JP2007133386A - Antireflection film and optical filter provided therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film, in which surface reflectivity is low, a reflection spectrum is more nearly flat, a reflected color hue is neutral and has no feeling of glaring, at a low cost and further to provide a multifunctional antireflection film, which is equipped with an antireflection layer excellent in abrasion resistance, a near infrared rays absorbing layer and/or a wavelength selectively absorbing layer capable of sharply absorbing visible light of a specific wavelength within a range between 550 nm and 610 nm, at a low cost. <P>SOLUTION: As shown in Fig. 1, a hard coat layer 4 is formed on one surface of a base material film and further an antireflection layer 9 composed of two layers, a high refractive index layer 3 and a low refractive index layer 2, is formed thereon in this order to constitute the antireflection film. A ratio (d<SB>H</SB>/d<SB>L</SB>) of thickness d<SB>H</SB>of the high refractive index layer 3 to thickness d<SB>L</SB>of the low refractive index layer 2 in the antireflection layer 9 is within a range of 1.0 to 1.9. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is excellent in antireflection performance and scratch resistance, more preferably an antireflection film having a function of selectively absorbing near infrared rays and / or visible light of a specific wavelength, and an optical film provided with this antireflection film on the surface layer The present invention relates to a filter and an image display device including the optical filter.

  Anti-reflection films improve visibility by reducing the reflection of external light sources such as sunlight and fluorescent lamps in image display devices such as cathode-ray tube TVs, large-screen flat-screen TVs such as liquid crystal displays and plasma displays, and computer monitors. Therefore, there is a demand for less visible light reflection.

  As an antireflection technique, it is known that the reflectance is reduced by coating the surface of a base material with a transparent film having a small refractive index (see Patent Document 1). Furthermore, reflection can be more effectively prevented by forming a high refractive index layer on the substrate and forming a low refractive index layer thereon. Also, a transfer material for an antireflection antistatic plate having a metal oxide-containing layer as a high refractive index layer on the surface of the base film having releasability and a siloxane resin layer as a low refractive index layer thereon. Is known (see Patent Document 2).

Examples of the low refractive index material for forming these low refractive index layers include MgF ₂ (refractive index 1.38) and SiO ₂ (refractive index 1.47) in the case of inorganic materials. In the case of organic materials, there are perfluoro resins (refractive index 1.34 to 1.40), siloxane resins (refractive index 1.40 to 1.45), and the like.

  On the other hand, attempts to further lower the refractive index are also being studied. For example, a technology for forming a transparent film having a low refractive index by applying a coating film forming paint obtained by dispersing silica fine particles having cavities in an organic material, which is a matrix material, and then drying and curing. (See Patent Documents 3 and 4). That is, by forming a cavity surrounded by an outer shell in the fine particle, the refractive index of the fine particle itself is reduced and dispersed in an organic material.

  However, when the amount of the silica fine particles introduced is excessively large, the refractive index of the transparent film obtained is further lowered, but the surface hardness is lowered because the silica fine particles and the matrix material cannot be sufficiently bonded, and the surface is cleaned. As a result, there is a problem that visibility is lowered due to the possibility of scratches on the surface, and it has been a problem to achieve both reduction in reflectivity by lowering the refractive index and scratch resistance by increasing hardness.

In general, when a hard coat layer is formed on a base film and an antireflection layer comprising two layers of a high refractive index layer and a low refractive index layer is further formed thereon, the refractive index of air is n ₀ , and the hard coat layer is formed. The refractive index of the layer is n _G , the refractive index of the high refractive index layer is n _H , the thickness is d _H , the refractive index of the low refractive index layer is n _L , the thickness is d _L , and the wavelength of light to be prevented from being reflected When λ, the following non-reflection condition must be satisfied.

n _H d _H = λ / 4 (6)
n _L d _L = λ / 4 (7)
_{n G / n 0 = (n} H / n L) 2 (8).

Here, when n ₀ = 1.00 and n _G = 1.50, n _H / n _L is 1.22, and when the thickness ratio d _H / d _L is 0.82, the lowest reflectance is obtained at the wavelength λ. However, the reflection spectrum generally obtained with two layers is the minimum reflectance at the wavelength λ, and the reflectance increases to a V-shaped spectrum on the shorter wavelength side and the longer wavelength side, thereby preventing reflection only in a relatively narrow region. The effect is not obtained, so the reflection color becomes blue or red, causing glare. If the antireflection layer is further multilayered, the reflection spectrum becomes flatter and an antireflection effect can be obtained over the entire visible light range, but this leads to an increase in cost due to an increase in the number of manufacturing steps.

