
The dispersity (mass average molecule / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

The ²⁹ Si-NMR analysis of the organosilane hydrolyzate and partial condensate used here confirms the state in which X in the general formula 1 is condensed in the form of -OSi.
At this time, when three bonds of Si are condensed in the form of -OSi (T3), when two bonds of Si are condensed in the form of -OSi (T2), one bond of Si is- When the condensation is performed in the form of OSi (T1), and the case where Si is not condensed at all (T0), the condensation rate α is expressed by the following formula (II).
Formula (II): α = (T3 × 3 + T2 × 2 + T1 × 1) / 3 / (T3 + T2 + T1 + T0)
The condensation rate α is preferably 0.2 to 0.95, more preferably 0.3 to 0.93, and particularly preferably 0.4 to 0.9.
If it is at least the lower limit, hydrolysis and condensation will proceed sufficiently and the monomer component will not increase, so that a film with sufficient curing can be obtained. If it is not more than the upper limit, hydrolysis and condensation will proceed excessively. Since the hydrolyzable group remains moderately, an excellent effect can be obtained by using these without reducing the interaction between the binder polymer, the resin substrate, the inorganic fine particles, and the like.

Next, the hydrolyzate and partial condensate of the organosilane compound used in the present optical film will be described in detail.
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, butyric acid, maleic acid, citric acid, formic acid, methanesulfonic acid and toluenesulfonic acid; sodium hydroxide, potassium hydroxide and ammonia Inorganic bases such as triethylamine, organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium, tetrabutyltitanate, dibutyltin dilaurate; and metals such as Zr, Ti or Al as the central metal Metal chelate compounds and the like; Fluorine-containing compounds such as KF and NH4F are listed.
The said catalyst may be used independently or may use multiple types together.

The organosilane hydrolysis / condensation reaction can be carried out in the absence of a solvent or in a solvent, but an organic solvent is preferably used in order to mix the components uniformly. For example, alcohols, aromatic hydrocarbons, ethers, Ketones and esters are preferred.
The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating liquid or a part of the coating liquid, and those that do not impair solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

Among these, examples of the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms.
Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. And monobutyl ether.

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone, cyclohexanone, and ethylene glycol monoethyl ether include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the hydrolysis / condensation reaction of organosilane is not particularly limited, but is usually in the range of 1% by mass to 100% by mass.

In the hydrolysis reaction, 0.05 to 2 mol, preferably 0.1 to 1 mol of water is added to 1 mol of hydrolyzable group of the organosilane, in the presence or absence of the solvent, and It is carried out by stirring at 25-100 ° C. in the presence of a catalyst.
Here, the general formula R ³ OH (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) in the alcohol of the general formula R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is C 1 -C 10 to 10 alkyl groups, R ⁵ is an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms) and is selected from Zr, Ti or Al. It is preferable to perform hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal as a central metal.
Alternatively, when a fluorine-containing compound is used as a catalyst, the degree of polymerization can be determined by selecting the amount of water to be added and the molecular weight can be set arbitrarily because the fluorine-containing compound has the ability to completely proceed with hydrolysis and condensation. Therefore, it is preferable. That is, in order to adjust the organosilane hydrolyzate / partial condensate having an average degree of polymerization M, (M-1) mol of water may be used with respect to M mol of hydrolyzable organosilane.

The metal chelate compound includes an alcohol represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ is 1 carbon atom). -10 alkyl group, R ⁵ is an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used here has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ COCHCOR ⁵ ) Those selected from the group of compounds represented by _r2 are preferred, and act to promote the condensation reaction of the hydrolyzate and partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.
Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonate) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. When the metal chelate compound is used within the above range, the condensation reaction of the organosilane compound is fast, the durability of the coating film is good, and the hydrolyzate and partial condensate of the organosilane compound and the metal chelate compound are contained. The storage stability of the composition is good.

In addition to the composition containing the sol component and the metal chelate compound, at least one of a β-diketone compound and a β-ketoester compound is preferably added to the coating solution used for the optical film. This will be further described below.
Used here is at least one of a β-diketone compound and a β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ , and acts as a stability improver for the composition used here. Is. That is, by coordinating with a metal atom in the metal chelate compound (at least one of zirconium, titanium and aluminum compounds), condensation of hydrolyzate and partial condensate of organosilane compound by these metal chelate compounds It is considered that the action of accelerating the reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ⁴ and R ⁵ constituting the β- diketone compound and β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate- sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and β-ketoester compounds can be used alone or in admixture of two or more. In this optical film, the β-diketone compound and β-ketoester compound are preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. By making it 2 mol or more, the storage stability of the composition obtained can be improved, which is preferable.

  The content of the hydrolyzate and partial condensate of the organosilane compound is preferably small in the case of a relatively thin antireflection layer and large in the case of a thick hard coat layer or light diffusion layer. The content is preferably 0.1 to 50% by mass based on the total solid content of the composition for forming a containing layer (added layer), considering the expression of the effect, the refractive index, the shape / surface shape of the film, and the like. 30 mass% is more preferable, and 1-15 mass% is the most preferable. Within this range, after coating, it is condensed by a drying and heating step to form a cured product, and becomes a part of the binder of the antireflection layer, hard coat layer, and light diffusion layer, and the scratch resistance is improved.

1- (5) Initiator Polymerization of monomers having various ethylenically unsaturated groups can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
In producing a film having this structure, a photoinitiator or a thermal initiator can be used in combination.

<Photoinitiator>
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A-2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether It is.
Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler ketone), 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and the like are included.

  Examples of the borate salt are described in, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. And the organic borate compounds described. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned. Examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014. Specific examples include organoboron transition metal coordination complexes and the like, and specific examples include ion complexes with cationic dyes.

Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the active esters include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], sulfonic acid esters, cyclic active ester compounds, and the like.
Specifically, Examples 1 to 21 described in JP 2000-80068 are particularly preferable.
Examples of the onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830 M.M. P. Examples include compounds described in Hutt "Journal of Heterocyclic Chemistry", Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds, such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl) Acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, No. pp. 443 to p444 of JP-A-60-239736. 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

These initiators may be used alone or in combination.
“Latest UV Curing Technology”, Technical Information Association, 1991, p. 159, and “UV curing system” written by Kiyomi Kato, 1989, General Technology Center, p. Various examples are also described in 65 to 148, and are useful for this configuration.

  Commercially available radical photopolymerization initiators include KAYACURE (DETX-S, BP-100, BDKM, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc.), Irgacure (651, 184, 500, 819, 907, 369, 1173, 1870, 2959, 4265, 4263, etc.) manufactured by Ciba Specialty Chemicals, Ltd., Esacure (KIP100F, KB1, manufactured by Sartomer) EB3, BP, X33, KT046, KT37, KIP150, TZT) and the like and combinations thereof are preferred examples.

  It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.

<Photosensitizer>
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Further, one or more auxiliary agents such as an azide compound, a thiourea compound, and a mercapto compound may be used in combination.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA) manufactured by Nippon Kayaku Co., Ltd.

<Thermal initiator>
As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Diazo compounds such as 2,2′-azobis (isobutyronitrile), 2,2′-azobis (propionitrile), 1,1′-azobis (cyclohexanecarbonitrile) as azo compounds such as ammonium sulfate and potassium persulfate And diazoaminobenzene, p-nitrobenzenediazonium and the like.

1- (6) Crosslinkable compound When the monomer or polymer binder constituting the optical film does not have sufficient curability alone, the necessary curability can be imparted by blending the crosslinkable compound. it can.
For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing one or both of a hydroxyalkylamino group and an alkoxyalkylamino group in total, specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. Various resinous materials can be used.

  In addition to urea, examples of the urea compound include polymethylolated urea, alkoxylated methylurea which is a derivative thereof, methylolated uron having a uron ring, and alkoxylated methyluron. And also about compounds, such as a urea derivative, the use of the various resinous materials described in said literature is possible.

1- (7) Curing Catalyst In this optical film, radicals and acids generated by irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

<Heat acid generator>
Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include acids and salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, amine salts, various metal salts, phosphoric acid and phosphoric acid esters of organic acids, and the like.
Examples of commercially available materials include catalyst 4040, catalyst 4050, catalyst 600, catalyst 602, catalyst 500, catalyst 296-9, and more made by Nippon Cytec Industries, Inc., and NACURE series 155, 1051, 5076, 4054J and its block type NACURE series 2500, 5225, X49-110, 3525, 4167 or more manufactured by King Corporation, and the like.
The use ratio of the thermal acid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming the containing layer (addition layer). Part. When the addition amount is within this range, the storage stability of the composition is good and the scratch resistance of the coating film is also good.

<Photosensitive acid generator, photoacid generator>
Furthermore, the photo-acid generator which can be used as a photoinitiator is explained in full detail.
Examples of the acid generator include a photoinitiator for photocationic polymerization, a photodecoloring agent for dyes, a photochromic agent, a known acid generator used in a microresist, and the like, a known compound, and a mixture thereof. Is mentioned. Examples of the acid generator include organic halogen compounds, disulfone compounds, onium compounds, and the like. Specific examples of the organic halogen compounds among these include the same as those described in <Photoinitiator>. .
Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts; (2) β-ketoesters, β-sulfonylsulfones, and these. sulfone compounds such as α-diazo compounds; (3) sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters and imino sulfonates; (4) sulfonimide compounds; and (5) diazomethane compounds. Can be mentioned.
Examples of onium salts include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, and selenonium salts. Of these, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like. Examples thereof include the compounds described in paragraph numbers [0058] to [0059] of JP-A-2002-29162.

The use ratio of the photosensitive acid generator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the total solid content of the composition for forming the containing layer (addition layer). Part.
In addition, as specific compounds and methods of use, for example, the contents described in JP-A-2005-43876 can be used.

1- (8) Translucent Particles Various translucent particles are used for the light diffusion layer in order to impart antiglare properties (surface scattering properties) and internal scattering properties.

  The translucent particles in the light diffusion layer are polymethyl methacrylate particles (refractive index 1.49), crosslinked poly (acryl-styrene) copolymer particles (refractive index 1.54), melamine resin particles (refractive index 1.. 57), polycarbonate particles (refractive index 1.57), polystyrene particles (refractive index 1.60), crosslinked polystyrene particles (refractive index 1.61), polyvinyl chloride particles (refractive index 1.60), benzoguanamine-melamine formaldehyde Particles (refractive index: 1.68), silica particles (refractive index: 1.44), alumina particles (refractive index: 1.63), zirconia particles, titania particles, or particles having hollow or pores are used.

Of these, crosslinked poly ((meth) acrylate) particles and crosslinked poly (acryl-styrene) particles are preferably used, and the refractive index of the binder is adjusted according to the refractive index of each light-transmitting particle selected from these particles. By adjusting, an internal haze suitable for the light diffusion layer of the optical film can be achieved.
Furthermore, a binder (having a refractive index after curing of 1.50 to 1.53) mainly composed of a tri- or higher functional (meth) acrylate monomer and a crosslinked poly (meth) acrylate weight having an acrylic content of 50 to 100 mass percent. It is preferable to use a combination of translucent particles made of a combination, and in particular, a binder mainly composed of a tri- or higher functional (meth) acrylate monomer and crosslinked poly ((meth) acrylate) particles (refractive index of 1.49) The combination of is preferable.

The refractive index of the binder (translucent resin) and the translucent particles is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
The difference between the translucent particles and the refractive index of the film of the light diffusing layer excluding the translucent particles (“refractive index of the translucent particles” − “film of the light diffusing layer excluding the translucent particles” The refractive index of “)” is preferably 0.001 to 0.03 as an absolute value, more preferably 0.001 to 0.020, and still more preferably 0.005 to 0.015. If the difference in refractive index is less than 0.001, a very large amount of light-transmitting particles must be contained in the binder in order to exhibit light diffusibility in the light diffusion layer. Film strength and coating suitability deteriorate. When the refractive index difference is larger than 0.03, the content of the light transmissive particles in the light diffusion layer is small and a uniform light diffusion layer cannot be formed. In order to obtain a desired refractive index difference, it is preferable to adjust the refractive index of the binder. The refractive index of the binder can be adjusted by using 1 to 90% by mass of inorganic particles described later in addition to the selection of the binder type.

  Here, the refractive index of the film of the light diffusion layer excluding the translucent particles can be quantitatively evaluated by directly measuring with an Abbe refractometer or by measuring a spectral reflection spectrum or spectral ellipsometry. The refractive index of the translucent particles is measured by measuring the turbidity by dispersing an equal amount of the translucent particles in the solvent in which the refractive index is changed by changing the mixing ratio of two types of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  In the case of the above translucent particles, the translucent particles easily settle in the binder, and therefore an inorganic filler such as silica may be added to prevent sedimentation. As the amount of the inorganic filler added increases, it is more effective in preventing the translucent particles from settling, but adversely affects the transparency of the coating film. Therefore, preferably, an inorganic filler having a particle size of 0.5 μm or less is contained in an amount of less than about 0.1 parts by mass with respect to 100 parts by mass of the binder-forming component so as not to impair the transparency of the coating film.

  The average particle diameter of the translucent particles is preferably 3 to 12 μm, more preferably 4.0 to 10.0 μm, and still more preferably 5 to 8 μm. If the average particle size is less than 3 μm, the scattering angle distribution of light spreads to a wide angle, which may cause blurring of characters on the display. On the other hand, if it exceeds 12 μm, it is necessary to increase the thickness of the layer to be added, which causes problems such as curling and cost increase. Increasing the film thickness further increases the coating amount during coating, and thus delays drying and causes surface defects such as drying unevenness.

  The measuring method of the average particle diameter of the translucent particles can be any measuring method as long as it is a measuring method for measuring the average particle diameter of the particles, but preferably a transmission electron microscope (magnification of 500,000 to 2,000,000 times) In this method, the particles are observed, 100 particles are observed, and the average value is set to the average particle diameter.

  Here, the shape of the translucent particles is not particularly limited, but in addition to the true spherical particles, translucent particles having different shapes such as irregularly shaped particles (for example, non-true spherical particles) may be used in combination.

  The translucent particles are preferably blended so as to be contained in an amount of 5 to 40% by mass in the total solid content of the light diffusion layer. More preferably, it is 5-25 mass%, More preferably, it is 7-20 mass%. If it is 5% by mass or more, the effect of addition is sufficiently exhibited, and if it is 40% by mass or less, it is possible to suppress the occurrence of problems such as image blur, surface turbidity and glare.

Moreover, the application amount of translucent particles is preferably 30 to 2500 mg / m ² , more preferably 100 to 2400 mg / m ² , and still more preferably 600 to 2300 mg / m ² .

The swelling rate is determined by dispersing resin particles in MiBK at a concentration of 30% by mass, and measuring the particle size (r1) measured one day after the completion of the dispersion and the particle size of the dispersion over time in a standing state at room temperature. Was obtained from the following equation from the particle size (r 2) when E was stopped and reached an equilibrium state.
Swelling ratio (volume%) = {(r2 / r1) ³ −1} × 100
The swelling rate is preferably 20% by volume or less, more preferably 10% by volume or less, and still more preferably 5% by volume or less.

Compressive strength of the resin particles is preferably from 4~10kgf / mm ^2, more preferably 4~8kgf / mm ^2, more preferably 4~6kgf / mm ^2. Within this range, there is also a contribution to increasing the film hardness, and particle breakage due to deterioration in brittleness is unlikely to occur.
The compressive strength refers to the compressive strength when the particle size (particle size) is deformed by 10%. The compressive strength when the particle size is deformed by 10% is the particle compressive strength (S10 strength). A compression test is performed on the resin particles using the Shimadzu Micro Compression Tester MCTW201, and the particle size is deformed by 10%. It is a value obtained by introducing the load and the particle diameter before compression into the following equation.
S10 strength (kgf / mm ² ) = 2.8 × load (kgf) / {(π × particle diameter (mm) × particle diameter (mm)}

<Translucent particle preparation, classification method>

  Examples of the method for producing translucent particles used in the present optical film include suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, seed polymerization, and the like. Also good. These production methods are described in, for example, “Experimental Methods for Polymer Synthesis” (Takayuki Otsu and Masaaki Kinoshita, Chemical Dojinsha), pages 130 and 146 to 147, “Synthetic Polymers”, Vol. 246-290, 3rd volume, p. 1 to 108, etc., and Japanese Patent Nos. 2543503, 3508304, 2746275, 3521560, 3580320, and Japanese Patent Laid-Open No. 10-1561. Reference can be made to methods described in JP-A No. 7-2908, JP-A No. 5-297506, JP-A No. 2002-145919, and the like.

The particle size distribution of the translucent particles is preferably monodisperse particles in terms of haze value and control of diffusibility, and uniformity of the coated surface. The CV value representing the uniformity of the particle diameter is preferably 15% or less, more preferably 13% or less, and still more preferably 10% or less. Further, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle is preferably 1% or less, more preferably 0.1% or less of the total number of particles. More preferably, it is 0.01% or less. Particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .
It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification.

1- (9) Inorganic Particles Various inorganic particles can be used in the functional layer of the present optical film in order to improve physical properties such as hardness, optical properties such as reflectance, and scattering properties.
As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO ₂ , TiO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and the like can be mentioned. Others include BaSO ₄ , CaCO ₃ , talc and kaolin.

  The particle diameter of the inorganic particles used here is preferably as fine as possible in the dispersion medium, and the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.

The specific surface area of the inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The inorganic particles used here are preferably added to the coating solution for the layer used as a dispersion in the dispersion medium.
As the dispersion medium for the inorganic particles, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methyl) Carboxymethyl-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.
Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic particles are dispersed using a disperser. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

<High refractive index particles>
For the purpose of increasing the refractive index of the functional layer provided as necessary in this optical film, curing of a composition in which inorganic particles having a high refractive index are dispersed in a monomer, an initiator, and an organically substituted silicon compound The product is preferably used.
In particular, ZrO ₂ and TiO ₂ are preferably used as the inorganic particles in this case from the viewpoint of refractive index. ZrO ₂ is most preferable for increasing the refractive index of the light diffusion layer and the hard coat layer, and TiO ₂ fine particles are most preferable as the particles for the high refractive index layer and the medium refractive index layer.

As the TiO ₂ particles, inorganic particles mainly containing TiO ₂ containing at least one element selected from cobalt, aluminum, and zirconium are particularly preferable. The main component means a component having the largest content (mass%) among the components constituting the particles.
Here, the particles containing TiO ₂ as a main component preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. Most preferably it is.
The mass average diameter of primary particles of TiO ₂ as a main component is preferably 1 to 200 nm, more preferably 1 to 150 nm, still more preferably 1 to 100 nm, and particularly preferably 1 to 80 nm.

The crystal structure of the particles containing TiO ₂ as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, and particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum), and Zr (zirconium) in particles containing TiO ₂ as a main component, the photocatalytic activity of TiO ₂ can be suppressed, and the film The weather resistance of can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination.
Here, the inorganic particles containing TiO ₂ as a main component may have a core / shell structure by surface treatment as described in JP-A No. 2001-166104.

  The addition amount of the inorganic particles in the layer is preferably 1 to 45% by mass and more preferably 1 to 30% by mass with respect to the binder. Two or more kinds of inorganic particles may be used in the layer.

