JP2005070435A - Manufacturing method for antidazzle antireflection coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To impart antidazzle characteristic to antireflection coating with simple configuration. <P>SOLUTION: A hard coat layer 12 is formed on a transparent support 11 composed of cellulose triacetate and embossed to form fine irregularities. A middle refractive index layer 13a, a high refractive index layer 13b and a low refractive index layer 13c are sequentially applied and dried on a surface where the fine irregularities is formed so as to form an antireflection layer 13. When the respective refractive index layers 13a to 13c are applied and dried, they are controlled to be dried so that coating film thickness may be constant along the irregularities with their coating surfaces downward by an infrared heater. By forming the coating 13 on the fine irregular surface by a coating method, mass-production is realized to reduce cost. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing an antiglare antireflection film used for optical applications and the like.

  The anti-glare antireflection film is provided in various image display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), and a cathode ray tube display (CRT). It is also used for glasses and camera lenses.

  Various methods for producing such an antiglare antireflection film have been proposed. For example, in order to realize an anti-glare antireflection film, a uniform film is laminated by vapor deposition on a support provided with irregularities as in Patent Document 1, and a smooth support as in Patent Document 2. For example, a film laminated on the body by coating, for example, forming surface irregularities by embossing, or a technique for forming irregularities by particles using a coating liquid containing particles in the surface layer as in Patent Document 3 is proposed. ing.

JP 2000-214302 A JP 2000-275404 A JP 2002-82207 A

  Although what is shown by the said patent document 1 is advantageous for uniform film formation since it is based on a vapor deposition method, there exists a problem that an apparatus cost becomes high, there exists a problem in productivity, and it is unsuitable for mass production. . Moreover, although what is shown by patent document 2 forms the unevenness | corrugation by embossing after forming an anti-reflective film by the coating method etc., although there is no problem like a vapor deposition method, it is uneven | corrugated There is a problem that the formation of is very difficult. This is because the anti-reflection film has a hard coat layer formed on the base material for imparting scratch resistance, and this layer makes it difficult to dent, This is because a phenomenon of returning even if it is temporarily recessed occurs. Moreover, as shown in Patent Document 3, when using a coating liquid containing particles in the surface layer to form irregularities with particles, it is necessary to embed particles of 1 μm or more in the coating layer thickness of 0.3 μm or less. In addition to the problem of powder falling off of the particles, there is a problem that the antireflection property is also lowered.

  As a result of diligent research on the conventional method, the present inventor has obtained an antiglare antireflection at a low cost and at a high speed by laminating an antireflection layer by a coating method on a support provided with irregularities in advance. It was noted that a film could be created. However, by simply using the conventional coating technique, when an antireflection layer is coated on a support having unevenness, the coating liquid flows from the convex portion to the concave portion on the surface, thereby causing a leveling problem. Therefore, there is a problem that unevenness occurs in the coating layer, and the antireflection function is remarkably lowered as compared with coating on a smooth surface. In order to solve the problem of leveling, Japanese Patent Application Laid-Open No. 2000-157923 proposes a technique for quickly drying a coating layer, and discloses that the progress of leveling is delayed. However, even if this rapid drying technique is used, the coating layer thickness unevenness due to leveling cannot be completely eliminated, and there is a problem that the coating layer thickness accuracy required for the antireflection film is insufficient. .

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for producing an antiglare antireflection film that can be produced easily and at high speed by a coating method.

  In order to achieve the above object, in the present invention, a concavo-convex forming step for forming concavo-convex on the surface of a substrate, and a coating liquid constituting an antireflection film is applied to the surface on which the concavo-convex is formed, and the coating layer is dried. And a coating / drying step of controlling the conditions to make the thickness of the coating layer substantially constant. Further, in the present invention, a coating process for applying a hard coat layer or a hard coat layer and an antiglare layer to a base material, and forming irregularities on the surface of the hard coat layer or antiglare layer applied in the coating process. And a coating / drying step in which a coating liquid constituting an antireflection film is applied to the surface on which the unevenness is formed, and the drying condition of the coating layer is controlled to make the thickness of the coating layer substantially constant. It is characterized by.

  In the coating and drying step, it is preferable to dry the coating layer with the coating layer facing downward. Moreover, in the said uneven | corrugated formation process, it is preferable to form the said unevenness | corrugation through the roll with an unevenness | corrugation on the surface, and to harden the said hard-coat layer or a glare-proof layer, or ionizing radiation hardening next. Furthermore, in the unevenness forming step, after the hard coat layer or the antiglare layer is applied, the hard coat layer or the antiglare layer may be cured by heat or ionizing radiation through a roll having an uneven surface. Good. Further, when applying the hard coat layer or the antiglare layer, it is preferable that fine particles are mixed into the hard coat layer coating solution or the antiglare layer coating solution, and surface irregularities are formed by the fine particles after the coating layer is dried. .

  The uneven shape preferably has an average uneven period (average unevenness interval (Sm)) of 2 μm to 100 μm, and an arithmetic average roughness (Ra) of 0.02 μm to 2 μm. Moreover, the shape of the unevenness is such that the average unevenness period is 2 μm or more and 100 μm or less and the arithmetic average roughness is 0.02 μm or more and 2 μm or less in any of the hard coat layer, the antiglare layer, and the coating layer. It is particularly preferred.

  In the drying in the coating and drying step, it is preferable to quickly dry using any one or more of an infrared heater, microwave, low dew point, and reduced pressure. Moreover, it is preferable to perform application | coating in the said application | coating drying process by either roll coating, reverse roll coating, gravure coating, reverse gravure coating, micro gravure coating, bar coating, and die coating. It is preferable that the base material is a long transparent polymer film, and the unevenness forming step and the coating and drying step are performed while continuously conveying the film. Furthermore, the transparent polymer film preferably contains cellulose acylate.

  According to the present invention, the unevenness is formed on the surface of the substrate, the coating liquid constituting the antireflection film is applied to the surface where the unevenness is formed, and the drying condition of the coating layer is controlled to control the thickness of the coating layer. Since the thickness is substantially constant, an antireflection film having antiglare properties can be easily produced by coating. In addition, mass production is possible, and manufacturing costs can be reduced. By using such an antiglare antireflection film, it is possible to prevent reflection of external light on the image display surface of the image display device and to suppress reflection of the background. In addition, the present invention is effective for providing high antireflection properties and antiglare properties in an antiglare antireflection film that requires high scratch resistance.

  In particular, unevenness is formed on the surface of the base material, and a hard coat layer or an antiglare layer is applied to the uneven surface. In this coating and drying, the surface unevenness after coating is applied to the arithmetic average roughness Ra of the surface unevenness before coating. By reducing the arithmetic average roughness Ra, the surface irregularities become smooth, irregularities with irregularities and irregularities with abrupt angle changes do not occur, the occurrence of coating film defects disappears, and the antireflection performance is impaired. It will not be done.