On the other hand, in an image display device such as a cathode ray tube (CRT), a plasma display (PDP), or a surface electrolytic display (SED), there is a possibility that electromagnetic waves that may affect the human body or equipment may be shielded or the remote control may malfunction. Form an optical filter on the front of the image display surface that has multiple functions such as shielding of infrared rays, shielding of ineffective wavelength visible light in the emission spectrum to prevent color purity degradation, antistatic, antireflection etc. It is common to install. Here, a film provided with a resin layer containing an organic dye that efficiently absorbs near-infrared rays and visible light having an ineffective wavelength for improving color purity is used (Patent Literature). 5, 6, 7, 8, 9). Further, it has been proposed to reduce the number of materials and the bonding process by integrating the functions of antireflection and near-infrared shielding on a single film (see Patent Document 10).
JP 2002-122704 A JP 2000-338306 A JP 2001-233611 A JP 2002-79616 A Japanese Patent No. 3308545 Japanese Patent No. 3334141 JP 58-153904 A JP 2000-193820 A JP 2002-40233 A Japanese Patent Laid-Open No. 10-156991

  The present invention is an antireflection film in which a hard coat layer, a high refractive index layer, and a low refractive index layer are formed in this order on one side of a base film. The minimum reflectance is low and the surface reflection spectrum is more flat. An object of the present invention is to provide an antireflection film having a neutral reflection color and no glare. Further, in a low refractive index layer in which silica fine particles having cavities therein are dispersed in a matrix material, the coating is made hard by strongly bonding the silica fine particles and the matrix material, the surface reflectance is low, and Obtaining an antireflection layer excellent in scratch resistance, and sharpening visible light with a specific wavelength in the range of 550 to 610 nm on the surface opposite to the antireflection layer obtained by the present invention. Provided is a multifunctional antireflection film provided with a wavelength selective absorption layer capable of absorbing light, an optical filter provided with the antireflection film on the surface layer, and an image display device provided with the optical filter. It is for the purpose.

In order to achieve this object, the present inventors have conducted intensive research, and as a result, determined the thickness d _L of the low refractive index layer, the thickness d _H of the high refractive index layer, and the ratio d _H / d _L of the thickness. By making it into this range, the antireflection film of the present invention was found. That is,
A first invention of the present invention is an antireflection film in which a hard coat layer, a high refractive index layer, and a low refractive index layer are formed in this order on one surface of a base film, and the high refractive index of the antireflection layer The thickness d _{H of the} layer is in the range of 105 to 160 nm, the thickness d _L of the low refractive index layer is in the range of 75 to 110 nm, and the thickness d _H of the high refractive index layer and the thickness d _L of the low refractive index layer are It is an antireflection film having a ratio d _H / d _L in the range of 1.0 to 1.9.

The second invention is a preferred embodiment of the present invention is the product _d H · _{n H} a thickness _{d H} and a refractive index _{n H} of the high refractive index layer is 165~276nm and a refractive the thickness _{d L} of the low refractive index layer product _d L · _{n L} rate _{n L} is antireflection film according to the first invention is in the range of 96～163Nm.

  According to a third aspect of the present invention, which is a preferred embodiment of the present invention, the low refractive index layer is a reflection according to the first or second aspect, wherein the low refractive index layer is formed of a coating obtained by curing a paint containing silica fine particles having cavities therein. It is a prevention film.

  4th invention which is a preferable aspect of this invention is an antireflection film as described in 3rd invention whose coating material which forms the said low-refractive-index layer is a coating material containing a siloxane compound and a hardening | curing agent further.

  According to a fifth aspect of the present invention, a siloxane compound is a hydrolyzate and / or condensate of one or more silane compounds selected from the following general formulas (1) to (5). 4 is an antireflection film according to the invention of item 4.