<Low refractive index particles>
The low refractive index layer preferably contains inorganic particles. The inorganic particles desirably have a low refractive index, and examples thereof include magnesium fluoride and silica fine particles. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

Further, at least one kind of silica fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (referred to as “small size particle size silica particles”) is used as silica fine particles having the above particle size (“large size particles”). It is preferably used in combination with “silica fine particles having a diameter”.
Since the fine silica particles having a small size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small size is preferably from 1 nm to 20 nm, more preferably from 5 nm to 15 nm, and particularly preferably from 10 nm to 15 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

The coating amount of the low refractive index particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.

<Hollow silica particles>
For the purpose of further reducing the refractive index, it is preferable to use hollow silica fine particles.

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, assuming that the radius of the cavity in the particle is a and the radius of the outer shell of the particle is b, the porosity x expressed by the following formula (VIII) is (Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10 to 60%, More preferably, it is 20 to 60%, Most preferably, it is 30 to 60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Therefore, a refractive index of 1.15 or more from the viewpoint of scratch resistance. Are preferred.

  A method for producing hollow silica is described in, for example, Japanese Patent Application Laid-Open Nos. 2001-233611 and 2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A-2002-79616.

The coating amount of the hollow silica is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of reducing the refractive index and the effect of improving the scratch resistance are reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
If the particle size of the silica particles is too small, the proportion of cavities will decrease and a decrease in refractive index cannot be expected.If it is too large, fine irregularities will be formed on the surface of the low refractive index layer, and the appearance such as black tightening and integrated reflectance will be reduced. Getting worse. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area here hollow silica is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

  Silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.

1- (10) Conductive Particles Various conductive particles can be used for imparting conductivity to the optical film.
The conductive particles are preferably formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred. The conductive inorganic particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and halogen atoms are included. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The average particle diameter of the primary particles of the conductive inorganic particles used for the antistatic layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive inorganic particles in the antistatic layer to be formed is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive inorganic particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the conductive inorganic particles is preferably from 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive inorganic particles may be surface treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive inorganic particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

Two or more kinds of conductive particles may be used in combination in a specific functional layer of the film or in different layers in the film.
The proportion of the conductive inorganic particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

  The conductive inorganic particles can be used for forming an antistatic layer in a dispersion state.

1- (11) Surface treatment agent The inorganic particles used here are plasma discharges in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding properties with the binder component. A physical surface treatment such as a treatment or a corona discharge treatment, or a chemical surface treatment with a surfactant or a coupling agent may be performed.

The surface treatment can be performed using a surface treatment agent of an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include inorganic compounds containing cobalt (CoO ₂ , Co ₂ O ₃ , Co ₃ O _4, etc.) and inorganic compounds containing aluminum (Al ₂ O ₃ , Al (OH) _3. Etc.), zirconium-containing inorganic compounds (ZrO ₂ , Zr (OH) ₄ etc.), silicon-containing inorganic compounds (SiO ₂ etc.), iron-containing inorganic compounds (Fe ₂ O ₃ etc.), etc. .
An inorganic compound containing cobalt, an inorganic compound containing aluminum, and an inorganic compound containing zirconium are particularly preferable, and an inorganic compound containing cobalt, Al (OH) ₃ , and Zr (OH) ₄ are most preferable.
Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. In particular, the surface treatment is preferably performed with at least one of a silane coupling agent (organosilane compound), a partial hydrolyzate thereof, and a condensate thereof.

Examples of titanate coupling agents include metal alkoxides such as tetramethoxy titanium, tetraethoxy titanium, and throat tetraisopropoxy titanium, and preneact (KR-TTS, KR-46B, KR-55, KR-41B, etc .; Ajinomoto Co., Inc. ))).
Examples of the organic compound used for the surface treatment include polyols, alkanolamines, and other organic compounds having an anionic group, and particularly preferable are organic compounds having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. is there. Stearic acid, lauric acid, oleic acid, linoleic acid, linolenic acid and the like can be preferably used.
The organic compound used for the surface treatment preferably further has a crosslinked or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acrylic groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, cationic polymerizable groups (Epoxy groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like can be mentioned, and groups having an ethylenically unsaturated group are preferred.

  Two or more kinds of these surface treatments can be used in combination, and it is particularly preferable to use an inorganic compound containing aluminum and an inorganic compound containing zirconium.

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present optical film include organosilane compounds and catalysts described in WO 2004/017105.
The amount of the surface treatment agent used with respect to the inorganic particles is preferably in the range of 10 to 150 parts by mass, more preferably in the range of 15 to 120 parts by mass, with respect to 100 parts by mass of the inorganic particles. Most preferably. Two or more surface treatment agents may be used in combination.

1- (12) Dispersant Various dispersants can be used for dispersing the particles used in the present optical film.
The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

It is preferable to use a dispersant having an anionic group for the dispersion of inorganic particles, particularly for the dispersion of inorganic particles containing TiO ₂ as a main component, more preferably having an anionic group and a crosslinkable or polymerizable functional group, It is particularly preferable that the dispersant has the cross-linked or polymerizable functional group in the side chain.

  As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersing agent per molecule may be plural, but is preferably 2 or more on average, more preferably 5 or more, Particularly preferred is 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

In the dispersant having an anionic group in the side chain, the composition of the anionic group-containing repeating unit is in the range of 10 ^{−4 to} 100 mol%, preferably 1 to 50 mol%, particularly preferably 5 in the total repeating units. ~ 20 mol%.

  The dispersant preferably further contains a crosslinkable or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.

  The average number of cross-linkable or polymerizable functional groups contained in the dispersant per molecule is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the crosslinking or polymerizable functional group contained in the dispersant may contain a plurality of types in one molecule.

In the preferred dispersant used in the present optical film, examples of the repeating unit having an ethylenically unsaturated group in the side chain include poly-1,2-butadiene and poly-1,2-isoprene structures or (meth) acrylic acid. An ester or amide repeating unit having a specific residue (the -COOR or -CONHR R group) bound thereto can be used. Examples of the specific residue (R _{group), - (CH 2) n} -CR 21 = CR 22 R 23, - (CH 2 O) n -CH 2 CR 21 = CR 22 R 23, - (CH _{2 CH 2 O) n -CH 2} CR 21 = CR 22 R 23, - (CH 2) n -NH-CO-O-CH 2 CR 21 = CR 22 R 23, - (CH 2) n -O-CO —CR ²¹ ═CR ²² R ²³ and — (CH ₂ CH ₂ O) ₂ —X (R ^{21 to} R ²³ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkoxy group. R ²¹ and R ²² or R ²³ may be bonded to each other to form a ring, n is an integer of 1 to 10, and X is a dicyclopentadienyl residue. There are). Specific examples of R of the ester residue include —CH ₂ CH═CH ₂ (corresponding to an allyl (meth) acrylate polymer described in JP-A No. 64-17047), —CH ₂ CH ₂ O—CH ₂ CH _{= CH 2, -CH 2 CH 2} OCOCH = CH 2, -CH 2 CH 2 OCOC (CH 3) = CH 2, -CH 2 C (CH 3) = CH 2, -CH 2 CH = CH-C 6 H ₅ , —CH ₂ CH ₂ OCOCH═CH—C ₆ H ₅ , —CH ₂ CH ₂ —NHCOO—CH ₂ CH═CH ₂ and —CH ₂ CH ₂ O—X (X is a dicyclopentadienyl residue) Is included. Specific examples of R of the amide residue include —CH ₂ CH═CH ₂ , —CH ₂ CH ₂ —Y (Y is a 1-cyclohexenyl residue) and —CH ₂ CH ₂ —OCO—CH═CH ₂ , _{-CH 2 CH 2 -OCO-C (} CH 3) = CH 2 are included.

  In the dispersant having an ethylenically unsaturated group, a free radical (a polymerization initiation radical or a growth radical of a polymerization process of a polymerizable compound) is added to the unsaturated bond group, and the polymer compound is directly or between molecules. Addition polymerization is carried out through the polymerization chain, and a crosslink is formed between the molecules to cure. Alternatively, atoms in the molecule (for example, hydrogen atoms on carbon atoms adjacent to the unsaturated bond group) are extracted by free radicals to form polymer radicals that are bonded together to form a bridge between the molecules. Harden.

  The weight average molecular weight (Mw) of the dispersant having an anionic group and a crosslinkable or polymerizable functional group and having the crosslinkable or polymerizable functional group in the side chain is not particularly limited, but is preferably 1000 or more. . The more preferable mass average molecular weight (Mw) of the dispersant is 2000 to 1000000, more preferably 5000 to 200000, and particularly preferably 10000 to 100000.

  The cross-linkable or polymerizable functional group-containing unit may constitute all repeating units other than the anionic group-containing repeating unit, preferably 5 to 50 mol% of the total cross-linking or repeating unit, particularly Preferably it is 5-30 mol%.

  The dispersant may be a copolymer with an appropriate monomer other than a monomer having a crosslinking or polymerizable functional group or an anionic group. Although it does not specifically limit regarding a copolymerization component, It selects from various viewpoints, such as dispersion stability, compatibility with another monomer component, and the intensity | strength of a formed film. Preferable examples include methyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene and the like.

  The form of the dispersant is not particularly limited, but is preferably a block copolymer or a random copolymer, and particularly preferably a random copolymer from the viewpoint of cost and ease of synthesis.

  The amount of the dispersant used relative to the inorganic particles is preferably in the range of 1 to 50 parts by mass, more preferably in the range of 5 to 30 parts by mass, and 5 to 20 parts by mass with respect to 100 parts by mass of the inorganic fine particles. Most preferably. Two or more dispersants may be used in combination.

  Specific examples of the dispersant preferably used are shown below, but the dispersant used here is not limited thereto. Unless otherwise specified, it represents a random copolymer.

1- (13) Antifouling agent For the purpose of imparting antifouling properties, water resistance, chemical resistance, slipping properties, etc., to the optical film, particularly the uppermost layer of the film, a known silicone type or fluorine type antifouling agent is used. It is preferable to add a soiling agent, a slipping agent and the like as appropriate.
When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is most preferable that it is 10,000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), manufactured by Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, and defender MCF-300 (named above), but are not limited thereto.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dainippon Ink Co., Ltd., MegaFace F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean.

1- (14) Surfactant In the present optical film, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., any one of fluorine-based and silicone-based surfactants, or its Both are preferably contained in the coating composition for forming the light diffusion layer. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

  Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl copolymerizable therewith, including a corresponding repeating unit or a repeating unit corresponding to the monomer (i) and a repeating unit corresponding to the monomer (ii) below A copolymer with a monomer is useful.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula A

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1-6, and n is an integer of 2-4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) Monomer represented by the following general formula (b) copolymerizable with the above (i)

In general formula B, R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents an optionally substituted 4 or more carbon atoms and 20 or less linear, branched or cyclic alkyl group. Examples of the substituent for the alkyl group of R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula A used in the fluorine-based polymer used here is 10 mol% or more based on each monomer of the fluorine-based polymer, preferably 15 It is -70 mol%, More preferably, it is the range of 20-60 mol%.

As for the preferable mass mean molecular weight of the fluorine-type polymer used here, 3000-100,000 are preferable and 5,000-80,000 are more preferable.
Furthermore, the preferable addition amount of the fluoropolymer used here is in the range of 0.001 to 5 parts by mass, more preferably in the range of 0.005 to 3 parts by mass with respect to 100 parts by mass of the coating solution. More preferably, it is the range of 0.01-1 mass part. If the addition amount of the fluorine-based polymer is 0.001 part by mass or more, the effect of adding the fluorine-based polymer is sufficiently obtained, and if the addition amount is 5 parts by mass or less, the coating film cannot be sufficiently dried or applied. There is no problem of adversely affecting the performance as a film (for example, reflectance, scratch resistance).

  Examples of the specific structure of the fluorine-based polymer derived from the repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

1- (15) Thickener

The optical film may use a thickener to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid increases by adding it. More preferably, it is 0.10-20 cP, Most preferably, it is 0.10-10 cP.

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral Polyvinyl formal Polyvinyl acetal Polyvinyl propanal Polyvinyl hexanal Polyvinyl pyrrolidone Polyacrylic acid ester Polymethacrylic acid ester Cellulose acetate Cellulose propionate Cellulose acetate butyrate

  Other known viscosity modifiers such as smectite, tetrasilica mica, bentonite, silica, montmorillonite and sodium polyacrylate, JP-A-10-219136, ethyl cellulose, polyacrylic acid, and organic clay described in JP-A-8-325491. Or a thixotropic agent can be used.

1- (16) Coating solvent As a solvent used in the coating composition for forming each layer of the optical film, each component can be dissolved or dispersed, and a uniform surface is likely to be formed in the coating process and the drying process. In addition, various solvents selected from the viewpoints of ensuring liquid storage stability and having an appropriate saturated vapor pressure can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable that a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature as a main component and a small amount of solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed.

Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as 79.6 ° C., same as ruketone, methanol (64.5 ° C.), ethanol (78.3 ° C.), 2-propanol (82.4 ° C.), 1-propanol (97.2 ° C.), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.) and propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.) and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable.

1- (17) Others In addition to the above components, the optical film includes a resin, a coupling agent, a coloring inhibitor, a coloring agent (pigment, dye), an antifoaming agent, a leveling agent, a flame retardant, an ultraviolet absorber, Infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, and the like can also be added.

1- (18) Support The support for the optical film is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, or transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.
Although the thickness of a support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.
Any width of the support can be used, but from the viewpoint of handling, yield, and productivity, a width of 100 to 5000 mm is usually used, preferably 800 to 3000 mm, and preferably 1000 to 2000 mm. More preferably.
The surface of the support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. Is more preferable.

<Cellulose acylate film>
Among the various films described above, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for polarizing plates is preferable.
For the cellulose acylate film, various improvement techniques are known for the purpose of improving mechanical properties, transparency, flatness and the like. Can be used for film.

Here, a cellulose triacetate film is particularly preferable among the cellulose acylate films, and it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used here has a value of Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution is narrow. It is preferable. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. Here, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total substitution degree is preferably substituted with 32% or more of an acyl group, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
Here, as cellulose acylate, paragraphs [0043] to [0044] [Example] [Synthesis Example 1], paragraphs [0048] to [0049] [Synthesis Example 2], and paragraph [0051] of JP-A No. 11-5851. ] To [0052] Cellulose acetate obtained by the method described in [Synthesis Example 3] can be used.

<Polyethylene terephthalate film>
Here, the polyethylene terephthalate film is also excellent in transparency, mechanical strength, flatness, chemical resistance and moisture resistance, and is preferably used because it is inexpensive.
In order to further improve the adhesion strength between the transparent plastic film and the light diffusion layer provided thereon, the transparent plastic film is more preferably subjected to an easy adhesion treatment.
Examples of commercially available PET films with an easily adhesive layer for optics include Cosmo Shine A4100 and A4300 manufactured by Toyobo Co., Ltd.

2. Next, the layers constituting the optical film will be described.

2- (1) Hard Coat Layer In order to impart physical strength of the film to the optical film, a hard coat layer is preferably provided on one surface of the transparent support. As will be described later in “2- (2) Light Diffusion Layer” and “3. Layer Structure of Film”, it is preferable that the light diffusion layer also has a hard coat property, and the light diffusion layer also serves as the hard coat layer. It is. When the hard coat layer is provided separately from the light diffusion layer, the position of the hard coat layer may be on the transparent support side or on the opposite side of the light diffusion layer from the transparent support side, but is preferably on the transparent support side. .

In this optical film, a hard coat layer for changing the arithmetic average roughness (Ra) of the optical film surface with respect to the arithmetic average roughness (Ra) of the light diffusion layer is laminated on the light diffusion layer of the optical film. An optical film is preferred. The hard coat layer that changes the arithmetic average roughness (Ra) of the optical film surface with respect to the arithmetic average roughness (Ra) of the light diffusing layer is, for example, a hard coat layer coated on the light diffusing layer. In this case, a method of smoothing the surface unevenness of the light diffusion layer to form smooth unevenness, a method of reducing the frequency of the peaks and widening the interval of the unevenness (increasing the Sm value), and reducing the height of the peaks (lowering the Ra value) It means a hard coat layer adjusted by the method of performing.
The hard coat layer may be composed of two or more layers.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 2 μm. 10 μm, most preferably 3 μm to 7 μm.
Further, the strength of the hard coat layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. Here, after the hard coat layer is formed, the polyfunctional monomer and / or the polymer formed by polymerizing the high refractive index monomer, and the inorganic particles dispersed therein are referred to as a binder.

Also, when it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to internal scattering of the hard coat layer, or to add the function of expanding the viewing angle by scattering, the internal haze value (from the total haze value) The value obtained by subtracting the surface haze value) is preferably 0% to 60%, more preferably 10% to 40%, and most preferably 20% to 30%.
In the present optical film, surface haze and internal haze can be freely set according to the purpose.

2- (2) Light Diffusing Layer As described above, the present optical film is an optical film having a light diffusing layer containing translucent particles and a binder on a transparent support, and the light diffusing layer is a specific one. It has an average thickness. The light diffusion layer contributes to the film with antiglare properties due to surface scattering, and preferably contributes to the film with a hard coat property for improving the scratch resistance of the film, that is, the light diffusion layer is a hard coat layer. It is also a preferred embodiment that serves as both.
The antireflection film is constituted by providing a low refractive index layer on the light diffusion layer of the optical film. More preferably, a medium refractive index layer and a high refractive index layer are provided between the light diffusion layer, a hard coat layer provided according to necessity, and a low refractive index layer. The refractive index of the light diffusion layer is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1.90, from the optical design for obtaining an antireflection film. Yes, more preferably from 1.55 to 1.80. Here, since there is at least one low refractive index layer on the light diffusion layer, when the refractive index is too small, the antireflection property is lowered, and when it is too large, the color of the reflected light tends to be strong. .

As a method for forming the antiglare property, a method of laminating and forming a mat-shaped shaped film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317. A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation, and as described in JP-A No. 2000-338310, when the mass ratio of a good solvent to a translucent resin is reduced by drying. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the surface of the coating film, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.
The light diffusing layer requires a light diffusing layer forming composition, preferably a coating composition, a binder forming component capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent. Contained as a component, when a light diffusion layer is formed, surface irregularities are formed by a convex shape formed by translucent particles themselves or a convex shape formed by an aggregate of a plurality of particles. It is preferable.

  Specific examples of the translucent particles are as described above for 1- (8) translucent particles. For example, resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Of these, crosslinked styrene particles, crosslinked poly (acryl-styrene) copolymer particles, and crosslinked acrylic particles are preferred.

Although the measuring method of the average thickness (average film thickness) of a light-diffusion layer is not specifically limited, For example, a cross-section is expanded 5000 times with an electron microscope, KOKUYO tracing paper (Ce-TD58: 50 g / m < ² >) It can be measured by copying the light diffusion layer and measuring the mass. The average thickness was calculated by measuring the length (parallel direction) of the light diffusion layer of 1500 μm. The average thickness of the light diffusion layer is 1.4 to 3.5 times the average particle diameter of the translucent particles, preferably 1.5 to 3.0 times, more preferably 1.5 to 2.5 times, 1.6 to 2.0 times is particularly preferable.