  Further, the present invention is effective when a hard coat layer having a high compression modulus is incorporated. Furthermore, the antiglare antireflection film of the present invention has antireflection performance, antiglare performance and high-definition suitability comparable to the antireflection film consisting of a vapor deposition layer even though the low refractive index layer is a coating layer. It can be manufactured by a simple process of embossing and coating. Therefore, it is suitable for mass production as compared with the antireflection film made of a vapor deposition layer, and the cost can be reduced. By using the antireflection film as described above, reflection of external light on the image display surface of the image display device can be effectively prevented, and at the same time, background reflection can be effectively reduced. The antiglare film obtained in the present invention is suitable as a constituent material for polarizing plates, antireflection films, and display devices.

  1A and 1B are schematic cross-sectional views showing an antiglare antireflection film produced according to the present invention. The antiglare antireflection film 10 shown in (A) is configured by sequentially providing a hard coat layer 12 and an antireflection layer 13 on a transparent support 11 as a substrate made of triacetylcellulose (TAC). Yes. Fine irregularities 14 are formed on the surface of the antireflection layer 13. Due to the light scattering by the fine irregularities 14 on the surface, the reflection of the background is reduced, so that the antiglare property is imparted. Similarly, the antiglare antireflection film 15 shown in (B) also has a hard coat layer 17, an antireflection layer 18, and fine irregularities 19 formed on the transparent support 16.

  The antireflection layers 13 and 18 have various layer structures depending on the purpose of use. The structure shown in FIG. 1 is configured in the order of medium refractive index layers 13a and 18a, high refractive index layers 13b and 18b, and low refractive index layers 13c and 18c on the hard coat layers 12 and 17. Although not shown in the drawings, the low-refractive index layers 13c and 18c are simply provided on the hard coat layers 12 and 17, or the high-refractive index layers 13b and 18b and the low-refractive index layers 13c and 18c are provided. May be good.

  In the layer structure as shown in FIG. 1, as described in JP-A-59-50401, the medium refractive index layer 13a is represented by the following formula (I), the high refractive index layer 13b is represented by the following formula (II), It is preferable that the refractive index layer 13c satisfies the following numerical formula (III) in that an antireflection film having more excellent antireflection performance can be produced.

Formula (I);
(Hλ / 4) × 0.7 <n ₃ d ₃ <(hλ / 4) × 1.3

In the formula (I), h is a positive integer (generally 1, 2 or 3), n ₃ is the refractive index of the medium refractive index layer 13a, and d ₃ is the thickness of the medium refractive index layer 13a ( nm). λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

Formula (II);
(Iλ / 4) × 0.7 <n ₄ d ₄ <(iλ / 4) × 1.3

In the formula (II), i is a positive integer (generally 1, 2 or 3), n ₄ is the refractive index of the high refractive index layer 13b, and d ₄ is the thickness of the high refractive index layer 13b ( nm). λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

Formula (III);
(Jλ / 4) × 0.7 <n ₅ d ₅ <(jλ / 4) × 1.3

In formula (III), j is a positive odd number (generally 1), n ₅ is the refractive index of the low refractive index layer 13c, and d ₅ is the layer thickness (nm) of the low refractive index layer 13c. . λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

  In the layer configuration as shown in FIG. 1, the medium refractive index layer 13a satisfies the following mathematical formula (IV), the high refractive index layer 13b satisfies the following mathematical formula (V), and the low refractive index layer 13c satisfies the following mathematical formula (VI). Is particularly preferred. Here, λ is 500 nm, h is 1, i is 2, and j is 1.

Formula (IV);
(Hλ / 4) × 0.80 <n ₃ d ₃ <(hλ / 4) × 1.00

Formula (V);
(Iλ / 4) × 0.75 <n ₄ d ₄ <(iλ / 4) × 0.95

Formula (VI);
(Jλ / 4) × 0.95 <n ₅ d ₅ <(jλ / 4) × 1.05

  In the layer structure as shown in FIG. 1, as described in JP-A-59-50401, the medium refractive index layer 13a is represented by the following formula (I), the high refractive index layer 13b is represented by the following formula (II), It is preferable that the refractive index layer 13c satisfies the following numerical formula (III) in that an antireflection film having more excellent antireflection performance can be produced.

  FIG. 2 is a flowchart showing a manufacturing process of the antiglare antireflection film 10 shown in FIG. The manufacturing process of the present invention includes a hard coat layer coating process in which a hard coat layer or a hard coat layer and an antiglare layer are applied to a substrate, and irregularities on the surface of the hard coat layer or the antiglare layer applied in this coating process. It comprises an unevenness forming step to be formed, and an application / drying step of an antireflection film coating solution for applying and drying a coating solution for forming an antireflection film on the surface on which the unevenness is formed. In this coating / drying process, the middle refractive index layer, the high refractive index layer, and the low refractive index layer are coated in that order, drying control is performed so that the film thickness becomes uniform, and the coating film is cured. Each refractive index layer is formed substantially uniformly along the surface irregularities of the coat layer without unevenness in thickness.

  The hard coat layer coating step is performed using the gravure coater 20 shown in FIG. 3, and the hard coat layer 12 is applied to the transparent support 11 as shown in FIG. Apply and dry. In addition, you may apply | coat an anti-glare layer on the hard-coat layer 12, and may dry it. This anti-glare layer is provided in the case where it becomes inconvenient in terms of formulation when fine particles are added to the hard coat layer 12, and is composed of a fine particle mixed layer separate from the hard coat layer 12. The hard coat layer 12 may be applied using a gravure coater shown in FIGS. 15 and 16 described later in addition to the gravure coater 20 shown in FIG.

  In the unevenness forming step, embossing is performed on the transparent support 11 on which the hard coat layer 12 is formed as shown in FIG. 4B, using an embossing calendar machine 30 as shown in FIG. The embossing calendar machine 30 includes an embossing roll 31 and a backup roll 32, and forms fine irregularities 12a on the surface of the hard coat layer 12, as shown in FIG. Immediately after the fine irregularities 12a are formed, the coating film is cured by the ultraviolet irradiation unit 33. By this unevenness forming step, for example, the hard coat layer 12 having fine unevenness having an arithmetic average roughness of 0.5 μm and an average unevenness period of 30 μm and an average film thickness of 9 μm is formed. The embossing roll 31 is formed by plating the surface of a cored bar made of S45C material having a diameter of 300 mm and a width of 200 mm, for example, by thermosetting to form a 50 μm hard chrome layer. Using an electric discharge machine, an embossed plate pattern having an arithmetic average roughness of 1 μm and an average unevenness period of 30 μm is formed.

  As shown in FIG. 3, the gravure coater 20 is provided with a web delivery machine 21 and a winder 22, and the transparent support 11 delivered from the web delivery machine 21 is coated with an antireflection film by the coater body 23. Liquid is applied. Thereafter, after being dried by the infrared heater 24, the transparent support 11 on which the coating film is cured by irradiating the coating film with ultraviolet rays by the ultraviolet irradiation unit 25, and the coating liquid for the antireflection coating is applied to the web winder 22 is wound up. Examples of the antireflection film coating liquid include a medium refractive index layer coating liquid, a high refractive index layer coating liquid, and a low refractive index layer coating liquid, which are sequentially coated on the hard coat layer 12.