R ¹ Si (OR ⁶ ) ₃ (1)
(R ¹ represents a fluoroalkyl group having 3 to 17 fluorine atoms. R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, which may be the same or different.)
R ² Si (OR ⁷ ) ₃ (2)
(R ² represents a group selected from vinyl group, allyl group, alkenyl group, acrylic group, methacryl group, methacryloxy group, cyano group, epoxy group, glycidoxy group, amino group, and substituted products thereof. R ⁷ Represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxyethyl group, or an acetyl group, which may be the same or different.
R ³ Si (OR ⁸ ) ₃ (3)
(R ³ represents a group selected from hydrogen, an alkyl group, an aryl group, and a substituent thereof. R ⁸ represents a methyl group, an ethyl group, a propyl group, or a butyl group, and each is the same or different. Is also good.)
R ⁴ R ⁵ Si (OR ⁹ ) ₂ (4)
(R ⁴ and R ⁵ each represents a group selected from hydrogen, an alkyl group, a fluoroalkyl group, an aryl group, an alkenyl group, a methacryloxy group, an epoxy group, a glycidoxy group, an amino group, and a substituent thereof. Each may be the same or different, and R ⁹ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, and each may be the same or different.)
Si (OR ¹⁰ ) ₄ (5)
(R ¹⁰ represents a methyl group or an ethyl group, and may be the same or different.)
A sixth invention that is a preferred embodiment of the present invention is the antireflection film according to the fourth or fifth invention, wherein the curing agent is an aluminum chelate compound and / or a magnesium chelate compound.

  According to a seventh aspect of the present invention, which is a preferred embodiment of the present invention, at least one organic dye is provided on the surface of the base film opposite to the surface on which the hard coat layer, high refractive index layer, and low refractive index layer are laminated. It is an antireflection film as described in any one of the 1st-6th invention by which the resin layer containing this was laminated | stacked.

  An eighth aspect of the present invention, which is a preferred embodiment of the present invention, is the antireflection film according to the seventh aspect, wherein the transmittance at a wavelength of 850 nm is 15% or less and the transmittance at a wavelength from 950 nm to 1150 nm is 10% or less.

  A ninth aspect of the invention, which is a preferred embodiment of the present invention, is the antireflection film according to the seventh or eighth aspect having a main absorption peak in the wavelength range of 550 to 610 nm.

  A tenth aspect of the present invention, which is a preferred embodiment of the present invention, is the antireflection film according to the ninth aspect, wherein the half width of the main absorption peak is 50 nm or less.

  An eleventh aspect of the present invention is an optical filter in which the antireflection film according to any one of the first to tenth aspects is provided on a surface layer.

According to a twelfth aspect of the present invention, which is a preferred embodiment of the present invention, a resin layer containing an organic dye having a main absorption peak in the wavelength range of 565 to 585 nm, and a surface resistivity of 10 ⁵ Ω / □ or more and 10 ⁹ Ω / □ or less. The optical filter according to the eleventh aspect, having an antistatic layer.

  A thirteenth aspect of the present invention is an image display device including the optical filter according to the eleventh or twelfth aspect.

  According to the present invention, it is possible to obtain an antireflection film having a low minimum reflectance, a surface reflection spectrum that is closer to flat, a neutral color, and no glare. Furthermore, according to a more preferred embodiment of the present invention, the scratch resistance is excellent, and further, visible light having a specific wavelength in the range of 550 to 610 nm is applied to the near-infrared absorbing layer and / or the surface opposite to the antireflection layer. It can be set as the multifunctional antireflection film provided with the wavelength selection absorption layer which can absorb sharply. By providing an optical filter with this antireflection film on the surface layer on the image display surface or its front surface, the reflection of external light can be suppressed, visibility can be improved, and scratching during cleaning can be prevented. An image display device can be provided in which an image with improved color purity and an expanded color reproduction range can be obtained, and further, malfunction of the remote controller can be prevented.

  FIG. 1 is a schematic cross-sectional view showing an example of a preferred embodiment of the antireflection film of the present invention. As an example of a preferred embodiment of the present invention, a hard coat layer (b) is laminated on one surface of the base film (a), and further, a high refractive index layer (d) and a low refractive index layer (e) are further formed thereon. The antireflection layer (c) is laminated. Furthermore, a protective film (f) for preventing the antireflection layer from being scratched or soiled in the production process may be laminated thereon.