In the graph shown in FIG. 11, the average film thickness / average particle ratio is taken on the horizontal axis, and the antiglare property is taken on the vertical axis. The evaluation of anti-glare on the vertical axis is
A: Not reflected so much that the outline of the fluorescent light is completely unknown.
○: The outline of the fluorescent lamp is slightly observed, but hardly reflected.
Δ: Fluorescent light is blurred but slightly reflected.
X: The outline of the fluorescent light is clearly visible or dazzling.
It is said. As shown in the figure, when the average film thickness of the light diffusing layer is 1.4 to 3.5 times the average particle diameter of the translucent particles, the antiglare property is almost constant. Therefore, even if the film thickness fluctuates due to streaks or unevenness of drying that occurs during coating, the anti-glare property is almost unchanged, so surface defects such as streaks and unevenness that are recognized by the difference in anti-glare property are recognized. I can't. When the average film thickness of the light diffusing layer is 1.4 to 3.5 times the average particle diameter of the light transmissive particles, the antiglare property is almost constant. If the particle distribution is caused to be distributed as shown in (b) among (a) to (c) of FIG. 12, it is estimated as follows. (B) schematically shows a state in which the translucent particles 87 are distributed in the light diffusion layer 83 when the average film thickness / average particle ratio is 1.4 to 3.5. In this state, the antiglare property is formed by surface irregularities due to protrusions formed by an aggregate of a plurality of particles. Even if the film thickness or particle diameter changes slightly, the size of the irregularities on the surface hardly changes, so the change in antiglare property is small. (A) is the case where the average film thickness / average particle ratio is less than 1.4. Since the particles exist in one layer in the film, if the film thickness or the particle diameter slightly changes, the size of the surface irregularities becomes small. The anti-glare property changes greatly. (C) is a case where the average film thickness / average particle ratio is larger than 3.5, and an aggregate of a plurality of particles is buried in the film, so that there is almost no surface irregularity and only a low antiglare property. Can't get.
In addition, when the average film thickness / average particle ratio is 1.4 to 3.5, the average particle size varies depending on the particle lot, and the antiglare property of the film is less likely to vary. You can also get

  The average film thickness of the light diffusion layer is preferably 7.5 to 30 μm, more preferably 8 to 20 μm, and still more preferably 10 to 16 μm. If it is too thin, the hard coat property will be insufficient, and if it is too thick, curling and brittleness may be deteriorated and the workability may be lowered.

(Also referred to as matte particles.) The light-transmitting particles, matting particles of a light diffusing layer formed is preferably 30~2500mg / m ^2, more preferably 100~2300mg / m ^2, more preferably 600 to It is contained in the light diffusion layer so as to be 2300 mg / m ² .
The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a CV value.
The particle size distribution CV value is expressed by the following formula, and the smaller the value, the narrower the particle size distribution.
CV (%) = {standard deviation of particle size (μm) / average particle size (μm)} × 100

  The strength of the light diffusion layer is preferably 4H or more, and most preferably 5H or more, in a pencil hardness test.

The surface haze of the light diffusing layer is preferably 0.3% to 20%, more preferably 0.3% to 10%, in order to achieve both antiglare properties and blackening. More preferably, the content is from 1.5% to 1.5%.
In addition, when it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to internal scattering of the light diffusing layer, or to add the function of expanding the viewing angle by scattering, the internal haze value (from the total haze value) The value obtained by subtracting the surface haze value) is preferably 0% to 60%, more preferably 10% to 40%, and most preferably 20% to 30%.
In the present optical film, surface haze and internal haze can be freely set according to the purpose.

  The arithmetic average roughness (Ra) of the light diffusion layer is preferably 0.03 to 0.30 μm and more preferably 0.05 to 0.12 μm in order to achieve both antiglare properties and blackening. 40-200 micrometers is preferable, as for the average space | interval (Sm) of an unevenness | corrugation, 50-170 micrometers is more preferable, and 60-150 micrometers is still more preferable.

2- (3) High Refractive Index Layer, Medium Refractive Index Layer The optical film can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties.
In this specification, the high refractive index layer, the middle refractive index layer, the low refractive index layer, and the like may be collectively referred to as an antireflection layer.

  In order to construct an antireflection film by constructing a low refractive index layer on a high refractive index layer, the refractive index of the high refractive index layer is preferably 1.55 to 2.40, more preferably It is 1.60 to 2.20, more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  When an antireflective film is prepared by coating a medium refractive index layer, a high refractive index layer, and a low refractive index layer in order from the support, the refractive index of the high refractive index layer is 1.65 to 2.40. Preferably, it is 1.70-2.20. The refractive index of the middle refractive index layer is adjusted to be a value between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the middle refractive index layer is preferably 1.55-1.80.

As the inorganic particles used for the high refractive index layer and the medium refractive index layer, as described above in 1- (9), inorganic particles containing TiO ₂ as a main component are preferable. Used to form layers and medium refractive index layers.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in the dispersion medium in the presence of a dispersant.

  The high refractive index layer and the medium refractive index layer used in the present optical film are preferably a binder precursor (for example, the above-mentioned ionizing radiation curability described above) required for matrix formation in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium. Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferably formed by applying a coating composition for formation and curing it by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

Furthermore, it is preferable to cause the binder component of the high refractive index layer and the medium refractive index layer to undergo a crosslinking reaction or a polymerization reaction with the dispersant at the same time as or after the coating of the layer.
The binder of the high refractive index layer and the medium refractive index layer produced in this way is, for example, the above-mentioned preferred dispersant and ionizing radiation curable polyfunctional monomer or polyfunctional oligomer are crosslinked or polymerized to form a binder. The anionic group of the dispersant is incorporated. Furthermore, the binder of the high refractive index layer and the medium refractive index layer has a function in which the anionic group maintains the dispersion state of the inorganic particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains inorganic particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  The binder forming component of the high refractive index layer is added so as to be 5 to 80 parts by mass in 100 parts by mass of the solid content of the coating composition of the layer.

The content of the inorganic particles in the high refractive index layer is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, and particularly preferably 15 to 75% by mass with respect to the mass of the high refractive index layer. . Two or more kinds of inorganic particles may be used in combination in the high refractive index layer.
When the low refractive index layer is provided on the high refractive index layer, the refractive index of the high refractive index layer is preferably higher than the refractive index of the transparent support.
The high refractive index layer contains an ionizing radiation curable compound containing an aromatic ring, an ionizing radiation curable compound containing a halogenated element other than fluorine (for example, Br, I, Cl, etc.), and atoms such as S, N, P, etc. A binder obtained by a crosslinking or polymerization reaction such as an ionizing radiation curable compound can also be preferably used.

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. The high refractive index layer can also be used as an interference unevenness preventing layer described later. In this case, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed by coating a light diffusing layer on the transparent support and directly or via another layer thereon.

2- (4) Low Refractive Index Layer As described above, the present optical film is an antireflection film having a low refractive index layer on the light diffusion layer of the optical film, and reduces the reflectance of the present film. Can do.

The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.46, and particularly preferably 1.30 to 1.46.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
Moreover, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with respect to water is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

  In the low refractive index layer, a binder is used to disperse and fix the fine particles. As the binder forming component, the binder described in 1- (1) above can be used, but the refractive index of the binder itself is low, the fluorine-containing polymer described in 1- (3), or the fluorine-containing sol-gel material. It is preferable to use it. As the fluorine-containing polymer or fluorine-containing sol-gel, a material that crosslinks by heat or ionizing radiation and has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the formed low refractive index layer is preferable.

  The composition for forming a low refractive index layer comprises 1- (3) the fluorine-containing polymer described above, 1- (9) the inorganic particles described above, and 1- (4) the organosilane compound described above. Is preferred.

2- (5) Antistatic layer, conductive layer In the present optical film, it is preferable to provide an antistatic layer from the viewpoint of preventing static electricity on the film surface. The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The conductive layer can be formed directly on the support or via a primer layer that strengthens adhesion to the support. Further, the antistatic layer can be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is preferably from 10 ⁵ ~10 ¹² Ω / sq, more preferably from 10 ⁵ ~10 ⁹ Ω / sq, most be 10 ⁵ ~10 ⁸ Ω / sq preferable. The surface resistance of the antistatic layer can be measured by a four probe method.

The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The antistatic layer used in the present optical film is preferably excellent in strength, and the specific antistatic layer strength is preferably H or higher, with a pencil hardness of 1 kg load, preferably 2H or higher. Is more preferably 3H or more, and most preferably 4H or more.

2- (6) Antifouling layer An antifouling layer can be provided on the outermost surface of the optical film. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to attach hydrophilic or lipophilic stains. The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent. The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

2- (7) Interference unevenness (rainbow unevenness) prevention layer When there is a substantial refractive index difference (refractive index difference of 0.03 or more) between the transparent support and the hard coat layer, or between the transparent support and the light diffusion layer, Reflected light is generated at the interface of the transparent support / hard coat layer or the transparent support / light diffusion layer. This reflected light interferes with the reflected light on the surface of the antireflection layer, and may cause interference unevenness due to subtle film thickness unevenness of the hard coat layer and the light diffusion layer. In order to prevent such interference unevenness, for example, the interference unevenness prevention has an intermediate refractive index n _P between the transparent support and the hard coat layer or the light diffusion layer, and the film thickness d _P satisfies the following formula: Layers can also be provided.

Formula (III)
d _P = (2N−1) × λ / (4n _P )
Where λ is the wavelength of visible light and any value in the range of 450 to 650 nm, and N is a natural number.

  Moreover, when bonding an antireflection film to an image display etc., an adhesive layer (or adhesive layer) may be laminated | stacked on the side which has not laminated | stacked the antireflection layer of a transparent support body. In such an embodiment, when there is a substantial refractive index difference (0.03 or more) between the transparent support and the pressure-sensitive adhesive layer (or adhesive layer), the transparent support / pressure-sensitive adhesive layer (or adhesive layer) ) Reflected light, and this reflected light interferes with the reflected light on the surface of the antireflection layer and causes interference unevenness due to uneven film thickness of the support, hard coat layer, and light interference layer in the same manner as described above. There is. For the purpose of preventing such interference unevenness, an interference unevenness preventing layer similar to the above can be provided on the side of the transparent support on which the antireflection layer is not laminated.

  Such an interference non-uniformity prevention layer is described in detail in Japanese Patent Application Laid-Open No. 2004-345333, and in this configuration, the interference non-uniformity prevention layer introduced here can also be used.

2- (8) Easy-Adhesion Layer An easy-adhesion layer can be applied to the optical film. The easy adhesion layer refers to, for example, a layer imparting a function of facilitating adhesion between the protective film for polarizing plate and its adjacent layer, the light diffusion layer and the support, or the hard coat layer and the support.
Examples of the easy adhesion treatment include a treatment of providing an easy adhesion layer on a transparent plastic film with an easy adhesive composed of polyester, acrylic acid ester, polyurethane, polyethyleneimine, silane coupling agent and the like.
Examples of the easy-adhesion layer preferably used in the present technology include a layer containing a polymer compound having a -COOM (M represents a hydrogen atom or a cation) group, and a more preferable embodiment is a film substrate. A layer containing a polymer compound having a —COOM group is provided on the side, and a layer containing a hydrophilic polymer compound as a main component is provided on the polarizing film side adjacent to the layer. Examples of the polymer compound having -COOM group herein include styrene-maleic acid copolymer having -COOM group, vinyl acetate-maleic acid copolymer having -COOM group, and vinyl acetate-maleic acid-maleic anhydride. For example, it is preferable to use a vinyl acetate-maleic acid copolymer having a —COOM group. These polymer compounds are used alone or in combination of two or more, and the preferred mass average molecular weight is preferably about 500 to 500,000. Particularly preferred examples of the polymer compound having a —COOM group include those described in JP-A-6-094915 and JP-A-7-333436.

The hydrophilic polymer compound is preferably a hydrophilic cellulose derivative (eg, methyl cellulose, carboxymethyl cellulose, hydroxy cellulose, etc.), a polyvinyl alcohol derivative (eg, polyvinyl alcohol, vinyl acetate-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl formal). , Polyvinyl benzal, etc.), natural polymer compounds (eg, gelatin, casein, gum arabic, etc.), hydrophilic polyester derivatives (eg, partially sulfonated polyethylene terephthalate), hydrophilic polyvinyl derivatives (eg, poly -N-vinylpyrrolidone, polyacrylamide, polyvinylindazole, polyvinylpyrazole and the like), and may be used alone or in combination of two or more.
The thickness of the easy adhesion layer is preferably in the range of 0.05 to 1.0 μm. If it is thinner than 0.05 μm, it is difficult to obtain sufficient adhesiveness, and if it is thicker than 1.0 μm, the effect of adhesiveness is saturated.

2- (9) Anti-curl layer The optical film can be subjected to anti-curl processing. The anti-curl processing is to impart a function of rounding with the surface to which the curl is applied. By applying this process, the surface of the transparent resin film is treated to prevent curling inward when a different degree or type of surface treatment is applied to each of the two surfaces of the transparent resin film. It works to do. The curl prevention process is performed on the surface opposite to the surface to be curled on the inner side of the transparent resin film. An example of the anti-curl process is a process of providing an anti-curl layer.
The anti-curl layer is provided on the side of the substrate opposite to the side having the light diffusion layer or anti-reflection layer, or for example, an easy-adhesion layer is coated on one side of a transparent resin film, and anti-curl processing is performed on the opposite side. Examples of such a method are as follows.

  Specific examples of the anti-curl processing include solvent coating, and a method of applying a solvent and a transparent resin layer such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate. The method using a solvent is specifically performed by applying a composition containing a solvent for dissolving or swelling a cellulose acylate film used as a protective film for a polarizing plate. Accordingly, the coating solution for the layer having a function of preventing curling preferably contains a ketone-based or ester-based organic solvent. Examples of preferred ketone-based organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl lactate, acetyl acetone, diacetone alcohol, isophorone, ethyl-n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, Examples thereof include methylcyclohexanone, methyl-n-butyl ketone, methyl-n-propyl ketone, methyl-n-hexyl ketone, methyl-n-heptyl ketone, etc. Examples of preferable ester organic solvents include methyl acetate, ethyl acetate, acetic acid Examples include butyl, methyl lactate, and ethyl lactate. However, as a solvent to be used, in addition to a solvent mixture to be dissolved and / or a solvent to be swollen, it may further contain a solvent that does not dissolve, and a composition in which these are mixed at an appropriate ratio depending on the curl degree of the transparent resin film and the type of resin This is done using the product and the coating amount. In addition, the anti-curl function is exhibited even if transparent hard processing or antistatic processing is applied.

2- (10) Water Absorbing Layer A water absorbent can be used for the optical film. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. For example, BaO, SrO, CaO, MgO, etc. are mentioned. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared using a vacuum deposition method or the like, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing a water absorbent may be added between the support and the functional layer, between the uppermost layer of the functional layer and the functional layer.

2- (11) Primer Layer / Inorganic Thin Film Layer In the present optical film, gas barrier properties can be enhanced by installing a known primer layer or inorganic thin film layer between the support and the functional layer.
As the primer layer, for example, an acrylic resin, an epoxy resin, a urethane resin, a silicone resin, or the like can be used. A dense inorganic coating thin film by the method is preferred. As an inorganic vapor deposition layer, vapor deposition layers, such as a silica, a zirconia, an alumina, are preferable. The inorganic vapor deposition layer can be formed by a vacuum vapor deposition method, a sputtering method, or the like.

3. Layer structure of film About this optical film, a well-known layer structure can be used using the above layers. For example, the following are typical examples.
a. Support / light diffusion layer b. Support / light diffusion layer / low refractive index layer (FIG. 9)
c. Support / light diffusion layer / high refractive index layer / low refractive index layer (FIG. 13)
d. Support / light diffusion layer / medium refractive index layer / high refractive index layer / low refractive index layer (FIG. 14)

When the light diffusing layer 83 is coated on the support 81 and the low refractive index layer 85 is laminated as shown in FIG. 9B (FIG. 9), it can be suitably used as an antireflection film. The low refractive index layer 85 can reduce surface reflection by the principle of thin film interference by forming the low refractive index layer 85 on the light diffusion layer 83 with a film thickness of about ¼ of the wavelength of light.
Moreover, even if the high-refractive index layer 84 and the low-refractive index layer 85 are laminated after the light diffusion layer 83 is applied on the support 81 as shown in c (FIG. 13), it is preferably used as an antireflection film. it can. Further, as shown in d (FIG. 14), by arranging the layer structure in the order of the support 81, the light diffusion layer 83, the middle refractive index layer 86, the high refractive index layer 84, and the low refractive index layer 85, the reflectance Can be made 1% or less.

  In the above configurations a to d, the light diffusion layer 83 has an antiglare property, and may be one layer or two or more layers. The antiglare property may be due to the dispersion of the matte particles 87 as shown in FIGS. 9 and 13 to 15, or may be formed by surface shaping by a method such as embossing as shown in FIG. 16. Good. The light diffusion layer formed by the dispersion of the matte particles contains a binder and translucent particles dispersed in the binder. As shown in FIG. 15, the light diffusion layer 83 may be provided on the hard coat layer 88, and conversely, the hard coat layer 88 is provided on the light diffusion layer 83, so that the hard coat layer 88 is changed to the light diffusion layer. A function of adjusting the surface unevenness of 83 may be provided. The light diffusion layer having antiglare properties preferably has both antiglare properties and hard coat properties. You may be comprised by multiple layers, for example, 2 layers-4 layers.

In addition, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the transparent support and the surface side layer or the outermost layer. In the case where there is dust on the surface or the like), another hard coat layer (in the case where the hardness is insufficient with only one hard coat layer 88 or light diffusion layer 83, for example, the embodiment shown in FIG. 15) , Gas barrier layer, water absorption layer (moisture-proof layer), adhesion improving layer, antifouling layer (contamination prevention layer), and the like.
The refractive index of each layer constituting the antireflection film preferably satisfies the following relationship.
Refractive index of light diffusion layer> Refractive index of transparent support> Refractive index of low refractive index layer

4). Manufacturing Method The optical film can be formed by the following method, but is not limited to this method.
4- (1) Adjustment of coating solution

<Preparation>
First, a coating solution containing components for forming each layer is prepared. In that case, the raise of the moisture content in a coating liquid can be suppressed by suppressing the volatilization amount of a solvent to the minimum. The moisture content in the coating solution is preferably 5% or less, more preferably 2% or less. The suppression of the volatilization amount of the solvent is achieved by improving the sealing property at the time of stirring after putting each material into the tank, minimizing the air contact area of the coating liquid at the time of liquid transfer operation, and the like. Moreover, you may provide the means to reduce the moisture content in a coating liquid during application | coating, or before and behind that.

<Physical properties of coating solution>
For coating liquids with a dry film thickness of 200 nm or less such as low refractive index layer, medium refractive index layer, high refractive index layer, antifouling layer, etc., the upper limit speed that can be applied is greatly affected by the liquid properties. It is necessary to control the liquid physical properties, particularly the viscosity and the surface tension, at the moment.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution, the viscosity is low at the time of coating with high shear, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur, which is preferable.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is preferably 2.0 to 5.0 [cc / m ² ]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the coating speed can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases, It is preferable to determine the optimal amount of coating solution to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed decreases, so the range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [ mN / m] is more preferable.
In the light diffusion layer containing translucent particles, the coating liquid is preferably prepared to have a viscosity of 4 cp or more, more preferably 6 cp or more from the viewpoint of preventing sedimentation of the particles.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 50 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 40 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution.
Further, it is also preferable that the filtered coating solution is ultrasonically dispersed immediately before coating to assist defoaming and dispersion holding of the dispersion.

4- (2) Treatment before coating The support used here is preferably subjected to a surface treatment before coating other layers. Specific examples include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, and ultraviolet irradiation treatment. In addition, as described in JP-A-7-333433, it is preferable to provide an undercoat layer.