  For example, first, the medium refractive index layer coating solution is applied by the gravure coater 20 and dried at 200 ° C. by the infrared heater 24 while keeping the coated surface facing downward, and then the ultraviolet ray is applied to the coating film by the ultraviolet irradiation unit 25. Irradiation is performed to cure the coating film to form a medium refractive index layer 13a having a film thickness of 60 nm. Thereafter, similarly, using the coater body 23, the infrared heater 24, and the ultraviolet irradiation unit 25, a coating solution for a high refractive index layer is applied onto the middle refractive index layer 13a, and the coated surface is kept downward. Then, after drying at 280 ° C. by the infrared heater 24, the coating film was cured by irradiating with ultraviolet rays to form a high refractive index layer 13b having a film thickness of 105 nm. Thereafter, a coating solution for the low refractive index layer is applied on the high refractive index layer in the same manner, and dried at 260 ° C. with the infrared heater 24 while keeping the coated surface facing downward, and then irradiated with ultraviolet rays. The coating film was cured to form a low refractive index layer having a thickness of 90 nm.

  FIG. 6 is a view for explaining the principle of making the thickness of each refractive index layer uniform in the coating and drying process of the antireflection film. (A) is a hard coat when a refractive index layer coating solution, for example, a low refractive index coating solution, is applied to the surface of the hard coat layer 41 on which fine irregularities 40 are formed and dried with the coating surface facing upward. FIG. 4 is a cross-sectional view of the layer 41 and the low refractive index layer 42 after drying. In such upward drying, the coating liquid flows in the recesses 40a and unevenness in thickness occurs in the low refractive index layer, thereby obtaining a uniform coating film. I can't. (B) represents an ideal cross section as an antiglare antireflection film, and shows a state in which the low refractive index layer 43 is uniformly applied to the surface of the hard coat layer 41. (C) is a cross-sectional view of the hard coat layer 41 and the low-refractive index layer 44 when the coated surface is dried downward, and the liquid easily flows to the convex portion 40b by gravity, and the convex portion 40b after drying. The film thickness becomes thicker.

  In order not to be in the state of (C), drying is performed with an optimum drying condition, thereby obtaining a coating film having a substantially uniform thickness along the unevenness. The optimum drying conditions vary depending on the physical properties of the coating solution, the coating thickness, and the uneven shape, but the optimum value that provides the most uniform thickness is obtained by experiments. In addition, even if the coating surface shown in (A) is dried upward, the film thickness can be made uniform by setting the drying conditions to be optimal, but the coating liquid tends to flow and accumulate on the concave portion 40a side. There is a narrower range of optimum drying conditions compared to drying with the coated surface facing downward, making it difficult to obtain a uniform film thickness.

  The drying conditions are controlled by, for example, arranging the infrared heater 24 on the coating surface immediately after coating and controlling the output of the infrared heater 24, thereby controlling the drying speed and uniforming the coating film thickness on the uneven surface. Set to the optimal drying conditions. In addition to the infrared heater 24, a microwave drying method, a low dew point drying method, a reduced pressure drying method, or the like may be employed.

  In addition to gravure coating, various coating methods such as reverse gravure coating, roll coating, reverse roll coating, micro gravure coating, bar coating, and die coating are used as the coating method of the hard coat layer 12 and the antireflection layer 13. .

  In the unevenness forming step, hot embossing was performed using an embossing calendar machine 30 as shown in FIG. 5, but instead of this, as shown in FIG. 7, the transparent support 11 is made of TAC, PET, or the like. When the hard coat layer 12 or the antiglare layer, which is a UV curable resin, is applied on the film by the coating head 50, the ultraviolet irradiation unit 52 irradiates ultraviolet rays while being wound around the embossing roll 51 having surface irregularities. Thus, irregularities may be formed on the surface of the hard coat layer or the antiglare layer.

  Further, as shown in FIG. 8, fine particles 56 are mixed in a coating liquid for a hard coat layer or an antiglare layer (not shown), and the coating liquid is applied to the transparent support 11 and dried, and then the fine particles 56 cause surface irregularities. A hard coat layer 55 or an antiglare layer may be formed.

  In addition, although the uneven | corrugated formation to the transparent support body 11 was performed by carrying out hot embossing through the film film which consists of the transparent support body 11 between the embossing roller 31 and the backup roller 32 as shown in FIG. Instead, as shown in FIG. 9, when the transparent support 60 is manufactured, a dope 63 is cast from a die 62 onto a band or drum 61 having an embossed peripheral surface, for example, and a peeling roller The surface irregularities may be formed by peeling the film with 64 to form a film. Further, as shown in FIGS. 10 and 11, when the transparent supports 66 and 67 are manufactured, the fine particles 68 and 69 are mixed into the dope and the surface is made uneven by the fine particles 68 and 69. May be. Regardless of which method is used to form irregularities, the irregular shape has an average irregularity period of 20 μm to 1000 μm, and an arithmetic average roughness of 0.2 μm to 10 μm. This is preferable.

  The anti-glare antireflection film to be incorporated in the image display device is required to have fine periodic irregularities due to the recent high definition, and in this case, the anti-glare antireflection film has 50 ppi (pixels / pixels). inch), the average asperity period is preferably 5 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and most preferably 5 μm or more and 30 μm or less.

  The size of the surface irregularities is determined by the required degree of antiglare property. If the unevenness on the surface is small, the effect of scattering the external light necessary as an antiglare film is reduced, and if the unevenness is too large, the resolution is reduced due to significant scattering, and the image is white. In the present invention, the arithmetic average roughness of the antiglare antireflection layers 13 and 18 is preferably 0.01 μm to 2 μm, more preferably 0.05 μm to 2 μm, and most preferably 0.05 μm to 1 μm.

  In the present invention, it is preferable that the inclination angle of the uneven profile is small. The inclination angle of the irregular concavo-convex profile is not unique and has a distribution, but the anti-glare antireflection films 10 and 15 may become white when the existence frequency of a large inclination angle increases. Is preferably distributed in the range of 0.5 ° to 10 °, more preferably in the range of 0.5 ° to 5 °.

  In the present embodiment, the average irregularity period, arithmetic average roughness, and average inclination angle are the two-dimensional roughness meter SJ-400 type manufactured by Mitutoyo Corporation or the micromap manufactured by Ryoka System Corporation. Although it measures using the machine, you may measure using another commercially available two-dimensional surface roughness measuring device.

  In the above embodiment, as shown in FIG. 1 (A), FIG. 2 and FIG. 3, the uneven support forming process is performed on the transparent support 11 provided with the hard coat layer 12 or the antiglare layer. As shown in FIG. 1B and FIGS. 12 to 14, after the unevenness forming process is performed on the transparent support 16, a hard coat layer, an antiglare layer, each refractive index layer, etc. May be sequentially applied and dried. FIG. 12 is a flowchart showing the manufacturing process in this embodiment. The unevenness forming step for forming unevenness on the surface of the transparent support, and the coating liquid for forming the hard coat layer and the antireflection layer on the surface on which the unevenness is formed are shown. It consists of a coating and drying step of coating and drying. In the coating and drying process, the drying condition of the coating layer is controlled so that the thickness of the coating layer is substantially constant.