  On the other hand, a resin layer (g) containing an organic dye that absorbs near infrared rays and / or an organic dye that absorbs visible light having a specific wavelength in the range of 550 to 610 nm is laminated on the opposite surface of the base film. Become. Furthermore, an adhesive layer (h) and a release film (i) for laminating with other filter members such as semi-tempered glass, or an electromagnetic wave shielding film, a near-infrared shielding film, and an antistatic film are laminated thereon. used. Moreover, you may contain the organic pigment | dye which absorbs the visible light of the specific wavelength which exists in the range of 550-610 nm in the adhesion layer (h).

  The antireflection film of the present invention has an absolute reflection spectrum of 5 ° at a wavelength of 400 to 700 nm, (1) a minimum reflectance of 0.6% or less, (2) a maximum reflectance of 2.5% or less, and (3 It is preferable to satisfy all three conditions that the difference between the maximum reflectance and the minimum reflectance is less than 2.5%. If the minimum reflectance exceeds 0.6%, the antireflection function becomes insufficient, which is not preferable. On the other hand, if the maximum reflectance exceeds 2.5%, the reflectance around 450 nm or around 700 nm increases, and the color tone of the reflected light becomes blue or red, which is not preferable. More preferably, the minimum reflectivity is 0.5% or less, more preferably 0.3% or less, the maximum reflectivity is 2.0% or less, and the maximum reflectivity and the minimum reflectivity. Is less than 2.0%, more preferably less than 1.5%, because a flatter reflection spectrum is obtained and the color is also neutral.

In the antireflection film of the present invention, the refractive index of the low refractive index layer and the high refractive index layer is used in order to set the minimum reflectance and the maximum reflectance of the absolute reflection spectrum at a wavelength of 400 to 700 nm and the reflectance difference within the above ranges. The rate is preferably adjusted as follows. The refractive index (n _L ) of the low refractive index layer is preferably 1.42 or less, and the refractive index difference between the low refractive index layer and the high refractive index layer is preferably 0.15 or more. Furthermore, the refractive index of the high refractive index layer _{(n H)} is preferably from 1.55 to 1.80, more preferably from 1.60 to 1.75. The refractive index of the low refractive index layer _{(n L)} is preferably from 1.23 to 1.42, more preferably from 1.34 to 1.38.

Furthermore, it is preferable to adjust the refractive index of the hard coat layer. The refractive index (n _G ) of the hard coat layer is preferably 1.45 to 1.55. Here, the refractive index (n _L ) of the low refractive index layer and the refractive index (n _H ) of the high refractive index layer satisfy the following formulas (9) and (10) to lower the minimum reflectance. It is preferable because it is possible.

(N _H ) = (n _L ) × (n _G ) ^1/2 ± 0.02 (9)
(N _L ) = (n _H ) / (n _G ) ^1/2 ± 0.02 (10).

In order for the antireflection film of the present invention to obtain a flatter reflection spectrum, the product of the refractive index (n _H ) of the high refractive index layer and the thickness (d _H ) of the high refractive index layer in the above-described range. (Corresponding to the optical thickness) is preferably set to a thickness (d _H ) that is 1.2 to 1.7 times 1/4 of the wavelength (λ) of visible light that is desired to prevent reflection. Is preferably 1.3 to 1.6 times. If it is less than 1.2 times, the difference between the maximum reflectance and the minimum reflectance also exceeds 2.5%, which is not preferable. On the other hand, if it exceeds 1.7 times, the minimum reflectance becomes higher than 0.6%, and the antireflection performance becomes insufficient. Here, the wavelength (λ) of visible light to be prevented from being reflected is arbitrarily selected as long as it is in the visible light range, but is preferably preferably in the range of 550 to 650 nm, and more preferably 580 to 620 nm. preferable.

Considering the range of the wavelength (λ) for which the above-described preferable reflection is to be prevented, the optical thickness (n _H d _H ) of the high refractive index layer is preferably in the range of 165 to 276 nm, more preferably 178 to 260 nm, particularly preferably. Is in the range of 188-248 nm.

In consideration of the range of the refractive index (n _H ) of the preferable high refractive index layer and the wavelength (λ) to be prevented from being reflected in the present invention, in order to obtain a flatter reflection spectrum in the present invention, The thickness (d _H ) of the high refractive index layer is in the range of 105 to 160 nm. The thickness (d _H ) of the high refractive index layer is preferably in the range of 110 to 155 nm, more preferably 115 to 150 nm.