Furthermore, as a dust removing method used in the dust removing step as a pre-process for application, a method of pressing a nonwoven fabric, a blade or the like on the film surface described in JP-A-59-150571, JP-A-10-309553 A method of blowing the air with high cleanliness described at a high speed to peel off the deposits from the film surface and sucking it with a suction port close to it, blowing compressed air that is ultrasonically vibrated as described in JP-A-7-333613 Examples thereof include a dry dust removing method such as a method for peeling and sucking adhered substances (manufactured by Shinkosha, New Ultra Cleaner, etc.).
In addition, a method of introducing a film into a cleaning tank and peeling off deposits with an ultrasonic vibrator, supplying a cleaning liquid to the film described in Japanese Patent Publication No. 49-13020, and then blowing and sucking high-speed air As described in JP-A-2001-38306, a wet dust removal method such as a method in which a web is continuously rubbed with a roll wetted with liquid and then the liquid is sprayed onto the rubbed surface for cleaning. Can do. Among such dust removal methods, a method using ultrasonic dust removal or a method using wet dust removal is particularly preferable in terms of dust removal effect.
In addition, it is particularly preferable to remove static electricity on the film support before performing such a dust removal step from the viewpoint of increasing dust removal efficiency and suppressing adhesion of dust. As such a static elimination method, a corona discharge ionizer, a light irradiation ionizer such as UV or soft X-ray, or the like can be used. The charged voltage of the film support before and after dust removal and coating is desirably 1000 V or less, preferably 300 V or less, and particularly preferably 100 V or less.

When a cellulose acylate film is used as the support, it is preferable that the temperature of the cellulose acylate film in these treatments is Tg or less, specifically 150 ° C. or less, from the viewpoint of maintaining the flatness of the film.
When the cellulose acylate film is adhered to the polarizing film as in the case where the present optical film is used as a protective film for a polarizing plate, acid treatment or alkali treatment, that is, cellulose acylate is used from the viewpoint of adhesiveness to the polarizing film. It is particularly preferable to carry out a saponification treatment.
From the viewpoint of adhesiveness and the like, the surface energy of the cellulose acylate film is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less, and it can be adjusted by the surface treatment. .

4- (3) Coating Each layer of the optical film can be formed by the following coating method, but is not limited to this method.
Dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method or extrusion coating method (die coating method) (see US Pat. No. 2,681,294), micro gravure coating method, etc. Known methods are used, and among them, the micro gravure coating method and the die coating method are preferable.

  The micro gravure coating method used here is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support. The gravure roll is rotated in reverse, and the surplus coating liquid is scraped off from the surface of the gravure roll by a doctor blade so that a predetermined amount of the coating liquid is removed from the lower surface of the support at a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred to the coating. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a light diffusion layer or a low-refractive index layer containing a fluorine-containing olefin polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

  As coating conditions by the micro gravure coating method, the number of gravure patterns imprinted on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. It is preferably 1 to 50 m / min.

  In order to supply this optical film with high productivity, an extrusion method (die coating method) is preferably used.

<Material and accuracy>
The longer the length of the tip lip on the traveling direction side of the web in the web running direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, the bead is caused by slight disturbance. It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.
Further, when the material of the tip lip of the slot die is made of a material such as stainless steel, the length of the slot die tip lip in the web running direction is set to 30 to 100 μm as described above. Even within this range, the accuracy of the tip lip cannot be satisfied. Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.
In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

<Application speed>
By achieving the accuracy of the backup roll and the tip lip as described above, the coating method preferably used has high film thickness stability during high-speed coating. Furthermore, since the coating method is a pre-weighing method, it is easy to ensure a stable film thickness even during high-speed coating. With respect to a coating solution of a low coating amount, the coating method can be applied at high speed with good film thickness stability. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is likely to occur due to eccentricity and deflection of the roll related to coating. Moreover, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. From the viewpoint of productivity, it is preferable to apply the die coating method at 25 m / min or more.

  In particular, when a hard coat layer is applied on the light diffusing layer, the light diffusing layer can be applied by a single application by applying the coating method described in JP-A-2002-86050 and JP-A-2003-260400. And a hard coat layer can be coated at the same time.

4- (4) <Drying>
The optical film is preferably applied on the support directly or via another layer and then conveyed by a web to a heated zone to dry the solvent.
Various knowledges can be used as a method of drying the solvent. Specific examples include JP-A Nos. 2001-286817, 2001-314798, 2003-126768, 2003-315505, and 2004-34002.
The temperature of the drying zone is preferably 25 ° C. to 140 ° C., the first half of the drying zone is relatively low temperature, and the second half is preferably relatively high temperature. However, it is preferably below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize. For example, some commercially available photo radical generators used in combination with ultraviolet curable resins may volatilize around several tens of percent within a few minutes in warm air at 120 ° C. Some acrylate monomers and the like undergo volatilization in hot air at 100 ° C. In such a case, it is preferable that it is below the temperature at which components other than the solvent contained in the coating composition of each layer start to volatilize as described above.

Moreover, the dry wind after apply | coating the coating composition of each layer on a support body has the wind speed of the coating-film surface of 0.1-2 m / sec while the solid content concentration of the said coating composition is 1-50%. It is preferable to be in the range in order to prevent drying unevenness.
Moreover, after apply | coating the coating composition of each layer on a support body, the temperature difference of the conveyance roll which contacts the surface opposite to the coating surface of a support body in a drying zone, and a support body is 0 to 20 degreeC or less. Then, the drying nonuniformity by the heat transfer nonuniformity on a conveyance roll can be prevented, and it is preferable.

4- (5) Curing After the solvent is dried, the optical film can pass through a zone where the coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

The ionizing radiation species is not particularly limited, and is appropriately selected from ultraviolet rays, electron beams, near ultraviolet rays, visible light, near infrared rays, infrared rays, X-rays, and the like according to the type of curable composition forming the film. However, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferable because they are easy to handle and high energy can be easily obtained.
As the ultraviolet light source for photopolymerizing the ultraviolet reactive compound, any light source that generates ultraviolet light can be used. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be preferably used.

  Moreover, an electron beam can be used similarly. As an electron beam, 50 to 1000 keV, preferably 100 to 100, emitted from various electron beam accelerators such as a cockroft Walton type, a bandegraph type, a resonance transformation type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. An electron beam having an energy of 300 keV can be given.

Irradiation conditions vary depending on each lamp, but the irradiation light amount is preferably 10 mJ / cm ² or more, more preferably 50 mJ / cm ^{2 to} 10000 mJ / cm ² , and particularly preferably 50 mJ / cm ^{2 to} 2000 mJ / cm ^2. It is. At that time, the irradiation distribution in the width direction of the web is preferably 50 to 100%, more preferably 80 to 100%, including both ends with respect to the central maximum irradiation.

In addition, at least one layer laminated on the support is irradiated with ionizing radiation and heated to a film surface temperature of 60 ° C. or more for 0.5 seconds or more from the start of ionizing radiation irradiation, and the oxygen concentration is 10% by volume or less. It is preferable to harden by the process of irradiating ionizing radiation in the atmosphere.
It is also preferable to heat in an atmosphere having an oxygen concentration of 3% by volume or less simultaneously and / or continuously with ionizing radiation irradiation.
In particular, it is preferable that the low refractive index layer which is the outermost layer and has a small film thickness is cured by this method. The curing reaction is accelerated by heat, and a film having excellent physical strength and chemical resistance can be formed.

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. If it is 0.5 seconds or less, the curing reaction cannot be completed, and sufficient curing cannot be performed. Also, maintaining low oxygen conditions for a long time is not preferable because the equipment becomes large and a large amount of inert gas is required.

  The oxygen concentration is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere of 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume of oxygen. Hereinafter, it is most preferably 1% by volume or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas such as nitrogen is required, which is not preferable from the viewpoint of production cost.

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

By supplying inert gas to the ionizing radiation irradiation chamber and making it slightly blown out to the web entrance side of the irradiation chamber, it is possible to effectively reduce the oxygen concentration in the reaction chamber by eliminating the carry air accompanying the web transfer, It is possible to efficiently reduce the substantial oxygen concentration on the pole surface where the inhibition of curing by oxygen is large. The direction of the inert gas flow on the web entrance side of the irradiation chamber can be controlled by adjusting the balance between the supply and exhaust of the irradiation chamber.
Direct blowing of an inert gas onto the web surface is also preferably used as a method for removing the carried air.

  Further, by providing a front chamber in front of the reaction chamber and excluding oxygen on the web surface in advance, the curing can proceed more efficiently. Further, the side surface constituting the web entrance side of the ionizing radiation reaction chamber or the front chamber is preferably 0.2 to 15 mm in gap with the web surface in order to use the inert gas efficiently, more preferably, 0.1%. The thickness is preferably 2 to 10 mm, and most preferably 0.2 to 5 mm. However, in order to continuously manufacture the web, it is necessary to join and connect the webs, and a method of sticking with a joining tape or the like is widely used for joining. For this reason, if the gap between the entrance surface of the ionizing radiation reaction chamber or the front chamber and the web is too narrow, there arises a problem that the joining member such as the joining tape is caught. For this reason, in order to narrow the gap, it is preferable to make at least a part of the entrance surface of the ionizing radiation reaction chamber or the front chamber movable, and to widen the gap by the junction thickness when the junction enters. In order to realize this, the entrance surface of the ionizing radiation reaction chamber or the front chamber is made movable in the forward and backward direction, and when the joint passes, the gap is moved back and forth to widen the gap, It is possible to move the chamber entrance surface vertically with respect to the web surface and move up and down to widen the gap as the joint passes.

  In curing, the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. Below 60 ° C., there is little curing by heating, and at 170 ° C. or higher, problems such as deformation of the substrate occur. Furthermore, this preferable temperature is 60 degreeC-100 degreeC. The film surface refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. If the time for maintaining the temperature of the film surface in the above temperature range is too short, the reaction of the curable composition that forms the film cannot be accelerated, and conversely, if it is too long, the optical performance of the film deteriorates and the equipment is large. Manufacturing problems such as

  There is no particular limitation on the heating method, but a method of heating a roll to contact the film, a method of spraying heated nitrogen, irradiation with far infrared rays or infrared rays is preferable. A method of heating a rotating metal roll described in Japanese Patent No. 2523574 by flowing a medium such as hot water, steam or oil can also be used. As a heating means, a dielectric heating roll or the like may be used.

  The ultraviolet irradiation may be performed every time one layer is provided for each of a plurality of constituent layers, or may be performed after lamination. Or you may irradiate combining these. From the viewpoint of productivity, it is preferable to irradiate ultraviolet rays after laminating multiple layers.

In this method, at least one layer laminated on the support can be cured by multiple times of ionizing radiation. In this case, it is preferable that at least two ionizing radiations are performed in a continuous reaction chamber in which the oxygen concentration does not exceed 3% by volume. By performing multiple times of ionizing radiation irradiation in the same low oxygen concentration reaction chamber, the reaction time required for curing can be effectively ensured.
In particular, when the production rate is increased for high productivity, it is necessary to perform ionizing radiation irradiation a plurality of times in order to ensure the energy of ionizing radiation necessary for the curing reaction.

  Further, when the curing rate (100-residual functional group content) is a certain value of less than 100%, the lower layer has a curing rate of the upper layer when a layer is provided thereon and cured by ionizing radiation and / or heat. When the height is higher than before, the adhesion between the lower layer and the upper layer is improved, which is preferable.

4- (6) Handling In order to continuously produce this optical film, a process of continuously feeding a roll-shaped support film, a process of applying and drying a coating liquid, a process of curing a coating film, a cured layer The process of winding up the support body film which has this is performed.
The film support is continuously sent from the roll-shaped film support to the clean room, and the static electricity charged on the film support is removed by the electrostatic charge-off device in the clean room, and then the film support adheres on the film support. Remove the foreign material that has been removed with a dust remover. Subsequently, the coating solution is applied onto the film support in the application section installed in the clean room, and the applied film support is sent to the drying chamber and dried.
The film support having the dried coating layer is fed from the drying chamber to the curing chamber, and the monomer contained in the coating layer is polymerized and cured. Furthermore, the film support having the cured layer is sent to the curing unit to complete the curing, and the film support having the layer that has been completely cured is wound up into a roll shape.

The above steps may be performed every time each layer is formed, or a plurality of coating portions-drying chambers-curing portions may be provided to continuously form each layer. In particular, when a hard coat layer is sequentially coated on the light diffusing layer, it is preferable to perform a method in which a plurality of coating portions-drying chambers-curing portions are provided.
In order to produce this optical film, as described above, simultaneously with the microfiltration operation of the coating liquid, the coating process in the coating unit and the drying process performed in the drying chamber are performed in a highly clean air atmosphere, and coating is performed. It is preferable that dust and dust on the film have been sufficiently removed before this is performed. The air cleanliness of the coating process and the drying process is preferably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably, it is preferably class 1 (particles of 0.5 μm or more are 35.5 particles / (cubic meter) or less) or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

4- (7) Saponification treatment When making a polarizing plate using this optical film as at least one of the two surface protective films of the polarizing film, the surface on the side to be bonded to the polarizing film should be hydrophilized. Thus, it is preferable to improve the adhesion on the bonding surface.

a. Method of immersing in alkaline solution This is a method of saponifying all surfaces that are reactive with alkali on the entire surface of the film by immersing the film in an alkaline solution under appropriate conditions, and no special equipment is required. From the viewpoint of cost. The alkaline liquid is preferably a sodium hydroxide aqueous solution. A preferred concentration is 0.5 to 3 mol / L, particularly preferably 1 to 2 mol / L. The liquid temperature of a preferable alkali liquid is 30-75 degreeC, Most preferably, it is 40-60 degreeC.
The combination of the saponification conditions is preferably a combination of relatively mild conditions, but can be set depending on the material and composition of the film and the target contact angle.
After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by immersing in a dilute acid so that the alkaline component does not remain in the film.

By saponification treatment, the surface opposite to the surface having the coating layer is hydrophilized. The protective film for polarizing plate is used by adhering the hydrophilic surface of the transparent support to the polarizing film.
The hydrophilized surface is effective for improving the adhesiveness with the adhesive layer mainly composed of polyvinyl alcohol.
In the saponification treatment, the lower the contact angle with respect to the surface of the transparent support opposite to the side having the coating layer, the better from the viewpoint of adhesion to the polarizing film, while the dipping method simultaneously has the coating layer. Since it is damaged by alkali from the surface to the inside, it is important to set the minimum reaction conditions. When the contact angle to water of the transparent support on the opposite surface is used as an index of damage to each layer due to alkali, particularly when the transparent support is triacetylcellulose, preferably 10 to 50 degrees, more preferably Is 30 to 50 degrees, more preferably 40 to 50 degrees. If it is 50 degrees or more, there is a problem in the adhesion to the polarizing film, which is not preferable. On the other hand, if it is less than 10 degrees, the film suffers too much damage, which impairs physical strength and is not preferable.

b. Method for applying alkaline solution As a means for avoiding damage to each film in the above-described immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, spraying, contact with a belt containing the solution, or the like may be performed. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the dipping method of a from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, it is possible to have a layer using a material weak against the alkali solution on the opposite surface. For example, in vapor deposition films and sol-gel films, various effects such as corrosion, dissolution, and peeling occur due to the alkaline solution. Is possible.

  In any of the saponification methods a and b, since each layer can be formed after being unwound from a roll-shaped support, it may be carried out by a series of operations in addition to the film production process. Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of saponification by protecting with a laminate film As in the case of b above, when the coating layer is insufficient in resistance to an alkaline solution, the laminate film is bonded to the surface on which the final layer is formed after the final layer is formed. Then, only the triacetyl cellulose surface opposite to the surface on which the final layer is formed is hydrophilized by dipping in an alkaline solution, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. Compared with the method b, there is an advantage that a laminating film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer: Up to lower layer is resistant to alkaline solution, but if insufficient resistance to alkaline solution of upper layer is insufficient, dip into alkaline solution after forming up to lower layer to make both sides hydrophilic The upper layer can also be formed after processing. Although the manufacturing process is complicated, for example, in an antireflection film composed of a light diffusion layer and a low refractive index layer, when it has a hydrophilic group, there is an advantage that the interlayer adhesion between the light diffusion layer and the low refractive index layer is improved. is there.

e. Method of forming a coating layer on a pre-saponified triacetyl cellulose film Saponification of the triacetyl cellulose film by immersing it in an alkaline solution in advance, and forming a coating layer directly on one side or via another layer May be. In the case of saponification by dipping in an alkaline solution, the interlayer adhesion with the triacetyl cellulose surface hydrophilized by saponification may deteriorate. In such a case, after saponification, only the surface on which the coating layer is to be formed is treated by corona discharge, glow discharge or the like to remove the hydrophilic surface and then form the coating layer. Further, when the coating layer has a hydrophilic group, the interlayer adhesion may be good.

(3) Other AGLR Films Next, other AGLR films other than the anti-glare film (AGLR film) described as the optical functional film 29 will be described.
Here, the other AGLR film will be described as an optical film.
The optical film is an optical film having at least a light diffusing layer on a transparent support, and substantially parallel light is incident on the film surface at an incident angle of 5 ° and measured in a plane including the film normal and the incident direction. The reflectance of the received light receiving portion with respect to the angle θ is R (θ), R (θ) is normalized with the reflectance of regular reflection, Rrel (θ), and the maximum amount of change with respect to the angle θ | dRrel (θ ) / Dθ | max is a scattering coefficient A (formula 1), the reflection coefficient B (formula 2) calculated from the scattering coefficient A and the 5 ° specular reflectance Rs is 2.0 to 5. 0.

(Expression 1) Scattering coefficient A = 1 / (10 × | dRrel (θ) / dθ | max)
(Expression 2) Reflection coefficient B = 2.2 × log ₁₀ (Rs) −7.5 × log ₁₀ (A) +5.9

  The present optical film has at least a light diffusion layer on a transparent support. The light diffusion layer only needs to have a function of scattering light and may have other functions, but has an internal scattering property and / or a surface scattering property, preferably due to the surface scattering property. The form which has anti-glare property and hard-coat property to do is good. In addition to the light diffusion layer, the optical film is preferably an antireflection film having an antireflection layer that reduces the reflectance by using the principle of optical interference. In the following description, unless otherwise specified, the optical film includes the antireflection film having the above-described configuration.

  The optical film of this structure is demonstrated with reference to drawings. In addition, it is not limited to this suitable aspect.

  FIG. 17A is a cross-sectional view schematically showing the layer structure of the optical film. The optical film shown in FIG. 17 has the same configuration as described above, but a transparent support 81, a light diffusion layer 83 formed on the support 81, and a low refraction formed on the light diffusion layer 83. Rate layer 85. By forming the low refractive index layer 85 on the light diffusion layer 83 with a film thickness of about ¼ of the wavelength of light, surface reflection is reduced by the principle of thin film interference. The antireflection film further preferably has at least a light diffusion layer 83 and a low refractive index layer 85 on a transparent support 81. The light diffusion layer 83 is preferably composed of a translucent resin and mat particles (translucent particles) 87 dispersed in the translucent resin. It is preferable that the refractive index of each layer which comprises the optical film of this structure satisfy | fills the following relationships.