  By the way, in order to provide an antireflection function, it is necessary to laminate coating films having different refractive indexes with an ultrathin dry film having a thickness of 1 μm or less, and if there is a film thickness defect, the reflection characteristics are greatly affected, and reflection Characteristics will be impaired. That is, even if there are surface irregularities, they are required to be sufficiently smooth. When forming unevenness on the surface, the embossing roll surface unevenness is transferred by pressure or UV curing through the embossing roll, but unevenness with unevenness or sudden angle change occurs There is. As a result, defects in antireflection characteristics are likely to occur when an ultrathin dry film is laminated.

  In the present embodiment, as shown in FIG. 14, a transparent support is provided so that even when such irregularities or irregularities with abrupt angle changes occur, these irregularities do not become defects in antireflection characteristics. A hard coat layer 17 having a maximum thickness larger than the height of the surface irregularities 16a of the body 16 is formed, and the shape of the surface irregularities 17a of the hard coat layer 17 is made smoother than the shape of the underlying irregularities 16a. For this reason, when the hard coat layer 17 is applied, it is meaningless if the surface unevenness 17a disappears. Therefore, the hard coat layer 17 is also dried downward, and the drying conditions are controlled so that the unevenness is lower than the underlying unevenness 16a. The coating is dried so that the desired unevenness 17a can be maintained although the height is lowered. That is, unevenness 16a having a larger amplitude than the final surface unevenness 17a is formed on the transparent support 16 in advance.

  Concavity and convexity formation on the transparent support 16 is performed by hot embossing through the TAC or PET base as the transparent support 16 between the embossing roller 31 and the backup roller 32 as shown in FIG. Further, although the hard coat layer 17 is applied to the transparent support 16, a smoothing layer that smoothes the surface irregularities is formed in place of the hard coat layer 17 but is not shown, and the smooth coating layer is formed on the smoothing layer. A hard coat layer 17 may be formed.

[Transparent support]
The transparent support 11 is preferably a plastic film. Examples of the plastic film include cellulose esters (eg, triacetylcellulose, diacetylcellulose, propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose) and polyolefins (eg, polypropylene, polyethylene, polymethylpentene, triacetylcellulose, Polyolefin is preferable for polarizing plates because of its low retardation and high optical uniformity, and triacetyl cellulose is particularly preferable when used for liquid crystal display devices.

  When the transparent support is a triacetyl cellulose film, a triacetyl cellulose solution prepared by dissolving triacetyl cellulose in a solvent (referred to as a dope) is cast by either a single layer casting method or a multi-layer co-casting method. The produced triacetyl cellulose film is preferable.

The film thickness of the transparent support 11 is not particularly limited, but the film thickness is preferably 1 to 300 μm, preferably 30 to 150 μm, particularly preferably 40 to 120 μm, and most preferably 40 to 100 μm. The light transmittance of the transparent support 11 is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support 11 is preferably 2.0% or less, and more preferably 1.0% or less (here, the haze is a haze in the sense that is usually used. It is recorded as a photographic term in the academic glossary issued by the Academic Term Council and is required by a general-purpose haze meter). The refractive index of the transparent support 11 is preferably 1.4 to 1.7. An infrared absorber or an ultraviolet absorber may be added to the transparent support 11. The addition amount of the infrared absorber is preferably 0.01 to 20% by mass of the transparent support 11 and more preferably 0.05 to 10% by mass. As a slip agent, particles of an inert inorganic compound may be added to the transparent support. Examples of the inorganic _{compound, SiO 2, TiO 2, BaSO} 4, CaCO 3, talc and kaolin.

[Inorganic fine particles]
Particles having a high refractive index for achieving a desired refractive index can be added to the middle refractive index layer 13a and the high refractive index layer 13b of the present invention. Examples of such particles include inorganic fine particles such as titanium dioxide, zirconium oxide, and aluminum oxide. Of these, titanium oxide has a particularly high refractive index and can be preferably used. However, since titanium dioxide has photocatalytic properties, it is particularly preferable to use it as inorganic fine particles mainly composed of titanium dioxide containing at least one element selected from cobalt, aluminum, and zirconium. The main component means a component having the largest content (mass%) among the components constituting the particles. The refractive index of the middle refractive index layer 13a and the high refractive index layer 13b of the present invention is 1.55 to 2.40. The inorganic fine particles mainly composed of titanium dioxide in the present invention preferably have a refractive index of 1.90 to 2.80, more preferably 2.10 to 2.80, and 2.20 to 2.80. 80 is most preferred. The primary particles of inorganic fine particles mainly composed of titanium dioxide preferably have a weight average diameter of 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 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. The crystal structure of the inorganic fine particles containing titanium dioxide as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

[Dispersant]
A dispersant can be used for dispersing inorganic fine particles mainly composed of titanium dioxide used for the medium refractive index layer 13a and the high refractive index layer 13b of the present invention. In order to disperse the inorganic fine particles mainly composed of titanium dioxide of the present invention, it is particularly preferable to use a dispersant having an anionic group. As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (and a sulfo group), a phosphoric acid group (and a phosphono group), or a sulfonamide group, or a salt thereof is effective. A sulfonic acid group, a phosphoric acid group and a salt thereof are preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. The number of anionic groups contained in the dispersant per molecule may be one or more. A plurality of anionic groups may be contained for the purpose of further improving the dispersibility of the inorganic fine particles. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.

  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. A preferred dispersant used for dispersion of inorganic fine particles mainly composed of titanium dioxide used in the high refractive index layer of the present invention has an anionic group and a crosslinkable or polymerizable functional group, and the crosslinkable or polymerizable functional group. In the side chain. 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 preferred weight average molecular weight (Mw) of the dispersant is 2,000 to 1,000,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000.

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

[Medium Refractive Index Layer 13a and High Refractive Index Layer 13b and Forming Method]
The inorganic fine particles used for the medium refractive index layer 13a and the high refractive index layer 13b are used for forming the medium refractive index layer 13a and the high refractive index layer 13b in a dispersion state. In the dispersion of the inorganic fine particles, it is dispersed in a dispersion medium in the presence of the dispersant. As the dispersion medium, 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 preferred. Particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The inorganic fine 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. The inorganic fine particles are preferably made as fine as possible in the dispersion medium, and the weight 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. By refining the inorganic fine particles to 200 nm or less, it is possible to form the middle refractive index layer 13a and the high refractive index layer 13b that do not impair the transparency.

  The medium refractive index layer 13a and the high refractive index layer 13b used in the present invention are preferably a binder precursor (for example, necessary for matrix formation), for example, in a dispersion liquid in which inorganic fine particles are dispersed in a dispersion medium as described above. Ionizing radiation curable polyfunctional monomers and polyfunctional oligomers described later), a photopolymerization initiator, etc. are added to form a coating composition for forming a medium refractive index layer and a high refractive index layer, and a medium refractive index on a transparent support. The coating composition for forming the layer and the high refractive index layer is preferably applied and cured 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 of the medium refractive index layer 13a and the high refractive index layer 13b to undergo a crosslinking reaction or a polymerization reaction with the dispersing agent at the same time as or after the coating of the layer. The binder of the medium refractive index layer 13a and the high refractive index layer 13b produced in this way is, for example, a crosslinking or polymerization reaction between the preferable dispersant and an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer, It becomes a form in which the anionic group of the dispersant is incorporated in the binder. Further, the binder of the medium refractive index layer 13a and the high refractive index layer 13b 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, thereby forming the inorganic fine particles. Improves the physical strength, chemical resistance and weather resistance of the medium refractive index layer 13a and the high refractive index layer 13b.