On the other hand, the preferred range of the thickness (d _L ) of the low refractive index layer of the present invention includes the refractive index (n _L ) of the low refractive index layer and the thickness (d _L ) of the low refractive index layer in the above-mentioned range. Is preferably a thickness (d _L ) such that it is 0.7 to 1.00 times 1/4 of the wavelength (λ) of visible light to be prevented from reflecting, and more preferably 0.75 to 0.75 0.95 times is preferable. In the present invention, as described above, in order to make the thickness (d _H ) of the high refractive index layer thicker than the thickness derived from the non-reflective conditions shown in the above formulas (6) to (8), When the product of the refractive index (n _L ) of the refractive index layer and the thickness (d _L ) of the low refractive index layer is set to a thickness that is ¼ of the wavelength (λ) of visible light to prevent reflection, the lowest reflection Since the wavelength that becomes the rate shifts to the longer wavelength side, it is preferable to make the thickness lower than 1/4 that of the wavelength (λ) of visible light to be prevented from being reflected.

Considering the range of the wavelength (λ) where the above-described preferable reflection is to be prevented, the optical thickness (n _L d _L ) of the low refractive index layer is preferably in the range of 96 to 163 nm, more preferably 103 to 154 nm, particularly preferably. Is in the range of 109 to 147 nm.

Considering the refractive index (n _L ) of the preferable high refractive index layer and the wavelength (λ) to prevent reflection in the present invention, in order to obtain a flatter reflection spectrum in the present invention, the low refractive index The rate layer thickness (d _L ) is in the range of 75-110 nm. The thickness (d _L ) of the low refractive index layer is preferably 85 to 110 nm, more preferably 85 to 105 nm.

Furthermore, in order to obtain a flat reflection spectrum, the ratio (d _H / d _L ) between the thickness (d _H ) of the high refractive index layer and the thickness (d _L ) of the low refractive index layer is set to 1.0. ˜1.9. If it is less than 1.0, the maximum reflectance is higher than 2.5%, the difference between the maximum reflectance and the minimum reflectance is also over 2.5%, the reflection spectrum becomes V-shaped, Blue interference color appears. On the other hand, if it exceeds 1.9, a flat reflection spectrum can be obtained, but the minimum reflectance becomes higher than 0.6%, and the antireflection performance becomes insufficient. When (d _H / d _L ) is preferably 1.1 to 1.8, more preferably 1.2 to 1.7, a flat reflection spectrum can be obtained and the minimum reflectance can be lowered.

  The antireflection film in the present invention is usually often installed and used on the outermost surface of a display. In that case, the scratch resistance is preferably 3 or more because it is difficult to damage the film when dust or the like adhering to the surface of the film is wiped off with a cloth. More preferably, it is quaternary or higher. Scratch resistance was measured by visually observing the surface of the antireflective film after subjecting the antireflective layer side surface to # 0000 steel wool by applying a load of 250 g and 10 strokes at a stroke width of 10 cm and a speed of 30 mm / sec. The method of scratching is evaluated in the following five stages. 5th grade: No scratches. Fourth grade: 1 to 5 scratches. 3rd grade: 6 to 10 scratches. Second grade: 11 or more scratches. First grade: Countless scratches on the entire surface.

  The surface of the low refractive index layer of the present invention has irregularities derived from fine particles. As for the surface roughness of the low refractive index layer, the center line average roughness Ra is preferably 0.5 to 15.0 nm, and the maximum height Rmax is preferably 5 to 150 nm. If Ra and Rmax are lower than this range, the antireflection effect may be reduced. Conversely, exceeding this range is not preferable because haze and scratch resistance may be deteriorated and fingerprints may be difficult to wipe off.

  As the substrate film used in the present invention, a film that can be formed into a melt or a solution is preferably used. Specific examples thereof include films made of polyester, polyolefin, polyamide, polyphenylene sulfide, acetate, polycarbonate, acrylic resin, and the like. Among these, a film made of a thermoplastic resin excellent in transparency, mechanical strength, dimensional stability and the like is particularly preferable. In order to use it for image display device applications, it is preferable that the film has at least one selected from polyester, acetate and acrylic resin because it has high light transmittance and low haze value. In view of transparency, haze value, and mechanical properties, a film made of polyester is particularly preferably used.