    Refractive index of light diffusion layer> Refractive index of transparent support> Refractive index of low refractive index layer

  The light diffusing layer 83 has an internal scattering property and / or a surface scattering property, and preferably has an antiglare property and a hard coat property due to the surface scattering property. In FIG. 17 (a), one formed by one layer is illustrated, and from the viewpoint of cost and process simplification, it is preferably formed by one layer, but a plurality of layers, for example, two to four layers. It may be comprised. In order to reduce the feeling of browning due to surface irregularities, it is preferable to provide an overcoat layer 91 on a light diffusion layer (layer containing translucent particles) having surface irregularities as shown in FIG. In order to prevent charging, it is desirable to have a transparent conductive layer between the light diffusion layer 83 and the support 81 or between the light diffusion layer 83 and the low refractive index layer 85. It is particularly desirable to have a transparent conductive layer between the support 81. It is further desirable to have a transparent conductive layer between the light diffusing layer 83 and the support 81 and to have conductive particles in the light diffusing layer. In addition to the transparent conductive layer, a functional layer such as a moisture-proof layer may be provided between the light diffusion layer 83 and the support 81.

  FIGS. 18A and 18B are cross-sectional views schematically showing an aspect in which a low refractive index layer is not provided. Even if it is an aspect like FIG. 18, although the effect by this structure may be acquired, it is preferable to provide the low-refractive-index layer 85 like FIG.

  This optical film is highly effective in reducing reflections. Reflection is affected by two optical properties, anti-glare and anti-reflection, but so far only defined by independent ranges. That is not enough. As a result of intensive studies, it has been found that the level of visibility of the contour of the reflected image is determined by the size of the function of the characteristics based on the antiglare property and the antireflection property. That is, it has been found that it is preferable to set the scattering coefficient A (formula 1) indicating surface scattering related to antiglare properties and the reflection coefficient B (formula 2) calculated from the 5 ° specular reflectance Rs within a specific range. It was.

(Scattering coefficient A)
FIGS. 19A and 19B are diagrams showing an example of a method for measuring the angle dependency of the reflected light intensity when the scattering coefficient A is calculated. FIG. 20 is a schematic diagram illustrating an example of the relative reflectance dRrel (θ) with respect to the angle θ of the light receiving unit and the calculation of | dRrel (θ) / dθ | max.
The scattering coefficient A is a value obtained by measuring substantially parallel light on an optical film surface having at least a light diffusing layer on a transparent support at an incident angle of 5 ° and measuring in a plane including the film normal and the incident direction. The reflectance with respect to the angle θ is R (θ), the value obtained by normalizing R (θ) with the reflectance of regular reflection is Rrel (θ), and the maximum amount of change with respect to the angle θ | dRrel (θ) / dθ | _The value calculated from _max is calculated from the scattering coefficient A (Equation 1). When the degree of blurring of the reflected image reflected on the film surface is small, the maximum amount of change | dRrel (θ) / dθ | _max increases with respect to the angle θ. Conversely, when the degree of blurring is large, the maximum amount of change is Get smaller. The scattering property can be expressed by the reciprocal of the degree of blur, and the scattering coefficient A is calculated from Equation 1. Θ is measured from 0 to 45 °.

(Expression 1) Scattering coefficient A = 1 / (10 × | dRrel (θ) / dθ | _max )

  The substantially parallel light means light traveling in parallel within a range of ± 3 °.

  The scattering coefficient A is one parameter that means the degree of scattering of light incident on the film surface. In particular, as an index indicating the degree of blurring of the outline of a reflected image reflected on the film surface, the correlation is higher than the glossiness and the surface haze. That is, it is a parameter that accurately represents the degree of blurring of the outline of the reflected image, which is a factor for reducing reflection. Further, the scattering coefficient A is related to the feeling of browning on the film surface and is a parameter that also affects the improvement of bright room contrast.

(Reflection coefficient B)
FIG. 21 is a diagram showing the relationship between the reflection coefficient B, the scattering coefficient A, and the 5 ° specular reflectance Rs.
The reflection coefficient B is calculated using (Expression 2) from the scattering coefficient A obtained from (Expression 1) and the 5 ° specular reflectance Rs.

(Expression 2) Reflection coefficient B = 2.2 × log ₁₀ (Rs) −7.5 × log ₁₀ (A) +5.9

  The reflection coefficient B is a parameter that means the intensity of reflection. The intensity of reflection indicates the degree to which a viewer (a person who appreciates the image display device) recognizes a reflected image reflected on the film surface provided on the surface of the image display device. The reflected image becomes harder to recognize as the outline becomes blurred and / or the amount of reflected light is smaller. However, depending on the screen size, viewing distance (distance from the screen to the viewer), etc. It was found that the degree of contribution changed.

  The formula for calculating the reflection coefficient B is a sample having different scattering coefficients A and 5 ° specular reflectance Rs, and a size suitable for an image display device having a large screen (a large screen of 20 inches or more, especially 32 inches or more). It is obtained by evaluating the reflection intensity at a viewing distance (2 m or more). The relationship between the scattering coefficient A of the reflection coefficient B and the 5 ° specular reflectance Rs is shown in FIG. Since the reflection coefficient B is a sensory evaluation value, the scattering coefficient A, which is a stimulation value, and a 5 ° specular reflectance are calculated based on Weber-Fechner's law that “a human sensory amount is proportional to the logarithm of a given stimulation amount”. Correlates with the logarithm of Rs. Further, the reflection coefficient B is also a parameter affecting the improvement of bright room contrast, which is also related to the feeling of browning on the film surface.

  Here, the reflection coefficient B is in the range of 2.0 to 5.0, preferably in the range of 2.5 to 4.8, and more preferably in the range of 3.0 to 4.5. A range of 3.5 to 4.5 is particularly preferable. If the reflection coefficient is more than 5.0, the reflection reduction effect of the optical film is not sufficient, and if it is less than 2.0, the bright room contrast of the optical film tends to deteriorate.

  In order to prevent the bright room contrast from deteriorating due to surface scattering, it is preferable to set the scattering coefficient A in a specific range together with the reflection coefficient B. The scattering coefficient A is preferably in the range of 1.0 to 3.0, more preferably 1.3 to 2.7, particularly preferably 1.5 to 2.5, and 1.7 to 2.3. Further preferred. If the scattering coefficient is too large, the bright room contrast deteriorates, and if it is too small, the effect of preventing reflection tends to be reduced.

  In order to sufficiently reduce the reflection, it is preferable that the 5 ° specular reflectance Rs is also in a specific range. The 5 ° specular reflectance Rs is preferably from 0.1% to 2.0%, more preferably from 0.1% to 1.5%, particularly preferably from 0.1% to 1.2%, % To 1.0% is more preferable. Most preferably, it is 0.1% or more and 0.8% or less. If the 5 ° specular reflectance Rs is too high, the reflection will deteriorate.

  In order to provide an optimum surface film for an image display device having a large screen, it is preferable to improve bright room contrast. In order to improve the bright room contrast, the integrated reflectance is preferably 0.2 to 2.0%, more preferably 0.2 to 1.8%, and particularly preferably 0.2 to 1.5%. Preferably, 0.2 to 1.3% is most preferable. If the integrated reflectance is too high, the image is reflected and the bright room contrast deteriorates. In particular, when a whitish object is reflected from the position of regular reflection of the person who appreciates the display, the bright room contrast is remarkably deteriorated.

  In order to improve the bright room contrast, it is preferable to set the difference between the integrated reflectance and the 5 ° specular reflectance Rs within a specific range in addition to the integrated reflectance. The difference between the integrated reflectance and the 5 ° specular reflectance Rs is preferably 0.1% to 1.0%, more preferably 0.15% to 0.8%, and further 0.2% to 0.6%. preferable. If the difference between the integrated reflectance and the 5 ° specular reflectance Rs is too large, the contrast deteriorates. In particular, when a blackish object is reflected from the position of regular reflection of the person viewing the display, the bright room contrast is remarkably deteriorated. On the other hand, if the difference between the integrated reflectance and the 5 ° specular reflectance Rs is too small, the surface scattering property is not sufficient and the effect of reducing the reflection is insufficient.

  Therefore, it is preferable to improve the bright room contrast regardless of the viewing environment of the display. For this purpose, it is preferable to satisfy the above-mentioned integral reflectance and the preferable range of the difference between the integral reflectance and the 5 ° specular reflectance Rs at the same time. Further, it is ideal that the reflection coefficient B, the scattering coefficient A, and the 5 ° specular reflectance Rs are simultaneously satisfied. In this case, the image display device having a large screen that simultaneously satisfies the reflection reduction effect and the bright room contrast improvement. The most suitable surface film can be provided.

In order to provide an optimal surface film for an image display device having a large screen, it is also preferable to set the neutrality of the color of the reflected light within a specific range. The CIE1976L ^* a ^* b ^* color space a ^* b ^* values of the specularly reflected light with respect to 5 ° incident light of the CIE standard light source D65 in the wavelength range of 380 to 780 nm are −7 ≦ a ^* ≦ 7 and −10 ≦ b, respectively. ^* ≦ 10 is preferable, −5 ≦ a ^* ≦ 5, −7 ≦ b ^* ≦ 7 is more preferable, and 0 ≦ a ^* ≦ 5, −7 ≦ b ^* ≦ 0 is set. Is more preferable. By setting a ^* and b ^* within a preferable range, when external light is reflected, the reflected color becomes neutral, and the viewer does not care about it. It is most preferable to set a ^* and b ^* within a preferable range simultaneously with the various reflection performances described above.

  In order to realize the reflection performance and color as described above, it is preferable to set the refractive index (na) of the light diffusion layer and the refractive index (nb) of the low refractive index layer within a specific range. The difference na-nb between the refractive index (na) of the light diffusion layer and the refractive index (nb) of the low refractive index layer is 0.04 or more, preferably 0.08 or more and 0.35 or less, and 0.10. More preferably, it is 0.30 or less, and particularly preferably 0.14 or more and 0.25 or less. Within the range of this refractive index difference, the reflectance can be lowered sufficiently, reflection of the reflected image on the surface can be sufficiently prevented, the strength of the film becomes higher, and the color becomes stronger. Can be prevented.

  The refractive index (na) of the light diffusion layer is preferably from 1.48 to 1.70, particularly preferably from 1.50 to 1.60, and particularly preferably from 1.50 to 1.55. If the refractive index of the light diffusion layer is too small, the difference in refractive index from the low refractive index layer becomes small, and the antireflection property is reduced. On the other hand, if the refractive index is too high, the materials that can be used are limited, which is not preferable because the cost becomes high and the color becomes strong. In addition, the refractive index of a light-diffusion layer is the value calculated | required from the refractive index of the coating film containing solid content except a translucent particle.

The refractive index (nb) of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.20 to 1.40, further preferably 1.30 to 1.38, and a display device having a large screen In order to provide the most suitable surface film, 1.31-1.37 is particularly preferable. If the refractive index of the low refractive index layer is too high, the reflectance is increased, and it is not preferable because the refractive index of the light diffusion layer needs to be increased in order to reduce the reflectance. On the other hand, if the refractive index is too low, the strength of the low refractive index layer decreases, which is not preferable. Moreover, since the material which can be used is limited and becomes high-cost, it is not preferable.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.

  Formula (I): (mλ / 4) × 0.7 <n1 × d1 <(mλ / 4) × 1.3

  In formula (I), m is a positive odd number, n1 is the refractive index of the low refractive index layer, and d1 is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm. In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

  It is preferable that the refractive index of the light diffusion layer and the refractive index of the low refractive index layer are simultaneously controlled within a specific range. The refractive index of the light diffusion layer is preferably 1.50 to 1.60, and the refractive index of the low refractive index layer is preferably 1.20 to 1.40, and the refractive index of the light diffusion layer is 1.50 to 1.50. More preferably, the refractive index of the low refractive index layer is 1.20 to 1.40, the refractive index of the light diffusion layer is 1.50 to 1.55, and the refractive index of the low refractive index layer is 1. More preferably, the refractive index of the light diffusion layer is 1.50 to 1.55, and the refractive index of the low refractive index layer is particularly preferably 1.31 to 1.37. .

  In this optical film, a structure in which a layer having a higher refractive index (high refractive index layer) and a low refractive index layer than the light diffusing layer may be laminated, or an intermediate refractive index may be provided between the light diffusing layer and the high refractive index layer. A structure in which a layer having a refractive index (medium refractive index layer), a high refractive index layer, and a low refractive index layer are stacked may be used. The film thickness of each of the medium refractive index layer, the high refractive index layer, and the low refractive index layer is preferably 200 nm or less. Regarding the film thickness and refractive index of each medium refractive index layer, high refractive index layer, and low refractive index layer. For example, a layer structure described in JP-A-2003-121606 can be used. However, from the viewpoint of cost, unevenness, productivity, etc., the low refractive index layer should be in the above-mentioned range without providing a middle refractive index layer or a high refractive index layer between the light diffusion layer and the low refractive index layer. It is particularly preferable to control the reflection performance.

  In order to realize the reflection performance and color as described above, it is preferable to control the irregularities on the surface of the optical film within a specific range. The optical film of this configuration has a center line average roughness Ra of 0.02 to 0.35 μm, preferably 0.02 to 0.20 μm, and more preferably 0.03 to 0.0. It is 15 μm, more preferably 0.05 to 0.15 μm. If Ra is too large, the bright room contrast is deteriorated, and if Ra is too small, the reflection is deteriorated. The 10-point average roughness Rz is 10 times or less of Ra, and the average mountain valley distance Sm is preferably 30 to 200 μm, particularly preferably 50 to 180 μm, still more preferably 50 to 150 μm, and particularly preferably 80 to 120 μm. It is preferable to design so that the standard deviation of the height of the convex part from the deepest part of the concavo-convex part is 0.5 μm or less and the surface with the inclination angle of 0 to 5 degrees is 10% or more.

  In order to improve the bright room contrast, it is also preferable to control the average inclination angle. The average inclination angle is preferably 0.1 to 4.0 degrees, particularly preferably 0.2 to 3.0 degrees, more preferably 0.2 to 2.0 degrees, and most preferably 0.2 to 1. Twice. When the average inclination angle is large, the bright room contrast is deteriorated, and when it is small, the reflection is deteriorated. In order to make both good characteristics, it is preferable that the Sm value satisfies the above-mentioned range as well as the average inclination angle, the average inclination angle is 0.2 to 1.2 degrees, and the Sm value is 50 to 120 μm. It is particularly preferred to satisfy this simultaneously.

  In order to provide a surface film having an excellent bright room contrast and a good reflection reduction effect for an image display device having a large screen, it is necessary to optimally design reflection performance and color. For that purpose, it is most preferable to set the surface irregularities at the same time as the refractive index of the scattering layer and the refractive index of the low refractive index layer, and the refractive index of the light diffusion layer is 1.50 to 1.55 and low. Most preferably, the refractive index of the refractive index layer satisfies 1.31 to 1.37 and Ra satisfies 0.08 to 0.13 μm at the same time, and more preferably, Sm and the average inclination angle are set to the above ranges at the same time. It is.

  In this optical film, haze due to surface scattering (hereinafter referred to as surface haze) is preferably 0.3% to 20%, particularly preferably 0.5% to 10%, and 0.5% to It is preferably 5%, particularly preferably 0.5 to 2%. When the surface haze is too large, the bright room contrast is deteriorated, and when it is too small, the reflection is deteriorated.

  In the present optical film, the haze due to internal scattering (hereinafter referred to as internal haze) is preferably 0% to 60%, more preferably 1% to 40%. -35% is particularly preferable, and 7% to 30% is more preferable. If the internal haze is too large, the front contrast is lowered and the brownishness is increased. If it is too small, combinations of materials that can be used are limited, it becomes difficult to combine antiglare and other characteristic values, and the cost is high.

The surface haze and internal haze can be measured by the following procedure.
(1) The total haze value (H) of the film is measured according to JIS-K7136.
(2) A few drops of silicone oil are added to the front and back surfaces of the low refractive index layer side of the film, and sandwiched from the front and back using two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSUNAMI), Two glass plates and a film are optically closely adhered to each other, the haze is measured with the surface haze removed, and only the silicone oil is sandwiched between two separately measured glass plates to subtract the measured haze. The calculated value is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

  The image clarity of the present optical film according to JIS K7105 is preferably 30% to 99%, more preferably 40% to 95%, still more preferably 50% to 90% when measured at an optical comb width of 0.5 mm. %, More preferably 60% to 80%. When the image clarity is low, the bright room contrast deteriorates, and when it is high, the reflection deteriorates.

(Light diffusion layer)
The light diffusing layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering, scattering properties inside the film, and preferably hard coat properties for improving the scratch resistance of the film. Accordingly, it preferably contains a translucent resin capable of imparting hard coat properties, and translucent particles for imparting antiglare properties and internal scattering properties.

(Translucent particles)
The average particle diameter of the translucent particles is preferably 0.5 to 10 μm, more preferably 3 to 10 μm, particularly preferably 5 to 10 μm, and further preferably 6 to 8 μm. When the average particle size is small, the average inclination angle of the surface becomes large and the bright room contrast tends to deteriorate. Further, the scattering in the high angle direction due to the internal scattering property of light becomes large, which is not preferable from the viewpoint of deteriorating dark room contrast and causing character blur of the display. On the other hand, if the particle size is too large, the film thickness becomes large and the curl deteriorates in order to obtain a preferable surface form. This is not preferable because the material cost becomes high.

Specific examples of the translucent particles include, for example, poly ((meth) acrylate) particles, crosslinked poly ((meth) acrylate) particles, polystyrene particles, crosslinked polystyrene particles, crosslinked poly (acryl-styrene) particles, and melamine resin particles. Preferred examples include resin particles such as benzoguanamine resin particles. Among these, crosslinked resin particles are preferable, and crosslinked polystyrene particles, crosslinked poly ((meth) acrylate) particles, and crosslinked poly (acryl-styrene) particles are preferably used, and particularly preferably crosslinked poly ((meth) acrylate) particles. . By adjusting the refractive index of the translucent resin in accordance with the refractive index of each translucent particle selected from these particles along with the particle size and type, the desired internal haze as well as the centerline average roughness , Surface haze, can be achieved. Specifically, a translucent resin (having a refractive index after curing of 1.50 to 1.1) having as a main component a trifunctional or higher functional (meth) acrylate monomer that is preferably used in the light diffusion layer of the present configuration as described later. 53) and a combination of translucent particles made of a crosslinked poly (meth) acrylate polymer having an acrylic content of 50 to 100 mass percent are preferred, and a combination of crosslinked poly ((meth) acrylate) particles is more preferred.
In addition, as the translucent particles, inorganic fine particles such as aggregating silica described later can also be used.

Further, the difference in refractive index between the translucent resin and the translucent particles (the refractive index of the translucent particles−the refractive index of the translucent resin) is preferably 0.001 to 0.100 as an absolute value. More preferably, it is 0.001-0.050, Most preferably, it is 0.001-0.040, More preferably, it is 0.001-0.030, Most preferably, it is 0.001-0.025. If it is within the above-mentioned range, problems such as film character blur, a decrease in dark room contrast, and surface turbidity are unlikely to occur. Using translucent particles having an average particle diameter of 6 to 8 μm made of a crosslinked poly (meth) acrylate polymer, the difference in refractive index between the translucent resin and the translucent particles is set to 0.01 to 0.025. Is particularly preferred.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring it with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the light-transmitting particles is measured by measuring the turbidity by equally dispersing the light-transmitting particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  Two or more different types of particles may be used in combination. Translucent particles with a larger particle size that form surface irregularities with translucent particles with a larger particle size, impart anti-glare properties, and reduce surface roughness with translucent particles with a smaller particle size Form surface irregularities with, impart anti-glare properties, mainly impart internal scattering with translucent particles of smaller particle diameter, adjust the scattering angle distribution of internal scattering with two types of particles, etc. Designs that take advantage of the characteristics of multiple particles are possible. Even when two or more different kinds of particles are used, it is preferable to use the aforementioned particles for one of them.