  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, 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, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like.

  Two or more polyfunctional monomers may be used in combination. 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. Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.

  As a commercially available photo radical polymerization initiator, 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 Geigy Japan, Ltd., Esacure (KIP100F, KB1, EB3, BP, X33, KT046) manufactured by Sartomer , KT37, KIP150, TZT).

  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 Geigy Japan.

  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. 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 coating and drying of the medium refractive index layer 13a and the high refractive index layer 13b.

  The inorganic fine particles have a function of controlling the refractive index of the medium refractive index layer 13a and the high refractive index layer 13b and a function of suppressing curing shrinkage. In the medium refractive index layer 13a and the high refractive index layer 13b, the inorganic fine particles are preferably dispersed as finely as possible, and the weight average diameter is 1 to 200 nm. The weight average diameter of the inorganic fine particles in the medium refractive index layer 13a and the high refractive index layer 13b is preferably 5 to 150 nm, more preferably 10 to 100 nm, and most preferably 10 to 80 nm. By refining the inorganic fine particles to 200 nm or less, it is possible to form the middle refractive index layer 13a and the high refractive index layer 13b that do not impair the transparency.

  The content of the inorganic fine particles in the medium refractive index layer 13a and the high refractive index layer 13b is preferably 10 to 90% by mass, more preferably 15 to 15% by mass with respect to the mass of the medium refractive index layer 13a and the high refractive index layer 13b. 80% by mass, particularly preferably 15 to 75% by mass. Two or more kinds of inorganic fine particles may be used in combination in the medium refractive index layer 13a and the high refractive index layer 13b. When the low refractive index layer 13c is provided on the middle refractive index layer 13a and the high refractive index layer 13b, the refractive index of the middle refractive index layer 13a and the high refractive index layer 13b is preferably higher than the refractive index of the transparent support. In the medium refractive index layer 13a and the high refractive index layer 13b, 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.), S, N Binders obtained by crosslinking or polymerization reactions such as ionizing radiation curable compounds containing atoms such as, P can also be preferably used. In order to construct the antireflective film by constructing the low refractive index layer 13c on the medium refractive index layer 13a and the high refractive index layer 13b, the refractive index of the medium refractive index layer 13a and the high refractive index layer 13b is 1. It is preferably .55 to 2.40, more preferably 1.60 to 2.20, still more preferably 1.65 to 2.10, and most preferably 1.80 to 2.00.

  For the medium refractive index layer 13a and the high refractive index layer 13b, in addition to the above components (inorganic fine particles, polymerization initiator, photosensitizer, etc.), resin, surfactant, antistatic agent, coupling agent, thickener Agent, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, ultraviolet absorber, infrared absorber, adhesion promoter, polymerization inhibitor, antioxidant, surface modifier, conductive Metal fine particles can be added. Further, the middle refractive index layer 13a and the high refractive index layer 13b can also serve as an antiglare layer that contains particles having an average particle size of 0.2 to 10 μm described later and has an antiglare function. The film thicknesses of the medium refractive index layer 13a and the high refractive index layer 13b can be appropriately designed depending on the application.

  In the formation of the middle refractive index layer 13a and the high refractive index layer 13b, it is preferable to carry out the crosslinking reaction or polymerization reaction of the ionizing radiation curable compound in an atmosphere having an oxygen concentration of 10% by volume or less. By forming the medium refractive index layer 13a and the high refractive index layer 13b in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, weather resistance of the medium refractive index layer 13a and the high refractive index layer 13b, Can improve the adhesion between the medium refractive index layer 13a and the high refractive index layer 13b and the adjacent layers. 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. Preferred coating solvents for the medium refractive index layer 13a and the high refractive index layer 13b are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. The coating solvent may contain a solvent other than the ketone solvent. For example, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic carbonization Hydrogen (eg, hexane, cyclohexane), halogenated hydrocarbon (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), and ether alcohol (eg, 1-methoxy-2-propanol).

  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. The strength of the medium refractive index layer 13a and the high refractive index layer 13b 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. The more preferable. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. The medium refractive index layer 13a and the high refractive index layer 13b are preferably constructed directly on the transparent support or via other layers.

[Low refractive index layer]
In the present invention, the low refractive index layer 13c is 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. The copolymer-derived component preferably occupies 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. From the viewpoint of compatibility between low refractive index and film hardness, and compatibility, a form of adding a curing agent such as polyfunctional (meth) acrylate is not preferable.

  The refractive index of the low refractive index layer 13c is preferably 1.20 to 1.49, more preferably 1.20 to 1.45, and particularly preferably 1.20 to 1.44. . The thickness of the low refractive index layer 13c is preferably 50 to 400 nm, and more preferably 50 to 200 nm. The haze of the low refractive index layer 13c 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 13c is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test under a 1 kg load. 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.

  The copolymer used for the low-refractive-index layer of this invention is demonstrated below. Fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (eg, biscoat) 6FM (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), M-2020 (trade name, manufactured by Daikin), etc., and fully or partially fluorinated vinyl ethers, and the like are preferable. From the viewpoints of properties, transparency, availability, etc., hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, the fluorine-containing vinyl monomer is preferably introduced 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%. This is a case of mass%.

  The copolymer of the present invention has a repeating unit having a (meth) acryloyl group in the side chain as an essential component. The method for introducing the (meth) acryloyl group into the copolymer is not particularly limited. For example, (1) after synthesizing a polymer having a nucleophilic group such as a hydroxyl group or an amino group, (meth) acrylic acid A method in which chloride, (meth) acrylic anhydride, (meth) acrylic acid and methanesulfonic acid mixed acid anhydride, etc. are allowed to act, (2) the polymer having the nucleophilic group in the presence of a catalyst such as sulfuric acid ( (3) a method of allowing methacrylic acid to act, (3) a method of causing a compound having both an isocyanate group such as methacryloyloxypropyl isocyanate and (meth) acryloyl group to act on the polymer having the nucleophilic group, and (4) a polymer having an epoxy group. (5) A method in which (meth) acrylic acid is allowed to act after synthesis of (5) a polymer having a carboxyl group and an epoxy group such as glycidyl methacrylate ( Method of reacting a compound having both an acryloyl group, and a method of performing dehydrochlorination after obtained by polymerizing a vinyl monomer having a (6) 3-chloropropionic acid ester moiety. Among these, in the present invention, it is particularly preferable to introduce a (meth) acryloyl group by the method (1) or (2) for a polymer containing a hydroxyl group.

  If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. 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.

  In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate 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%. Is particularly preferably in the range of 0 to 30 mol%.

  The composition for forming a low refractive index layer of the present invention is usually in the form of a liquid, and the copolymer is an essential constituent, and various additives and a radical polymerization initiator are dissolved in an appropriate solvent as necessary. Produced. 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. %.

  As described above, it is not always advantageous to add an additive such as a curing agent from the viewpoint of the film hardness of the low refractive index layer 13c, but interfacial adhesion between the medium refractive index layer 13a and the high refractive index layer 13b, etc. In view of the above, a curing agent such as a polyfunctional (meth) acrylate compound, a polyfunctional epoxy compound, a polyisocyanate compound, an aminoplast, a polybasic acid or an anhydride thereof, or a small amount of inorganic fine particles such as silica can be added. When adding these, it is preferable that it is the range of 0-30 mass% with respect to the total solid of a low refractive index layer film | membrane, It is more preferable that it is the range of 0-20 mass%, 0-10 mass % Range is particularly preferred.

  In addition, for the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, known silicone-based or fluorine-based antifouling agents, slipping agents, and the like can be appropriately added. When these additives are added, it is preferably added in the range of 0 to 20% by mass of the total solid content of the low refractive index layer, more preferably in the range of 0 to 10% by mass. Particularly preferred is 0 to 5% by mass.

  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.

  When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays. 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 any amount that can initiate polymerization of a carbon-carbon double bond, but in general, the total amount in the composition for forming a low refractive index layer is not limited. 0.1-15 mass% is preferable with respect to solid content, More preferably, it is 0.5-10 mass%, Most preferably, it is a case of 2-5 mass%.

  The solvent contained in the low refractive index layer coating liquid composition is not particularly limited as long as the composition containing the fluorine-containing copolymer is uniformly dissolved or dispersed without causing precipitation. A solvent can also be used in combination. 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.

  The low refractive index layer 13c contains a filler (for example, inorganic fine particles and organic fine particles), a silane coupling agent, a slipping agent (silicone compound such as dimethyl silicone), a surfactant and the like in addition to the fluorine-containing compound. Can do. In particular, it is preferable to contain inorganic fine particles, a silane coupling agent, and a slip agent.

  As the inorganic fine particles, silicon dioxide (silica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride) and the like are preferable. Particularly preferred is silicon dioxide (silica). The primary particles of the inorganic fine particles preferably have a weight average diameter of 1 to 150 nm, more preferably 1 to 100 nm, and most preferably 1 to 80 nm. It is preferable that the inorganic fine particles are more finely dispersed in the outermost layer. The shape of the inorganic fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape, a short fiber shape, a ring shape, or an indefinite shape.

  The low-refractive index layer 13c is a crosslinking reaction caused by light irradiation, electron beam irradiation, or heating at the same time as or after application of a coating composition in which a fluorine-containing compound and other optional components contained therein are dissolved or dispersed. Alternatively, it is preferably formed by a polymerization reaction. In particular, when the low refractive index layer 13c is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction may be performed in an atmosphere having an oxygen concentration of 10% by volume or less. preferable. 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.

[Hard coat layer]
The hard coat layer is provided on the surface of the transparent support in order to impart physical strength to the antireflection film. In particular, it is preferably provided between the transparent support and the medium refractive index layer 13a. 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.

  Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include those exemplified in the middle refractive index layer 13a and the high refractive index layer 13b, and a photopolymerization initiator and a photosensitizer are used. Polymerization is preferred. The photopolymerization reaction is preferably performed by ultraviolet irradiation after the hard coat layer is applied and dried. The hard coat layer is preferably added with inorganic fine particles having an average particle diameter of 0.001 to 0.1 μm for imparting the physical strength. Specific examples of the inorganic particles include particles such as silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide, tin oxide, ITO, zinc oxide, and calcium carbonate. Since light scattering is reduced as the refractive index difference with the binder is smaller, silicon dioxide and aluminum oxide are preferably used. The addition amount is preferably about 5 to 50 weight percent. If the amount is too large, brittleness is insufficient, and if the amount is too small, the effect of adding inorganic fine particles is insufficient.

  The hard coat layer is preferably added with an oligomer and / or polymer having a weight average molecular weight of 500 or more in order to impart brittleness depending on the application. 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 content of the oligomer and / or polymer in the hard coat layer is preferably 5 to 50% by mass, more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass with respect to the total mass of the hard coat layer. It is. As described above, the medium refractive index layer 13a can also serve as a hard coat layer. In the case where the medium refractive index layer 13a also serves as a hard coat layer, it is preferable to form by dispersing fine particles of inorganic fine particles having a high refractive index in the hard coat layer using the method described in the medium refractive index layer 13a. .

  The hard coat layer can also serve as an antiglare layer to which an antiglare function is imparted by containing particles having an average particle size of 0.2 to 10 μm, which will be described later. The film thickness of the hard coat layer can be appropriately designed depending on the application. The film thickness of the hard coat layer is preferably 0.2 to 10 μm, more preferably 1 to 9 μm, and particularly preferably 5 to 8 μm.

  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 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, a hard coat layer excellent in physical strength and chemical resistance can be formed. 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 middle refractive index layer 13a and the high refractive index layer 13b. By using the ketone solvent, the adhesion between the surface of the transparent support (particularly, the triacetyl cellulose 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 middle refractive index layer 13a and the high refractive index layer 13b. 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.

[Saponification]
(1) Immersion method This is a technique in which 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 N, particularly preferably 1 to 2 N. 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 with water on the surface of the transparent support opposite to the side having the medium refractive index layer 13a and the high refractive index layer 13b, the more preferable in terms of adhesiveness to the polarizing film. In the dipping method, the surface having the medium refractive index layer 13a and the high refractive index layer 13b is damaged by alkali at the same time. Therefore, it is important to set the necessary minimum reaction conditions. When the contact angle to water of the support on the opposite surface is used as an index of damage received by the antireflection layer due to alkali, particularly when the support is triacetylcellulose, it is preferably 20 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 the angle is less than 20 degrees, the damage received by the antireflection film is too large, and physical strength and light resistance are impaired.

(2) Alkaline liquid application method As a means for avoiding damage to the antireflection film in the above-described immersion method, the alkaline liquid is applied only on 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 alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, peeling, etc. caused by alkali solution, so it is not desirable to use the immersion method, but this coating method does not contact the solution and should be used without problems. Is possible.

  In any of the saponification methods (1) and (2) above, since each layer can be formed by unwinding from a roll-shaped support, a series of operations can be performed in addition to the above-described antireflection film production process. You can go. 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.

  When the antireflection layers 13 and 18 in the production method of the present invention are used as one side of the surface protective film of the polarizer, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), It can be preferably used for transmissive, reflective, or transflective liquid crystal display devices such as in-plane switching (IPS) and optically compensated bend cells (OCB). Further, an optical compensation film such as a viewing angle widening film for improving the viewing angle of the liquid crystal display device, a retardation plate, and the like can be used in combination. When used in a transmissive or transflective liquid crystal display device, it is used in combination with a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, such as D-BEF manufactured by Sumitomo 3M Co., Ltd.). Thus, a display device with higher visibility can be obtained.