  The translucent particles are preferably blended so as to be contained in an amount of 5 to 40% by mass in the total solid content of the light diffusion layer. More preferably, it is 5-25 mass%, More preferably, it is 7-20 mass%. If it is less than 5% by mass, the effect of addition is insufficient, and if it exceeds 40% by mass, problems such as image blurring, surface turbidity and glare are likely to occur.

The coating amount of the light-transmitting particle is preferably 30~2500mg / ^{m 2,} more preferably 100~2400mg / ^{m 2,} more preferably 600~2300mg / ^{m 2,} particularly preferably, 1000~2000mg / ^{m 2} It is.

The average film thickness of the light diffusion layer is preferably 2 to 30 μm, more preferably 7.5 to 30 μm, particularly preferably 8 to 20 μm, and still more preferably 10 to 16 μm. If it is too thin, the hard coat property will be insufficient, and if it is too thick, curling and brittleness may be deteriorated and the workability may be lowered. The average film thickness of the diffusion layer is measured by enlarging the cross section to 5000 times with an electron microscope, copying the light diffusion layer with a tracing paper (SE-TD58: 50 g / m ² ) manufactured by KOKUYO, and measuring the mass. To do.

  The average film thickness of the light diffusion layer is 1.4 to 3.5 times the average particle diameter of the translucent particles, preferably 1.5 to 3.0 times, more preferably 1.5 to 2.5 times. 1.6 to 2.0 times is particularly preferable. When the average film thickness of the light diffusion layer is 1.4 to 3.5 times the average particle diameter of the translucent particles, the film thickness dependence and particle diameter dependence of the antiglare property are reduced. For this reason, even if the film thickness fluctuates due to streaks or drying unevenness generated during application, it is difficult to recognize planar defects such as streaks or unevenness. The anti-glare property is that the surface irregularities are formed by protrusions due to the three-dimensional structure formed by an aggregate of a plurality of particles, and the size of the surface irregularities is small even if the film thickness or particle diameter changes slightly. Is hardly changed, and the change in antiglare property is small and preferable. A preferred surface morphology can be obtained. If the average film thickness / average particle ratio is too small, the particles are present in one layer in the film, so if the film thickness or particle diameter changes slightly, the size of the surface irregularities changes and the antiglare property changes greatly. Also, the bright room contrast tends to deteriorate. On the other hand, if it is too large, an aggregate of a plurality of particles is buried in the film, so that there are almost no surface irregularities and the required antiglare property cannot be obtained.

  When the average film thickness / average particle ratio is 1.4 to 3.5, the average particle diameter varies depending on the particle lot, and the antiglare property of the film is less likely to vary, and a film with little lot variation is obtained. You can also From the viewpoint of reflection and bright room contrast, if the average film thickness / average particle ratio is too small, the bright room contrast is deteriorated, and if it is too large, the reflection is deteriorated.

  When this optical film is used for the surface of a display, it is preferable that pencil hardness is high. The pencil hardness is preferably 2H or more, more preferably 3H to 7H, and still more preferably 4H to 6H.

(Translucent resin)
The translucent resin is preferably a binder polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a binder polymer having a saturated hydrocarbon chain as a main chain. The binder polymer preferably has a crosslinked structure.

  As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable. It is particularly preferred that the binder polymer is polymerized and formed after being applied as an ethylenically unsaturated monomer onto the substrate.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di ( (Meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3- Chlorohexane tetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide-modified products and caprolactone-modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2- Acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.

  In order to sufficiently reduce the surface reflection or to control the internal scattering property, it is also preferable to control the refractive index of the light diffusion layer. In order to increase the refractive index of the light diffusion layer, a method of dispersing inorganic fine particles with a high refractive index in the binder of the light diffusion layer to increase the refractive index as described later, the refractive index of the binder polymer itself is increased, A method of increasing the refractive index of the light diffusion layer without using high refractive index inorganic fine particles is preferably used. In order to increase the refractive index of the binder polymer, this monomer structure has a high refractive index containing at least one atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. Monomers or oligomers, monomers or oligomers having a fluorene skeleton in the molecule, and the like can also be selected. Specific examples of the high refractive index monomer include (meth) acrylates having a fluorene skeleton, (meth) acrylates having a urethane structure, bis (4-methacryloylthiophenyl) sulfide, vinylnaphthalene, vinylphenyl sulfide, 4-methacrylate. Examples include loxyphenyl-4′-methoxyphenyl thioether. Two or more of these monomers may be used in combination.

Moreover, it is preferable that translucent resin has a (meth) acrylate monomer more than trifunctional as a main component. By forming the translucent resin from such a monomer, the hardness of the light diffusion layer is increased, and an effect that hard coat properties can be imparted with a thinner film thickness is obtained.
Here, the “translucent resin having a trifunctional or higher functional (meth) acrylate monomer as a main component” means that a resin component composed of a trifunctional or higher functional (meth) acrylate monomer is 40 to 100 in the translucent resin. It means that mol% is contained. The content of repeating units composed of a tri- or higher functional (meth) acrylate monomer is preferably 60 to 100 mol%.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Therefore, the light diffusion layer is composed of a monomer for forming a translucent resin such as the above-mentioned ethylenically unsaturated monomer, a photo radical initiator or a thermal radical initiator, translucent particles, and an inorganic material as described later if necessary. It can be formed by preparing a coating liquid containing a filler, and applying the coating liquid on a transparent support, followed by curing by a polymerization reaction with ionizing radiation or heat.

Photo radical (polymerization) initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfides Examples include compounds, fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (p.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful.
Preferable examples of commercially available photocleavable photoradical (polymerization) initiators include Irgacure (651, 184, 907) manufactured by Ciba Specialty Chemicals.
The photo radical (polymerization) initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the polyfunctional monomer.
In addition to the photoradical (polymerization) initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

As the thermal radical initiator, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

The binder polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, translucent particles and inorganic fine particles is prepared, and the coating liquid is applied onto a transparent support and then polymerized by ionizing radiation or heat. It can be cured by reaction to form a light diffusion layer.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

(Inorganic fine particles)
To improve the hardness of the light diffusion layer and adjust the refractive index of the layer to adjust the haze value resulting from internal scattering to the desired range, and to adjust the viscosity of the coating solution to obtain a preferred surface morphology In addition to the above light-transmitting particles, inorganic fine particles can also be used. In the case of using inorganic fine particles, the main component is an oxide of at least one metal selected from silicon, titanium, zirconium, aluminum, indium, zinc, tin, and antimony, and the average particle size is 1 μm or less, preferably Inorganic fine particles having a size of 0.2 μm or less, more preferably 0.1 μm or less, particularly preferably 0.06 μm or less, and further preferably 0.02 μm or less are preferred. These inorganic fine particles generally have a specific gravity higher than that of the organic substance and can increase the density of the coating composition, and thus have the effect of slowing the sedimentation rate of the translucent particles.

The inorganic fine particles are selected from metal oxides mainly composed of oxides of at least one metal selected from titanium, zirconium, indium, zinc, tin, and antimony, in order to increase the refractive index. It is particularly desirable to use at least one metal oxide selected from the group consisting of at least one metal oxide selected from the group consisting of oxides of at least one metal selected from titanium and zirconium. It is particularly desirable to use a product. Among them, from the viewpoint of the light resistance of the light diffusion layer, zirconium having no photocatalytic action is desirable, but it is also desirable to use titanium with suppressed photocatalytic action.
Also, from the viewpoint of antistatic, it is desirable to use conductive inorganic fine particles, more than inorganic fine particles mainly composed of an oxide of at least one metal selected from indium, zinc, tin, and antimony. It is desirable to use at least one selected metal oxide.

  Moreover, you may add at least 1 sort (s) of the inorganic particle whose refractive index is lower than the said translucent resin for the purpose of a hardness improvement and refractive index adjustment. Silica particles are preferably used as the inorganic fine particles having a low refractive index.

  As another preferred form of the silica particles, agglomerated silica in which particles having a primary particle diameter of several tens of nm form an aggregate is used. Agglomerated silica can stably impart an appropriate surface haze, and can also be preferably used as the above-described translucent particles imparting the antiglare property. Aggregating silica may be used alone or in combination with other light-transmitting particles and inorganic fine particles. The cohesive silica can be obtained, for example, by a so-called wet method synthesized by a neutralization reaction between sodium silicate and sulfuric acid, but is not limited thereto. The wet method is further roughly classified into a precipitation method and a gelation method, and either method may be used. The secondary particle size of the cohesive silica is preferably in the range of 0.1 to 10.0 μm, but is selected in combination with the layer thickness of the light diffusion layer containing the particles. The adjustment of the secondary particle size is performed by the degree of particle dispersion (control by mechanical dispersion using a sand mill or the like, or chemical dispersion using a dispersant or the like).

The surface of the inorganic fine particles used in the light diffusion layer is preferably subjected to silane coupling treatment or titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with the binder species on the filler surface is preferably used. The surface treatment agent may be used by mixing it in the coating composition without performing a coupling treatment in advance.
When using these inorganic fine particles, the addition amount is preferably 10 to 90% of the total mass of the light diffusion layer, more preferably 20 to 80%, and particularly preferably 30 to 75%.
Such inorganic fine particles have a particle size sufficiently smaller than the wavelength of light and therefore do not scatter, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.
Moreover, the organosilane compound and its derivative which can be used by the below-mentioned low refractive index layer can be used for a light-diffusion layer. The addition amount of the organosilane compound and its derivative is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and particularly preferably 3 to 15 mass%, based on the total solid content of the light diffusion layer.

(Leveling agent)
The light diffusion layer preferably uses various leveling agents for the purpose of preventing unevenness. Specifically, the leveling agent is preferably a fluorine-based leveling agent or a silicone-based leveling agent. Particularly, the fluorine-based leveling agent is preferable because of its high unevenness preventing ability.
The leveling agent is preferably an oligomer or a polymer rather than a low molecular compound.
When a leveling agent is added to the light diffusion layer, the leveling agent is quickly unevenly distributed on the surface of the applied liquid film. The surface energy is lowered by the leveling agent.
Therefore, from the viewpoint of preventing unevenness of the light diffusion layer, it is preferable that the surface energy of the light diffusion layer is low.

The surface energy of light diffusion layer (γs ^v : unit, mJ / m ² ) is experimental on anti-glare light diffusion layer with reference to DKOwens: J.Appl.Polym.Sci., 13,1741 (1969) is represented by the sum of pure water between H ₂ O and methylene iodide CH ₂ respective contact angle theta _{H2 O} of I _2, where theta following simultaneous equations from _CH2I2 (1) (2) from the obtained gamma] s ^d and gamma] s ^h obtained in It is the energy conversion value of the surface tension of the antiglare light diffusing layer defined by the value γs ^v (= γs ^d + γs ^h ). (The mN / m unit is mJ / m ² unit.) Before the sample is measured, it is necessary to adjust the humidity for a certain period of time under a predetermined temperature and humidity condition. In this case, the temperature is preferably in the range of 20 ° C. to 27 ° C., the humidity is preferably in the range of 50 RH% to 65 RH%, and the humidity control time is preferably 2 hours or more.

(1) 1 + cos θH ₂ O = 2√γs ^d (√γH ₂ Od / γH ₂ Ov) + 2√γs ^h (√γH ₂ Oh / γH ₂ Ov)
_{(2) 1 + cosθCH 2 I} 2 = 2√γs d (√γCH 2 I 2 d / γCH 2 I 2 v) + 2√γs h (√γCH 2 I 2 h /
γCH ₂ I ₂ v)
Here, γ _H2O ^d = 21.8 °, γ _H2O ^h = 51.0 °, γ _H2O ^v = 72.8 °, γ _CH2I2 ^d = 49.5 °, γ _CH2I2 ^h = 1.3 °, and γ _CH2I2 ^v = 50.8 °.

The surface energy of the light diffusion layer is in the range of 45 mJ / m ² or less, preferably in the range of 20~45mJ / ^{m 2,} range 22~40mJ / m ² is more preferable.
By setting the surface energy of the light diffusion layer to 45 mJ / m ² or less, it is possible to obtain an effect that uneven coating of the light diffusion layer hardly occurs.
However, since an upper layer such as a low refractive index layer is further coated on the light diffusing layer, the leveling agent is preferably eluted into the upper layer, and the light diffusing layer is coated with a solvent (for example, methyl ethyl ketone) in the upper layer coating solution It is preferable that the surface energy of the light diffusion layer after the immersion is rather high, and it is preferable that the surface energy is 35 to 70 mJ / m ² .

  Hereinafter, a preferred fluorine-based leveling agent as a leveling agent for the light diffusion layer will be described. The silicone leveling agent will be described later.

The fluorine-based leveling agent is preferably a polymer having a fluoroaliphatic group, and further a polymer of a repeating unit (polymerization unit) corresponding to the monomer (i) below, or a repeating unit corresponding to the monomer (i) below. A copolymer of an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith, containing (polymerized unit) and a repeating unit (polymerized unit) corresponding to the monomer (ii) below is useful. Examples of such monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 can be used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

(I) Fluoroaliphatic group-containing monomer represented by the following general formula <1> General formula <1>

In the above general formula <1>, R ¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, more preferably an oxygen atom or —N (R ¹² ) —, and still more preferably an oxygen atom. R ¹² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. R _f represents —CF ₃ or —CF ₂ H.
M in the general formula <1> represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1.
N in the general formula <1> represents an integer of 1 to 11, more preferably 1 to 9, and still more preferably 1 to 6. R _f is preferably —CF ₂ H.
Further, two or more kinds of polymerized units derived from the fluoroaliphatic group-containing monomer represented by the general formula 1 may be contained in the fluoropolymer as a constituent component.

(Ii) Monomer represented by the following general formula <2> copolymerizable with the above (i) General formula <2>

In the above general formula <2>, R ¹³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, more preferably an oxygen atom or —N (R ¹⁵ ) —, and still more preferably an oxygen atom. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ¹⁴ is a linear, branched or cyclic alkyl group having 1 to 60 carbon atoms which may have a substituent, or an aromatic group which may have a substituent (for example, phenyl group or naphthyl). Group). The alkyl group may include a poly (alkyleneoxy) group. Furthermore, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is very preferable.

  The amount of the fluoroaliphatic group-containing monomer represented by the above general formula <1> used for the production of a preferred fluoropolymer is 10% by mass or more based on the total amount of the monomer of the fluoropolymer, preferably It is 50 mass% or more, More preferably, it is 70-100 mass%, More preferably, it is the range of 80-100 mass%.

Hereinafter, although the specific structural example of a preferable fluorine-type polymer is shown, it is not this limitation.
In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

  The amount of the polymerization unit of the fluoroaliphatic group-containing monomer constituting the fluorine-based polymer is preferably more than 10% by mass, more preferably 50 to 100% by mass, and the viewpoint of preventing unevenness of the light diffusion layer In view of the above, it is most preferably 75 to 100% by mass, and when the low refractive index layer is applied on the light diffusion layer, it is most preferably 50 to 75% by mass. (Described in all polymer units constituting the fluoropolymer)

  The silicone leveling agent will be described. Examples of the silicone-based leveling agent include polydimethylsiloxane having various substituents such as oligomers such as ethylene glycol and propylene glycol, and the side chain and the terminal of the main chain are modified. KF-96 manufactured by Shin-Etsu Chemical Co., Ltd. X-22-945.

In addition, a nonionic surfactant having a hydrophobic group composed of dimethylpolysiloxane and a hydrophilic group composed of polyoxyalkylene can also be preferably used.
Specific examples of these nonionic surfactants include, for example, Nippon Unicar Co., Ltd., silicone surfactants SILWET L-77, L-720, L-7001, L-7002, L-7604, Y-7006, FZ-2101, FZ-2104, FZ-2105, FZ-2110, FZ-2118, FZ-2120, FZ-2122, FZ-2123, FZ-2130, FZ-2154, FZ-2161, FZ-2162, FZ- 2163, FZ-2164, FZ-2166, FZ-2191, and SUPERSILWET SS-2801, SS-2802, SS-2803, SS-2804, SS-2805, and the like.
In addition, as a preferable structure of the nonionic surfactant in which the hydrophobic group is composed of dimethylpolysiloxane and the hydrophilic group is composed of polyoxyalkylene, a dimethylpolysiloxane structure portion and a polyoxyalkylene chain are alternately and repeatedly bonded. A linear block copolymer is preferable, and JP-A-6-49486 can be referred to.
Specific examples thereof include, for example, silicone surfactants ABN SILWET FZ-2203, FZ-2207, FZ-2208 and the like manufactured by Nippon Unicar Co., Ltd.

  The amount of the fluorine-containing leveling agent and silicone leveling agent added to the coating solution is preferably 0.001% by mass to 1.0% by mass, more preferably 0.01% by mass to 0.2% by mass. It is.

  When applying the light diffusion layer, a fluorine-containing leveling agent or a silicone leveling agent is used to lower the surface tension of the coating solution to improve surface uniformity and maintain high productivity by high-speed application. Surface treatment such as treatment, UV treatment, heat treatment, saponification treatment, solvent treatment, particularly preferably corona treatment, to prevent the surface free energy from decreasing, thereby reducing the surface energy of the light diffusion layer before coating the low refractive index layer. The purpose can also be achieved by controlling the range.

The preferred weight average molecular weight of the fluoropolymer is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of a fluorine-type polymer is the range of 0.001-5 mass% with respect to a coating liquid, Preferably it is the range of 0.005-3 mass%, More preferably, it is 0.01-1. It is the range of mass%. If the addition amount of the fluorine-based polymer is less than 0.001% by mass, the effect is insufficient, and if it exceeds 5% by mass, the coating film is not sufficiently dried and performance as a coating film (for example, reflectance, It may adversely affect the (scratch resistance).

The film having this configuration may use a thickener in order to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and the amount by which the viscosity of the coating liquid is increased by addition is preferably 1 to 50 cP, and more preferably. Is 3 to 20 cP, most preferably 5 to 10 cP.

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral polyvinyl formal polyvinyl acetal polyvinyl propanal polyvinyl hexanal polyvinyl pyrrolidone polyacrylic acid ester polymethacrylic acid ester polystyrene cellulose acetate cellulose propionate cellulose acetate butyrate

  In addition, layered compounds such as smectite, mica, bentonite, silica, and montmorillonite described in JP-A-8-325491 and polyacrylic acid soda, ethylcellulose, polyacrylic acid, organic clay described in JP-A-10-219136, and the like are known. Viscosity modifiers and thixotropic agents can be used. As the thixotropic agent, those obtained by organically treating a layered compound having a particle size of 0.3 μm or less are particularly preferable. A particle size of 0.1 μm or less is more preferable. The particle size of the layered compound can be considered as the length of the long axis. Usually, it is suitable to set it as about 1-10 mass parts with respect to 100 mass parts of ultraviolet curable resin.

  In many cases, the light diffusing layer having this configuration is directly wet-coated on a transparent support, and therefore the solvent used in the coating composition is an important factor. The requirements include sufficiently dissolving various solutes such as the translucent resin, not dissolving the translucent particles, and being less likely to cause coating unevenness and drying unevenness during the coating to drying process. In addition, it is also preferable characteristics that the support is not dissolved (necessary for preventing failure such as deterioration in flatness and whitening), and conversely, the support is swollen to a minimum extent (necessary for adhesion). One kind of the solvent may be used, but it is particularly preferable to adjust the swelling property of the support, the solubility of the material, the drying property, the aggregation property of the particles and the like by using two or more kinds of solvents.