  Moreover, it can use for the objective of reducing the reflected light from the surface and an inside as a surface protection board for organic EL displays by combining with (lambda) / 4 board. Furthermore, the antireflection layer of the present invention is formed on a transparent support such as PET or PEN, and can be applied to an image display device such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto. A hard coat layer coating solution was applied to a TAC film having a thickness of 80 μm (trade name; TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) using the gravure coater 20 shown in FIG. 3 and dried at 100 ° C. for 2 minutes. Next, using the embossing calender machine (manufactured by Yuri Roll Co., Ltd.) shown in FIG. 5 on the coated surface, the embossing roll 31 and the embossing roll 31 under conditions of a wire thickness of 6000 N / cm, an embossing roll temperature of 100 ° C., and a conveying speed of 1 m / min. A press operation was performed with the backup roll 32, and immediately thereafter, the ultraviolet irradiation unit 33 was irradiated to cure the coating film. Thereby, a hard coat layer (average film thickness: 9 μm) having irregularities with an average irregularity period of 30 μm and an arithmetic average roughness of 0.5 μm was formed. As the embossing roll 31, the surface of a cored metal roll made of an S45C material having a diameter of 300 mm and a width of 200 mm was plated to obtain a hard chromium layer having a thickness of 50 μm. What was surface-treated using the engraving electric discharge machine EA8 type was used, and the embossed plate pattern of this embossing roll 31 had an average unevenness period of 30 μm and an arithmetic average roughness of 1 μm.

  A medium refractive index layer is applied by a gravure coater 20 shown in FIG. 3 to a transparent support having an uneven shape formed by an embossing roll 31, and dried to 200 ° C. by an infrared heater 24 while keeping the coated surface facing downward. After that, the coating film was cured by irradiating with ultraviolet rays to obtain a medium refractive index layer 13a having a film thickness of 60 nm. Next, a coating solution for a high refractive index layer is applied onto the middle refractive index layer 13a, and after drying at 280 ° C. by an infrared heater 24 with this coating surface kept downward, the coating is performed by irradiating with ultraviolet rays. The film was cured to form a high refractive index layer 13b having a thickness of 105 nm. Thereafter, a coating solution for a low refractive index layer is applied on the high refractive index layer 13b, and the coating surface is kept downward and dried at 260 ° C. by an infrared heater 24. The film was cured to form a low refractive index layer 13c having a thickness of 90 nm. These drying conditions are optimally set in order to obtain the uniformity of the thickness of the applied film.

  Surface irregularities are formed on an TAC film having a thickness of 80 μm by an embossing calendar machine 30 shown in FIG. The hot embossing at this time was performed under the same conditions except that the embossed plate pattern of Example 1 and the embossing roll 31 were different. The embossing plate pattern of the embossing roll 31 was one having an average irregularity period of 30 μm and an arithmetic average roughness of 1 μm.

  The hard coat layer coating solution is applied to the film with the irregularities using the gravure coater 20 shown in FIG. 3, and dried at 100 ° C. for 2 minutes with the coating surface kept downward, and the film thickness is 6 μm. A hard coat layer was obtained. Further, a medium refractive index layer was applied by the gravure coater 20, and similarly, the coated surface was kept downward, dried at 200 ° C. by the infrared heater 24, then irradiated with ultraviolet rays to cure the coating film, and the film thickness was 60 nm. A medium refractive index layer was obtained. A coating solution for a high refractive index layer is applied onto the middle refractive index layer using the gravure coater 20, dried at 280 ° C. by the infrared heater 24, then irradiated with ultraviolet rays to cure the coating film, and the film thickness is 105 nm. The high refractive index layer was provided. Further, a low refractive index layer coating solution is applied onto the high refractive index layer using the gravure coater 20, dried at 260 ° C. by the infrared heater 24, and then irradiated with ultraviolet rays to cure the coating film. A low refractive index layer having a thickness of 90 nm was provided. In this way, an antiglare antireflection film was produced. These drying conditions are optimally set in order to obtain the uniformity of the thickness of the applied film.

  The hard coat layer coating solution, titanium dioxide fine particle dispersion, medium refractive index layer coating solution, high refractive index layer coating solution, and low refractive index layer coating solution were prepared as follows.

(Preparation of coating solution for hard coat layer)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 230 parts by weight, ethylene oxide modified trimethylolpropane triacrylate (Biscoat 360, Osaka Organic Chemical Co., Ltd.) 76 Parts by weight, 181 parts by weight of methyl ethyl ketone, 55 parts by weight of cyclohexanone, 8 parts by weight of a photopolymerization initiator (Irgacure 184, manufactured by Nippon Ciba-Geigy Co., Ltd.), and 450 parts by weight of silica sol (MEK-ST, manufactured by Nissan Chemical Co., Ltd.) Added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

(Preparation of titanium dioxide fine particle dispersion)
As titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO2: Co3O4: Al2O3: ZrO2 = containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide = 90.5: 3.0: 4.0: 0.5 weight ratio). To this particle 257.1 g, 38.6 g of a dispersing agent (KAYARAD PM-21, Nippon Kayaku Co., Ltd.) and 704.3 g of cyclohexanone were added and dispersed by dynomill, and a titanium dioxide dispersion having a weight average diameter of 70 nm. Was prepared.

(Preparation of coating solution for medium refractive index layer)
To 88.9 g of the above titanium dioxide dispersion, 58.4 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), photopolymerization initiator (Irgacure 907, Ciba Specialty) Chemicals Co., Ltd. (3.1 g), photosensitizer (Kayacure DETX, Nippon Kayaku Co., Ltd.) 1.1 g, methyl ethyl ketone 482.4 g and cyclohexanone 1869.8 g were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution A for medium refractive index layer.

(Preparation of coating solution for high refractive index layer)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 47.9 g, photopolymerization initiator (Irgacure 907, Nippon Ciba Geigy ( 4.0 g), photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1.3 g, methyl ethyl ketone 455.8 g, and cyclohexanone 1427.8 g were added and stirred. The solution was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of coating solution for low refractive index layer)
The copolymer (P-1) according to the present invention is dissolved in methyl isobutyl ketone so as to have a concentration of 7% by mass, and a terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) is solidified. Teflon (registered trademark) having a pore diameter of 0.45 μm (absolute filtration diameter) after adding 3% by weight and 5% by mass of the photo radical generator Irgacure 907 (trade name) with respect to the solid content and sufficiently stirring. A low refractive index layer coating solution was prepared by filtration through a filter manufactured by the manufacturer.

[Comparative Example 1]
The substrate having the unevenness on the surface is configured in the same manner, and in the subsequent steps, an anti-glare antireflection film is formed in accordance with Example 1 except that the coating surface is dried upward as shown in FIG. did. Note that the gravure coater 80 shown in FIG. 15 is dried by the infrared heater 81 with the coating surface facing upward with respect to the gravure coater 20 shown in FIG. Are given the same reference numerals.
[Comparative Example 2]
The same structure is applied to the support having irregularities on the surface, and in the subsequent steps, an antiglare antireflection film is formed in accordance with Example 1 except that the coated surface is dried sideways as shown in FIG. did. The gravure coater 85 shown in FIG. 16 is dried by the infrared heater 86 with the coating surface facing upward with respect to the gravure coater 20 shown in FIG. The code | symbol is attached | subjected.

  Evaluation was carried out by the following items and methods using the thus obtained antiglare antireflection film as a sample.

(A) Evaluation of anti-glare property Each of the obtained samples was projected with a louverless exposed fluorescent lamp (8000 cd / m ² ), and the degree of blur of the reflected image of the fluorescent lamp reflected on each sample was visually observed according to the following criteria. evaluated.
Fluorescent light is blurred (with anti-glare property): ○
Fluorescent lamp is hardly blurred (insufficient anti-glare property): ×

(B) Glitter evaluation Each of the obtained samples was placed on a cell imitating 133 ppi at a distance of 1 mm, and the degree of glare (brightness variation caused by the surface convex portion of the antiglare film) was determined according to the following criteria. Visual evaluation was performed.
No glare is seen: ◎
Almost no glare seen: ○
There is slight glare: △
There is an unpleasant glare: ×

(C) Average reflectance A spectrophotometer V-550 (manufactured by JASCO Corporation) is fitted with an adapter ARV-474, and in the wavelength region of 380 to 780 nm, the mirror surface has an output angle of -5 degrees at an incident angle of 5 °. The reflectance was measured, the average reflectance at 450 to 650 nm was calculated from this data, and this value was used as the antireflection evaluation.

(D) Pencil hardness evaluation Pencil hardness evaluation according to JIS K 5400 was performed as an index of scratch resistance. Each sample was conditioned for 2 hours at a temperature of 25 ° C. and a relative humidity of 60% RH, and then, using the H-5H test pencil specified in JIS S 6006, with a load of 500 g, the following determination was made. The highest hardness that was evaluated as OK was taken as the evaluation value.
No scratch in 5 tests-1 wound: OK
3 or more scratches in 5 tests: NG

(E) The arithmetic average roughness was measured using a micromap machine (manufactured by Ryoka System Co., Ltd.) on the embossed film surface.

  The samples of Examples 1 and 2 were evaluated for (a) anti-glare property, (b) glare, (c) average reflectance, and (d) pencil hardness, and no anti-glare property and no glare. As a result, the reflectance was 0.3% and the hardness was 2H, and the desired performance was obtained. The arithmetic average roughness of the surface irregularities of this antiglare antireflection film was 0.4 μm.

  In the samples of Comparative Example 1 and Comparative Example 2, the same results as in Example 1 were obtained for (a), (b), and (d), but the reflectance of (c) was obtained. The arithmetic average roughness of the surface irregularities was 0.1 to 0.2 μm. From this, it can be seen that, in both Comparative Examples 1 and 2, since the coating film was not faced down and dried after coating, the coating film was uneven in thickness and the reflectance was increased.

It is general | schematic sectional drawing which shows the layer structure of the glare-proof antireflection film of this invention. It is a flowchart explaining the process of this invention. It is the schematic which shows an example of a gravure coater. It is general | schematic sectional drawing in each process. It is the schematic which shows an example of an embossing calendar machine. It is the schematic explaining the application | coating drying method of this invention. It is the schematic in another embodiment which performs embossing after application | coating. It is a schematic sectional drawing which shows an example of the base material in another embodiment which mixed the microparticles | fine-particles in the coating liquid of the hard-coat layer, and formed unevenness | corrugation. It is the schematic of the film forming installation in another embodiment which also performs embossing at the time of film forming. FIG. 5 is a schematic cross-sectional view showing an example of a transparent support in another embodiment in which fine particles are mixed into a dope to form a film and form irregularities. FIG. 5 is a schematic cross-sectional view showing an example of a transparent support in another embodiment in which fine particles are mixed into a dope to form a film and form irregularities. It is a flowchart explaining the process in another embodiment. It is general | schematic sectional drawing in each process in another embodiment. It is sectional drawing which shows the example of application | coating of the hard-coat layer in another embodiment. It is the schematic which shows the gravure coater which dries with an application surface up. It is the schematic which shows the gravure coater which dries with an application surface sideways.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Anti-glare antireflection film 11 Transparent support 12 Hard coat layer 12a, 14 Concavity and convexity 13 Antireflection layer 13a Medium refractive index layer 13b High refractive index layer 13c Low refractive index layer 15 Base material 16 Transfer film 30 Embossing calendar machine 40 Transfer Machine

Claims (12)

An irregularity forming step for forming irregularities on the surface of the substrate;
And a coating / drying step of applying a coating liquid constituting an antireflection film on the surface having the irregularities and controlling the drying conditions of the coating layer to make the thickness of the coating layer substantially constant. A method for producing an antiglare antireflection film. An application step of applying a hard coat layer or a hard coat layer and an antiglare layer to a substrate;
Concavity and convexity forming step for forming concavities and convexities on the surface of the hard coat layer or the antiglare layer applied in the application step,
And a coating / drying step of applying a coating liquid constituting an antireflection film on the surface having the irregularities and controlling the drying conditions of the coating layer to make the thickness of the coating layer substantially constant. A method for producing an antiglare antireflection film. 3. The method for producing an antiglare antireflection film according to claim 1, wherein in the coating drying step, the coating layer is dried with the coating layer facing downward in the direction of gravity. The said uneven | corrugated formation process forms the said unevenness | corrugation through a roll with an unevenness | corrugation on the surface, and then hardens or hardens the hard-coat layer or anti-glare layer by ionizing radiation. Manufacturing method of anti-glare antireflection film.   In the unevenness forming step, after the hard coat layer or the antiglare layer is applied, the hardcoat layer or the antiglare layer is cured by heat or ionizing radiation through a roll having an uneven surface. The manufacturing method of the anti-glare antireflection film according to claim 2 or 3. When applying the hard coat layer or the antiglare layer, fine particles are mixed into the hard coat layer coating solution or the antiglare layer coating solution, and surface irregularities are formed by the fine particles after the coating layer is dried. A method for producing an antiglare antireflection film according to any one of claims 2 to 5. The antiglare reflection according to any one of claims 1 to 6, wherein the uneven shape has an average uneven period of 2 µm to 100 µm and an arithmetic average roughness of 0.02 µm to 10 µm. Manufacturing method of prevention film. The shape of the unevenness is such that the average unevenness period is 2 μm or more and 100 μm or less and the arithmetic average roughness is 0.02 μm or more and 10 μm or less in any of the hard coat layer, the antiglare layer, and the coating layer. The method for producing an antiglare antireflection film according to any one of claims 1 to 7. 9. The antiglare property according to claim 1, wherein in the drying in the coating and drying step, the coating is quickly dried using at least one of an infrared heater, a microwave, a low dew point, and a reduced pressure. Manufacturing method of antireflection film. 10. The coating in the coating / drying step is performed by any one of roll coating, reverse roll coating, gravure coating, reverse gravure coating, micro gravure coating, bar coating, and die coating. Manufacturing method of anti-glare antireflection film. The anti-glare property according to any one of claims 1 to 10, wherein the substrate is a long transparent polymer film, and the unevenness forming step and the coating drying step are performed while continuously conveying the film. Manufacturing method of antireflection film. The method for producing an antiglare antireflection film according to any one of claims 1 to 11, wherein the transparent polymer film contains cellulose acylate.

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