  As specific examples of the solvent, various ketones (such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone) and various cellosolves (such as ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether) are preferably used. In addition, various alcohols (propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol, etc.), toluene and the like are preferably used.

  When triacetylcellulose is used for the support, as specific examples, the main solvent is various ketones (methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, etc.), various cellosolves (ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc.), toluene Is preferably used. Moreover, antiglare property can be adjusted by adding a small amount of solvent having a hydroxyl group to the main solvent selected from the above, which is particularly preferable. Since the small amount solvent having a hydroxyl group can strengthen the antiglare property by remaining until after the main solvent in the drying step of the coating composition, the main solvent can be used at any temperature within a range of 20 to 30 ° C. The vapor pressure of the small amount solvent is preferably lower than that of the solvent. For example, a preferred example is a combination of propylene glycol (vapor pressure at 20.0 ° C .: 0.08 mmHg) as a small amount solvent having a hydroxyl group with respect to methyl isobutyl ketone (vapor pressure at 21.7 ° C .: 16.5 mmHg) as the main solvent. As mentioned. The mixing ratio of the main solvent and the small amount solvent having a hydroxyl group is preferably 99: 1 to 50:50, more preferably 95: 5 to 70:30 in terms of mass ratio as the former: the latter. Within the said range, stability of a coating liquid becomes favorable. When three or more kinds of solvents are used, it is preferable that the amount of the solvent having the largest amount: the sum of the other solvents is within the above range.

  In addition, by adding a small amount of highly swellable solvent to the main solvent having low swellability of the transparent support selected from the above solvents, the transparent support can be obtained without deteriorating other performance and surface condition. Adhesion with the body can be improved. Specifically, methyl isobutyl ketone and toluene are used as a main solvent, and methyl ethyl ketone, acetone, cyclohexanone, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like are used as a small amount of solvent. It is particularly preferable to use methyl isobutyl ketone and toluene as the main solvent and methyl ethyl ketone and cyclohexanone as the small amount of solvent. Further, for controlling the hydrophilicity of the solvent, propylene glycol, ethylene glycol, ethanol, methanol, isopropyl alcohol, 1-butanol, 2-butanol and the like can be added and used, and propylene glycol and ethylene glycol are particularly preferably used. be able to.

  The mixing ratio of the main solvent and the small amount of solvent is preferably 99: 1 to 50:50, more preferably 95: 5 to 60:40, by weight. Within this range, variations in surface quality in the drying process after coating are prevented. When three or more kinds of solvents are used, it is preferable that the amount of the solvent with the largest amount: the sum of the other solvents is within the above range.

(Low refractive index layer)
The low refractive index layer used here has a thermosetting property and / or a photocuring property mainly comprising a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. It is preferably formed by applying a composition.

The low refractive index layer is a cured film formed by, for example, applying, drying and curing a curable composition containing a fluorine-containing compound as a main component.
The curable composition used in forming the low refractive index layer contains at least two of (A) a fluorine-containing compound, (B) inorganic fine particles, and (C) an organosilane compound. Is preferable, and it is particularly preferable that all three types are contained. As the fluorine-containing compound, it is preferable to use a fluorine-containing monomer, oligomer, polymer or fluorine-containing sol-gel material having a low refractive index. The fluorine-containing monomer, oligomer, polymer, or fluorine-containing sol-gel material has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the low refractive index layer formed by crosslinking with heat or ionizing radiation, and has a contact angle of 85 with water. The material which becomes ˜120 ° is preferable.
The material for forming the low refractive index layer will be described below.

(Fluoropolymer for low refractive index layer)
The fluorine-containing polymer is preferably a polymer that is crosslinked by heat or ionizing radiation from the viewpoint of improving productivity in the case of coating and curing the roll film while transporting the web.

  Further, when the optical film is mounted on an image display device, the lower the peel strength from a commercially available adhesive tape, the easier it is to peel off after sticking a sticker or memo, so the peel strength is 500 gf (4.9 N) or less. Preferably, 300 gf (2.9 N) or less is more preferable, and 100 gf (0.98 N) or less is most preferable. Further, the higher the surface hardness measured with a microhardness meter, the harder it is to scratch. Therefore, the surface hardness is preferably 0.3 GPa or more, and more preferably 0.5 GPa or more.

  The fluorine-containing polymer used in the low refractive index layer is preferably a fluorine-containing polymer containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. In addition to hydrolyzate and dehydration condensate of alkyl group-containing silane compound [for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane], a fluorine-containing monomer unit and a crosslinking reactive unit are constituted. Examples thereof include a fluorine-containing copolymer as a unit. In the case of a fluorinated copolymer, the main chain preferably consists of only carbon atoms. That is, it is preferable that the main chain skeleton does not have an oxygen atom or a nitrogen atom.

  Specific examples of the fluorine-containing monomer unit include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, perfluorooctylethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3- Dioxoles, etc.), (meth) acrylic acid partial or fully fluorinated alkyl ester derivatives (for example, Biscoat 6FM (manufactured by Osaka Organic Chemicals) and M-2020 (manufactured by Daikin)), fully or partially fluorinated vinyl ethers, etc. However, perfluoroolefins are preferable, and hexafluoropropylene is particularly preferable from the viewpoint of refractive index, solubility, transparency, availability, and the like.

  Examples of the crosslinking reactive unit include a structural unit obtained by polymerization of a monomer having a self-crosslinking functional group in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether; carboxyl group, hydroxy group, amino group, sulfo group A structural unit obtained by polymerization of a monomer having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. And a structural unit in which a crosslinkable reactive group such as a (meth) acryloyl group is introduced by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group).

  In addition to the fluorine-containing monomer unit and the cross-linking reactive unit, from the viewpoint of solubility in a solvent, film transparency, and the like, a monomer not containing a fluorine atom is appropriately copolymerized to introduce another polymerization unit. You can also. There are no particular limitations on the monomer units that can be used in combination, such as olefins [ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.], acrylic esters [methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid 2 -Ethylhexyl], methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers (methyl) Vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.], vinyl esters [vinyl acetate, vinyl propionate, vinyl cinnamate, etc.], acrylamides [N-tertbutylacrylamide, N-silane] B hexyl acrylamide], methacrylamides, and acrylonitrile derivatives.

  As described in JP-A-10-25388 and JP-A-10-147739, a curing agent may be appropriately used in combination with the fluoropolymer.

The fluorine-containing polymer particularly useful here is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters, particularly a radically reactive group such as a crosslinking reactive group [(meth) acryloyl group, epoxy Group, ring-opening polymerizable group such as oxetanyl group, etc.].
It is preferable that the polymerized units having the crosslinking reactive group occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymerized units of the polymer.

As a preferred form of the fluorine-containing polymer for the low refractive index layer used in the present optical film, a copolymer represented by the general formula L-1 can be mentioned.
Formula L-1

In General Formula L-1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, and particularly preferably a linking group having 2 to 4 carbon atoms, which is linear. Alternatively, it may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N and S.
Preferred examples include * — (CH ₂ ) ₂ —O — **, * — (CH ₂ ) ₂ —NH — **, * — (CH ₂ ) ₄ —O — **, * — (CH ₂ ). _{6 -O - **, * - (} CH 2) 2 -O- (CH 2) 2 -O - **, * - CONH- (CH 2) 3 -O - **, * -CH 2 CH (OH ) CH ₂ —O — **, * —CH ₂ CH ₂ OCONH (CH ₂ ) ₃ —O — ** (* represents the connecting site on the polymer main chain side, and ** represents the connecting on the (meth) acryloyl group side Represents a part). m represents 0 or 1;

  In general formula L-1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula L-1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. The polymer Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc., can be selected as appropriate, depending on the purpose, single or multiple vinyls You may be comprised by the monomer.

  Preferred examples of A include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, and vinyl propionate. , Vinyl esters such as vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane ( (Meth) acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaco Can be mentioned unsaturated carboxylic acids and derivatives thereof such as acid, more preferably a vinyl ether derivative, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

x, y, and z represent mol% of each constituent component, and 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65 are preferable, and 35 ≦ x ≦ 55, and 30 ≦ y ≦ 65 are more preferable. 60, 0 ≦ z ≦ 20, particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10. However, x + y + z = 100. The general formula L-1 in this configuration is preferably the general formula L-2.
Formula L-2

In general formula L-2, X represents the same meaning as in general formula <1>, and the preferred range is also the same. n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said general formula L-1 is applicable.
x, y, z1 and z2 each represent mol% of each repeating unit, and x and y preferably satisfy 30 ≦ x ≦ 60 and 5 ≦ y ≦ 70, respectively, more preferably 35 ≦ x ≦. 55, 30 ≦ y ≦ 60, particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55. z1 and z2 preferably satisfy 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65, more preferably 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10, and 0 ≦ z1 ≦ 10, 0 It is particularly preferable that ≦ z2 ≦ 5. However, x + y + z1 + z2 = 100.

The copolymer represented by the general formula L-1 or L-2 is, for example, a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component having a (meth) acryloyl group by any one of the methods described above. It can be synthesized by introduction. As the reprecipitation solvent used in this case, isopropanol, hexane, methanol and the like are preferable.
Preferable specific examples of the copolymer represented by the general formula L-1 or L-2 include those described in paragraph numbers [0035] to [0047] of JP-A-2004-45462, It can be synthesized by the method described in the publication.

(Inorganic fine particles for low refractive index layer)
The amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance may deteriorate. It is preferable to be inside.
Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index. Examples thereof include fine particles of magnesium fluoride and silicon oxide (silica). In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle size of the inorganic fine particles is, for example, preferably 10% to 100%, preferably 30% to 100%, more preferably 35% to 80%, and still more preferably 40% to 60% of the thickness of the low refractive index layer. It is as follows. That is, when the thickness of the low refractive index layer is 100 nm, the particle size of the silica fine particles is preferably 30 nm to 100 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. Therefore, it is preferable to be within the above range. The inorganic fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to achieve both the reflection and bright room contrast, which are the effects of this configuration, it is necessary to control the refractive index within the above-mentioned range, and the inorganic fine particles preferably have a hollow structure. The refractive index is preferably 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.32. Here, the refractive index represents the refractive index of the whole particle, and does not represent the refractive index of only the inorganic material of the outer shell in the case of hollow structure inorganic fine particles. At this time, the radius of the cavity inside the particle a, when the radius of the outer shell of the particle b, the porosity x represented by the following formula (II) (Formula ^{II): x = (4πa 3} /3) / (4πb ^3/3) × 100
Preferably, it is 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%.
If the refractive index of the hollow inorganic fine particles is made lower and the porosity is increased, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the refractive index is 1 Particles with a low refractive index of less than .17 do not hold. The refractive index of the inorganic fine particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  In order to achieve both the reflection and bright room contrast, which are the effects of the present optical film, it is preferable to control the content of the hollow inorganic fine particles so that the refractive index of the low refractive index layer falls within the aforementioned range. The amount of the inorganic fine particles is preferably 20 to 60% by mass in the total solid content of the low refractive index layer, more preferably 30 to 55% by mass, and particularly preferably 35 to 50% by mass. . If the amount of hollow inorganic fine particles is too large, the film becomes weak, and if it is too small, the refractive index cannot be lowered sufficiently.

At least one kind of inorganic fine particles having an average particle size of less than 25% of the thickness of the low refractive index layer (hereinafter referred to as “small size inorganic fine particles”) is an inorganic fine particle having a particle size within the above-mentioned preferred range (hereinafter referred to as “large”). It may be used in combination with “size inorganic fine particles”.
Since the small-sized inorganic fine particles can be present in the gaps between the large-sized inorganic fine particles, they can contribute as a retaining agent for the large-sized inorganic fine particles.
When the low refractive index layer is 100 nm, the average particle size of the small-sized inorganic fine particles is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm, and particularly preferably 8 nm to 15 nm. Use of such inorganic fine particles is preferable in terms of raw material costs and a retaining agent effect.

Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Further, chemical surface treatment with a surfactant, a coupling agent or the like may be performed. Of these, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, silane coupling treatment is particularly effective.
The coupling agent is used as a surface treatment agent for the inorganic fine particles of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is preferable to make it contain in a layer.
The inorganic fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.

(Organosilane compound for low refractive index layer)
The curable composition includes an organosilane compound, a hydrolyzate of the organosilane, and a partial condensate of the hydrolyzate of the organosilane (hereinafter, the obtained reaction solution is also referred to as “sol component”). It is preferable to contain at least one selected from the viewpoint of scratch resistance, particularly from the viewpoint of achieving both antireflection ability and scratch resistance.
These components function as a binder for the low refractive index layer by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, in this structure, since it has preferably the said fluorine-containing polymer as a fluorine-containing compound, the binder which has a three-dimensional structure is formed by irradiation of actinic light.
The organosilane compound is preferably one represented by the following general formula (A1).
Formula _{^{(A1) :( R 10) m}} -Si (X) 4-m

In the general formula (A1), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group. m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively.
The substituent contained in R ¹⁰ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.

When there are a plurality of R ^{10 s} , at least one of them is preferably a substituted alkyl group or a substituted aryl group. Among the organosilane compounds represented by the general formula (A1), an organosilane compound having a vinyl polymerizable substituent represented by the following general formula (A2) is preferable.
General formula (A2)

In the general formula (A2), R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

  L represents a divalent linking chain. Specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group having a linking group (for example, ether, ester, amide, etc.) inside, and a linking group inside. A substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, an alkylene group having a linking group therein is preferred, an unsubstituted alkylene group, an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferable. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula (A1), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in formula (A1), preferably a halogen atom, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, or a carbon number of 1 -3 alkoxy groups are more preferred, and methoxy groups are particularly preferred.

  Two or more compounds of the general formula (A1) and general formula (A2) may be used in combination. Although the specific example of a compound represented by general formula (A1) and general formula (A2) below is shown, it is not limited to these.

  Of the compounds represented by M-1 to M-10, M-1, M-2, and M-5 are preferable.

  The hydrolyzate and / or partial condensate of the organosilane compound is generally produced by treating the organosilane compound in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. In this configuration, it is preferable to use a metal chelate compound, an acid catalyst of inorganic acids and organic acids. Inorganic acids are preferably hydrochloric acid and sulfuric acid, and organic acids are preferably those having an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and further, acid dissociation constants in hydrochloric acid, sulfuric acid and water. Is preferably an organic acid having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferably an organic acid having an acid dissociation constant of 2.5 or less in water. Specifically, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

As the metal chelate compound, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is the number of carbon atoms 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in this configuration has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.

R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ may be an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, or n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Moreover, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

  Specific examples of these metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum.

  Among the specific examples of the metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. is there. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can be used.

  It is preferable that a β-diketone compound and / or a β-ketoester compound is further added to the curable composition. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used here, and acts as a stability improver for the curable composition used in this configuration. To do. Here, R ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In this configuration, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. Within the above range, good storage stability can be obtained.

The compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass based on the total solid content of the low refractive index layer.
The organosilane compound may be added directly to the curable composition (coating liquid for light diffusion layer, low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance to prepare the organosilane compound. It is preferable to prepare a hydrolyzate and / or partial condensate of a silane compound and prepare the curable composition using the obtained reaction solution (sol solution). A composition containing a decomposition product and / or a partial condensate and a metal chelate compound is prepared, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound thereto is used as at least one of a light diffusion layer and a low refractive index layer. It is preferable to coat it by adding it to the coating solution for the layer.
Further, both the light diffusion layer and the low refractive index layer are coated with a curable coating composition containing a hydrolyzate of organosilane represented by the general formula (A1) and / or a partial condensate thereof. A cured film formed by curing is preferable.

  5-100 mass% is preferable, the usage-amount of the sol component of the organosilane with respect to a fluorine-containing polymer in a low refractive index layer has more preferable 5-40 mass%, 8-35 mass% is still more preferable, 10-30 mass % Is particularly preferred. If the amount used is small, it is difficult to obtain the effect, and if the amount used is too large, the refractive index increases or the shape / surface shape of the film deteriorates.

  An inorganic filler other than the above-mentioned inorganic fine particles can be added to the curable composition in an addition amount within a range that does not impair the desired effect of the present configuration. As the inorganic filler, inorganic fine particles described for the light diffusing layer are preferable, and it is particularly preferable to add a material that can impart conductivity, such as indium, tin, and antimony, within a range that does not greatly affect the refractive index.

(Sol-gel material)
Various sol-gel materials can also be used as the material for the low refractive index layer. As such a sol-gel material, metal alcoholates (alcohols such as silane, titanium, aluminum, and zirconium), organoalkoxy metal compounds, and hydrolysates thereof can be used. In particular, alkoxysilane, organoalkoxysilane and its hydrolyzate are preferable. Examples of these include tetraalkoxysilane (tetramethoxysilane, tetraethoxysilane, etc.), alkyltrialkoxysilane (methyltrimethoxysilane, ethyltrimethoxysilane, etc.), aryltrialkoxysilane (phenyltrimethoxysilane, etc.), dialkyl. Examples thereof include dialkoxysilane and diaryl dialkoxysilane. In addition, organoalkoxysilanes having various functional groups (vinyl trialkoxysilane, methylvinyl dialkoxysilane, γ-glycidyloxypropyltrialkoxysilane, γ-glycidyloxypropylmethyl dialkoxysilane, β- (3,4-epoxy) Dicyclohexyl) ethyltrialkoxysilane, γ-methacryloyloxypropyltrialkoxysilane, γ-aminopropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, γ-chloropropyltrialkoxysilane, etc.), perfluoroalkyl group-containing silane compounds ( For example, it is also preferable to use (heptadecafluoro-1,1,2,2-tetradecyl) triethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc.). In particular, the use of a fluorine-containing silane compound is preferable from the viewpoint of lowering the refractive index of the layer and imparting water and oil repellency, and it is also preferable to contain the fluorine-containing compound (A) described above.

[Other substances contained in the low refractive index layer]
In the curable composition, various additives, a radical polymerization initiator, and a cationic polymerization initiator are added to the above-mentioned (A) fluorine-containing compound, (B) inorganic fine particles, and (C) an organosilane compound as necessary. Further, they are prepared by dissolving them in a suitable solvent. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

  From the viewpoint of interfacial adhesion with the lower layer directly in contact with the low refractive index layer and improvement in hardness of the low refractive index layer, etc., a polyfunctional (meth) acrylate compound, polyfunctional epoxy compound, polyisocyanate compound, aminoplast, polybasic acid or A small amount of a curing agent such as an anhydride can be added to the low refractive index layer. When adding these, it is preferable to set it as the range of 40 mass% or less with respect to the total solid of a low-refractive-index layer film, It is more preferable to set it as the range of 30 mass% or less, The range of 20 mass% or less It is particularly preferable that

  In addition, for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance, and slipperiness, a known silicone compound or fluorine compound antifouling agent, slipping agent, etc. are appropriately added to the low refractive index layer. You can also. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

  Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like. It is done. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferred silicone compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), manufactured by Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (named above) but not limited thereto.

As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF ₂ CF ₃ , —CH ₂ (CF ₂ ) ₄ H, —CH ₂ (CF ₂ ) ₈ CF ₃ , —CH ₂ CH ₂ (CF ₂ ) ₄ H, etc.), even branched structures (eg, —CH (CF ₃ ) ₂ , —CH ₂ CF (CF ₃ ) ₂ , —CH (CH ₃ ) CF ₂ CF ₃ , —CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), but alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl groups) , A perfluorocyclopentyl group or an alkyl group substituted with these, and may have an ether bond (for example, —CH ₂ OCH ₂ CF ₂ CF ₃ , —CH ₂ CH ₂ OCH ₂ C). ₄ F ₈ H, —CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , —CH ₂ C H ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H, etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172, F-179A, defender MCF-300 (trade name), etc., but are not limited thereto.

  In addition, the aforementioned silicone compound or fluorine compound, which can be appropriately added for the purpose of imparting properties such as antifouling property, water resistance, chemical resistance and slipperiness, has a molecular structure for the low refractive index layer. (A) It is also preferable to include in the molecular structure of the fluorine-containing compound in the curable composition. That is, it is desirable to contain it in the form of a block or a graph in the molecular structure of the aforementioned fluorine-containing polymer or fluorine-containing sol-gel.

  For the purpose of imparting properties such as dust resistance and antistatic properties, a known cationic surfactant or a dustproof agent such as a polyoxyalkylene compound, an antistatic agent, or the like can be appropriately added to the low refractive index layer. These dustproofing agent and antistatic agent may contain the structural unit as a part of the function in the above-mentioned silicone compound or fluorine compound. When these are added as additives, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass. Examples of preferred compounds include, but are not limited to, Dainippon Ink Co., Ltd., Megafac F-150 (trade name), Toray Dow Corning Co., Ltd., SH-3748 (trade name), and the like. Do not mean. it can. As the inorganic fine particles, those described above can be used.

[Solvent for low refractive index layer]
As a solvent used in the coating composition for forming the low refractive index layer, it is possible to dissolve or disperse each component, to easily form a uniform surface in the coating process and the drying process, and to ensure liquid storage stability. Various solvents selected from the viewpoint of having an appropriate saturated vapor pressure can be used. From the viewpoint of the drying load, it is preferable that the main component is a solvent having a boiling point of 100 ° C. or lower at normal pressure and room temperature, and it is more preferable to contain a small amount of a solvent having a boiling point of 100 ° C. or higher for adjusting the drying speed. .

  Examples of the solvent having a boiling point of 100 ° C. or lower include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), ethers such as tetrahydrofuran (66 ° C), ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as Luketone, 79.6 ° C, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C.), propionitrile (97.4 ° C.), carbon disulfide (46.2 ° C.), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

Examples of the solvent having a boiling point of 100 ° C. or more include, for example, octane (125.7 ° C.), toluene (110.6 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), and chlorobenzene (131.7 ° C.). , Dioxane (101.3 ° C), dibutyl ether (142.4 ° C), isobutyl acetate (118 ° C), cyclohexanone (155.7 ° C), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C) 1-butanol (117.7 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl sulfoxide (189 ° C.) and the like. Cyclohexanone and 2-methyl-4-pentanone are preferable. For example, when 2-butanone and cyclohexanone are used in combination, the mixing ratio (mass ratio) is preferably 99: 1 to 50:50, more preferably 99: 1 to 80:20, and further 99: 1 to 90:10. 99: 1 to 95: 5 are particularly preferable.

[Transparent conductive layer]
The optical film is preferably provided with a transparent conductive layer for the purpose of preventing static electricity from the viewpoint of preventing static electricity on the film surface. The transparent conductive layer is effective when there is a demand for lowering the surface resistance value from the display side or when dust on the surface or the like becomes a problem. As a method of forming the transparent conductive layer, for example, a method of applying a conductive coating liquid containing conductive particles and a reactive curable resin, or a metal or metal oxide that forms a transparent film is deposited or sputtered. And a known method such as a method of forming a conductive thin film. In the case of coating, the method is not particularly limited, and an optimum method is selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics of the coating liquid and the coating amount. Just do it. The transparent conductive layer can be formed on the transparent support or the light diffusing layer directly or via a primer layer that strengthens the adhesion with them.

The thickness of the transparent conductive layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and further preferably from 0.05 to 5 μm. When used in a layer close to the outermost layer, sufficient antistatic properties can be obtained even if the film is thin. The surface resistance of the transparent conductive layer is ^preferably from ¹⁰ 5 ~10 ¹² Ω / ^sq, more preferably from 10 5 ~10 ⁹ Ω / ^sq, it is 10 5 ~10 ⁸ Ω / sq Most preferred. The surface resistance of the transparent conductive layer can be measured by a four-probe method.

It is preferable that the transparent conductive layer is substantially transparent. Specifically, the haze of the transparent conductive layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. preferable. The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The transparent conductive layer preferably has excellent strength, and the strength of the specific antistatic layer is preferably 1 kg load pencil hardness (as defined in JIS-K-5400), preferably H or higher. More preferably, it is more preferably 3H or more, and most preferably 4H or more.

(Electrically conductive particles)
The average particle diameter of primary particles of the conductive particles used for the transparent conductive layer is preferably 1 to 150 nm, more preferably 5 to 100 nm, and most preferably 5 to 70 nm. The average particle diameter of the conductive particles in the formed transparent conductive layer is 1 to 200 nm, preferably 5 to 150 nm, more preferably 10 to 100 nm, and more preferably 10 to 80 nm. Most preferred. The average particle diameter of the conductive particles is an average diameter weighted by the mass of the particles and can be measured by a light scattering method or an electron micrograph.
The specific surface area of the energizing particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

The conductive particles are preferably inorganic fine particles made of a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide and titanium nitride. Tin oxide and indium oxide are particularly preferred.
The conductive particles are mainly composed of oxides or nitrides of these metals, and can further contain other elements. The main component means a component having the largest content (mass%) among the components constituting the particles. Examples of other elements include Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, S, B, Nb, In, V and a halogen atom are mentioned. In order to increase the conductivity of tin oxide and indium oxide, it is preferable to add Sb, P, B, Nb, In, V and a halogen atom. Particularly preferred are tin oxide containing Sb (ATO) and indium oxide containing Sn (ITO). The ratio of Sb in ATO is preferably 3 to 20% by mass. The ratio of Sn in ITO is preferably 5 to 20% by mass.

The conductive particles may be surface-treated. The surface treatment can be performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of organic compounds used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.

  The ratio of the conductive inorganic fine particles in the transparent conductive layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass. Two or more kinds of conductive particles may be used in combination in the transparent conductive layer.

  The conductive particles can be used in the transparent conductive layer in a dispersion state. As the dispersion medium for the conductive particles, it is preferable to use a liquid having a boiling point of 60 to 170 ° C. Examples of dispersion media include water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofurane), ether alcohol (eg, 1 Methoxy-2-propanol). Among these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferable. The conductive particles can be dispersed in the medium using a disperser. Examples of the disperser include a sand grinder mill (for example, a bead mill with pins), a high speed impeller mill, a pebble mill, a roller mill, an attritor and a colloid mill, and a sand grinder mill and a high speed impeller mill are particularly preferable. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The conductive particles can be added to the light diffusion layer.

(Binder for transparent conductive layer)
The transparent conductive layer can use a crosslinked polymer as a binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersed state of the conductive particles. The crosslinked structure has a function of reinforcing the transparent conductive layer by imparting a film-forming ability to the polymer.

  Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.

The polyolefin main chain is composed of a saturated hydrocarbon. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group.
The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group.
In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. The polyurethane main chain has repeating units bonded by urethane bonds (—NH—CO—O—).
The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group).

The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group).
In the polyamine main chain, repeating units are bonded by an imino bond (—NH—). The polyamine main chain is obtained, for example, by a ring-opening polymerization reaction of an ethyleneimine group.
The polyamide main chain has repeating units bonded by an amide bond (—NH—CO—). The polyamide main chain is obtained, for example, by a reaction between an isocyanate group and a carboxyl group (including an acid halide group).
The melamine resin main chain is obtained, for example, by a polycondensation reaction between a triazine group (eg, melamine) and an aldehyde (eg, formaldehyde). In the melamine resin, the main chain itself has a crosslinked structure.

The anionic group is bonded directly to the main chain of the polymer or bonded to the main chain via a linking group. The anionic group is preferably bonded to the main chain as a side chain via a linking group.
Examples of the anionic group include a carboxylic acid group (carboxyl), a sulfonic acid group (sulfo), and a phosphoric acid group (phosphono), and a sulfonic acid group and a phosphoric acid group are preferable.
The anionic group may be in a salt state. The cation that forms a salt with the anionic group is preferably an alkali metal ion. Moreover, the proton of the anionic group may be dissociated.
The linking group that binds the anionic group and the polymer main chain is preferably a divalent group selected from —CO—, —O—, an alkylene group, an arylene group, and combinations thereof.

  The crosslinked structure chemically bonds (preferably covalently bonds) two or more main chains. The cross-linked structure is preferably covalently bonded to three or more main chains. The cross-linked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

  The crosslinked polymer having an anionic group is preferably a copolymer having a repeating unit having an anionic group and a repeating unit having a crosslinked structure. The proportion of the repeating unit having an anionic group in the copolymer is preferably 2 to 96% by mass, more preferably 4 to 94% by mass, and most preferably 6 to 92% by mass. The repeating unit may have two or more anionic groups. The proportion of the repeating unit having a crosslinked structure in the copolymer is preferably 4 to 98% by mass, more preferably 6 to 96% by mass, and most preferably 8 to 94% by mass.

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or quaternary ammonium group has a function of maintaining the dispersed state of the inorganic fine particles, like the anionic group. In addition, even if the amino group, the quaternary ammonium group and the benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure, the same effect can be obtained.

In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group.
The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6.

  The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the proportion is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. % Is more preferable, and 0.1 to 28% by mass is most preferable.

  For example, the following reactive organosilicon compound described in JP-A-2003-39586 can be used in combination with the binder. The reactive organosilicon compound is used in the range of 10 to 100% by weight with respect to the total of the ionizing radiation curable resin and the reactive organosilicon compound. In particular, when the ionizing radiation curable organosilicon compound (3) below is used, it is possible to form a conductive layer using only this as a resin component.

(1) Silicon alkoxide is a compound represented by RmSi (OR ') n, wherein R and R' represent an alkyl group having 1 to 10 carbon atoms, and m and n are integers such that m + n = 4, respectively. . For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyl tributoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl ethoxy silane, dimethyl methoxy silane, dimethyl propoxy silane, dimethyl butyl Kishishiran, methyldimethoxysilane, methyldiethoxysilane, hexyl trimethoxysilane.

(2) Silane coupling agent For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxy Silane, aminosilane, methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3 (Trimethoxysilyl) propyl] ammonium chloride, methyl trichlorosilane, dimethyl dichlorosilane, and the like.

(3) Ionizing radiation curable silicon compound A plurality of groups that undergo reactive crosslinking by ionizing radiation, for example, organosilicon compounds having a molecular weight of 5,000 or less having a polymerizable double bond group. Such reactive organosilicon compounds may be one end vinyl functional polysilane, both end vinyl functional polysilane, one end vinyl functional polysiloxane, both end vinyl functional polysiloxane, or a vinyl functionality obtained by reacting these compounds. Examples include polysilane, vinyl functional polysiloxane, and the like.

  Examples of other compounds include (meth) acryloxysilane compounds such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldimethoxysilane.

  In order to further develop the antistatic function, it is also preferable to disperse conductive particles in the light diffusion layer and to have a function as an anisotropic conductive film as disclosed in JP-A-2003-39586. .

[Transparent support]
The transparent support for the optical film is preferably a plastic film. Examples of the polymer that forms the plastic film include cellulose acylate (eg, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, typically TAC-TD80U, TD80UL, etc. manufactured by Fuji Film), polyamide , Polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON Corporation), etc. Is mentioned. Among these, triacetyl cellulose, polyethylene terephthalate, norbornene resin, and amorphous polyolefin are preferable, and triacetyl cellulose is particularly preferable.

  Cellulose acylate consists of a single layer or a plurality of layers. A single-layer cellulose acylate is prepared by drum casting or band casting disclosed in JP-A No. 7-11055 and the like. The latter cellulose acylate comprising a plurality of layers is a feature of the published patent publication. It is prepared by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) with various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent, and a peeling accelerator is added to the horizontal endless as necessary. When casting by a dope supply means (called a die) on a support composed of a metal belt or a rotating drum, a single dope is cast in a single layer if it is a single layer, and a high concentration in the case of multiple layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

  A typical solvent for dissolving the cellulose acylate is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).

  The cellulose acylate film (a film made of triacetyl cellulose or the like) and a method for producing the same are described in JIII Journal of Technical Disclosure No. 2001-1745 (issued on March 15, 2001).

Although the thickness of a support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers. In consideration of handling suitability, coating suitability, etc., about 80 μm is preferable, but from the viewpoint of thinning of the display device, there is a great need for thinning the polarizing plate, and from the viewpoint of thinning the polarizing plate, about 40 μm to 60 μm is preferable. When such a thin cellulose acylate film is used as a transparent support for an optical film, the above-mentioned handling is achieved by optimizing the solvent, film thickness, cross-linking shrinkage ratio, etc. of the layer directly applied to the cellulose acylate film. It is preferable to avoid problems such as application suitability.
Any width of the support can be used, but from the viewpoint of handling, yield, and productivity, a width of 100 to 5000 mm is usually used, preferably 800 to 3000 mm, and preferably 1000 to 2000 mm. More preferably.
Any length of the support can be used, but from the viewpoint of handling, yield, and productivity, a length of 100 to 10,000 m is usually used, preferably 300 to 5000 m, and preferably 500 to 3000 m. More preferably it is.

[About other layers]
Other layers that may be provided between the transparent support and the light diffusing layer include other light diffusing layers (when the light diffusing layer alone is insufficient in hardness), moisture-proof layer, adhesion improving layer, and rainbow unevenness (interference unevenness). Examples include a prevention layer. These layers can be formed by a known method.

1 is a schematic cross-sectional view of a liquid crystal display device for explaining an embodiment of the present invention. FIG. 2 is a plan view of a main part of the liquid crystal display device shown in FIG. 1. It is AA sectional drawing of FIG. It is a top view of a color filter. It is a schematic diagram showing the imaging | photography method of the ceiling illumination reflected in a liquid crystal display device. It is explanatory drawing which shows an example of a captured image. It is sectional drawing which shows the layer structure of an antireflection film (AR film). A graph (a) showing an intensity distribution of a relative luminance of a liquid crystal display device in which an AR film is attached to the surface of the liquid crystal panel, and an AR film is attached to the surface of the liquid crystal panel and an antireflection film is provided on the conductive layer of the electrode. It is a graph (b) which shows intensity distribution of the relative luminance of a liquid crystal display device. It is sectional drawing which shows typically the laminated constitution of an anti-glare film (AGLR film). The graph (a) showing the intensity distribution of the relative luminance of the liquid crystal display device in which the AGLR film is attached to the surface of the liquid crystal panel, the AGLR film is attached to the surface of the liquid crystal panel, and the antireflection film is provided on the conductive layer of the electrode It is a graph (b) which shows intensity distribution of the relative luminance of a liquid crystal display device. It is the graph which took the average film thickness / average particle ratio of the light-diffusion layer on the horizontal axis, and took anti-glare property on the vertical axis. It is sectional drawing which shows the mode (a)-(c) of distribution of the translucent particle | grain with respect to the average thickness of a light-diffusion layer. It is sectional drawing of the optical film which consists of a support body / light-diffusion layer / high refractive index layer / low refractive index layer. It is sectional drawing of the optical film which consists of a support body / light-diffusion layer / medium refractive index layer / high refractive index layer / low refractive index layer. It is sectional drawing of the optical film which provided the light-diffusion layer on the hard-coat layer. It is sectional drawing of the optical film which formed the glare-proof layer by the shaping of the surface by methods, such as embossing. It is sectional drawing which shows typically layer structure (a), (b) of another anti-glare film (AGLR film). (A) And (b) is sectional drawing which shows typically the aspect of the optical film which does not provide a low refractive index layer. (A) And (b) is a figure which shows an example of the measuring method of the angle dependence of reflected light intensity at the time of scattering coefficient A calculation. It is a schematic diagram of an example of a graph showing the relative reflectance dRrel (θ) with respect to the angle θ of the light receiving unit and calculation of | dRrel (θ) / dθ | _max . It is a figure which shows the relationship between the reflection coefficient B, the scattering coefficient A, and 5 degree specular reflectance Rs. It is a correlation diagram of relative luminance and position in a conventional AG film mounted liquid crystal display device.

Explanation of symbols

10 LCD panel 11 Lower substrate (transparent substrate)
13 Upper substrate (transparent substrate)
DESCRIPTION OF SYMBOLS 15 Liquid crystal layer 17 Pixel electrode 19 Common electrode 20 Backlight 21 Phase difference film 23 Polarizing plate 25 Phase difference film 27 Polarizing plate 29 Optical function film 31 Polarizing film 33, 34 Transparent protective film 35 Switching element 37 Gate signal line 39 Source signal line 41 Gate electrode 43 Source electrode 45 Gate insulating film 46 Channel layer 47 Contact hole 49 Drain electrode 51 Protective film 53 Antireflection film 55 Ceiling illumination 57 Two-dimensional luminance meter 59 Fluorescent lamp image 61 Captured image 65 AR film 67 Transparent support 69 Low Refractive index layer 71 Light refractive index layer 73 Medium refractive index layer 75 Hard coat layer 79 Anti-glare film 81 Transparent support 83 Light diffusion layer 84 High refractive index layer 85 Low refractive index layer 86 Medium refractive index layer 87 Translucent particle 88 Hard coat layer 91 Overcoat layer 100 liquid Crystal Display Device CF Color Filter Layer CF1, CF2, CF3 Color Filter

Claims (8)

A liquid crystal panel having a liquid crystal layer sandwiched between a pair of transparent substrates and a polarizing plate disposed on the outside of the pair of transparent substrates, and disposed on at least one side of the liquid crystal panel to suppress reflection of external light An active function type liquid crystal display device, wherein switching elements for driving the liquid crystal layer are arranged in a matrix on the inner surface of one of the pair of transparent substrates,
At least one of a conductive film forming a gate signal line to which a driving signal for driving the switching element is input and a conductive film forming a source signal line to which a display signal to the liquid crystal panel is input A liquid crystal display device in which an antireflection film is formed on the film. The liquid crystal display device according to claim 1,
The liquid crystal display device, wherein the antireflection film is one of a light-transmitting oxide film and a light-transmitting nitride film. The liquid crystal display device according to claim 2,
A liquid crystal display device, wherein the oxide film includes a chromium oxide film. The liquid crystal display device according to claim 2,
A liquid crystal display device, wherein the nitride film includes a tantalum nitride film. A liquid crystal display device according to any one of claims 1 to 4,
A liquid crystal display device in which the antireflection film is laminated in a multilayer shape. A liquid crystal display device according to any one of claims 1 to 5,
The liquid crystal panel has a color filter formed in a number of lands corresponding to the switching element on the transparent substrate, and a light-shielding black matrix that fills the gaps between the adjacent color filters, A liquid crystal display device in which an antireflection film is formed at least on the arrangement region of the color filter excluding a light shielding region by the black matrix. The liquid crystal display device according to any one of claims 1 to 6,
A liquid crystal display device, wherein the optical functional film is a thin film interference type antireflection film. The liquid crystal display device according to any one of claims 1 to 6,
A liquid crystal display device, wherein the optical functional film is a light diffusion film having a light diffusion layer.

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