  For example, the light transmittance at 400 to 800 nm of the substrate film is preferably 40% or more, more preferably 60% or more. The haze value of the substrate film is preferably 5% or less, more preferably 3% or less. Satisfying both of these conditions is more preferable in terms of sharpness when used as a member for an image display device. Further, the upper limit of the light transmittance is about 99.5%, and the lower limit of the haze value is about 0.1%.

  Examples of the polyester preferably used in the present invention include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, and polypropylene naphthalate. Two or more of these may be mixed. In addition, these may be a polyester copolymerized with other dicarboxylic acid components and diol components, but the copolymerization ratio is preferably 25% or more in the degree of crystallinity in a film in which crystal orientation is completed. More preferably, the range is 30% or more, and more preferably 35% or more. When the crystallinity is less than 25%, dimensional stability and mechanical strength tend to be insufficient. The degree of crystallinity can be measured by a Raman spectrum analysis method.

  The base film used in the present invention may be a composite film having a laminated structure of two or more layers. As the composite film, for example, a composite film that is substantially free of particles in the inner layer portion and provided with a layer containing particles in the surface layer portion, has coarse particles in the inner layer portion, and fine particles in the surface layer portion. And a composite film having a layer in which the inner layer portion contains fine bubbles. In the composite film, the polymer constituting the inner layer portion and the surface layer portion may be a chemically different polymer or the same kind of polymer.

  The base film in the present invention is a film that is crystallized by biaxial stretching from the viewpoint of ensuring sufficient thermal stability, particularly dimensional stability and mechanical strength of the film, and improving flatness. preferable. The crystal orientation by biaxial stretching means that the thermoplastic film before unstretched, that is, before the crystal orientation is completed, is preferably stretched about 2.5 to 5 times in the longitudinal direction and the width direction, respectively, and then heat-treated. The crystal orientation is completed by the above, and it indicates a biaxial orientation pattern by wide-angle X-ray diffraction.

  The thickness of the base film used in the present invention is preferably 10 to 500 μm, more preferably 20 to 300 μm, from the viewpoint of mechanical strength and handling properties.

  The base film of the present invention may contain various additives, resin compositions, cross-linking agents and the like within a range that does not impair the effects of the present invention. For example, antioxidants, heat stabilizers, UV absorbers, organic and inorganic particles, pigments, dyes, antistatic agents, nucleating agents, acrylic resins, polyester resins, urethane resins, polyolefin resins, polycarbonate resins, alkyd resins, epoxy resins , Urea resin, phenol resin, silicone resin, rubber resin, wax composition, melamine crosslinking agent, oxazoline crosslinking agent, methylolated, alkylolized urea crosslinking agent, acrylamide, polyamide, epoxy resin, isocyanate compound , Aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like.

  Among these, when inorganic particles such as silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate, barium sulfate, carbon black, zeolite, titanium oxide, metal fine powder, etc. are added, it is easy to slip. This is particularly preferable since the property and scratch resistance are improved. The average particle size of the inorganic particles is preferably 0.005 to 5 μm, more preferably about 0.05 to 1 μm. The particle diameter here is a value obtained using a laser diffraction particle size distribution measuring apparatus. The average particle size is 50% distributed particle size. The 50% distribution particle size refers to the particle size where the particle size distribution is 50%, and the average particle size refers to this particle size unless otherwise specified. Moreover, the addition amount of inorganic particles is 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass in 100 parts by mass of the base film.

  The base film used in the present invention preferably has an easy-adhesion layer formed on at least one surface of the base film for the purpose of improving the adhesion with the hard coat layer and the resin layer containing an organic dye. It is still more preferable that it is formed on both surfaces of the base film. The easy-adhesion layer as used in the field of this invention means the film-form thing which exists in the laminated structure formed on both surfaces of a base film.

The component constituting the easy-adhesion layer is not particularly limited as long as it has sufficient adhesion with the hard coat layer or the resin layer containing an organic dye, but is not limited to polyester resin, polycarbonate resin, epoxy resin, alkyd resin, acrylic resin. Resins, urea resins, urethane resins and the like can be suitably used. In particular, when a film substrate made of polyester is used, it is more preferable to use a resin selected from a polyester resin, an acrylic resin, and a urethane resin from the viewpoint of adhesion, and two different resins, for example, a polyester resin and a urethane are used. A combination of resin, polyester resin and acrylic resin, or acrylic resin and urethane resin may be used.

  Moreover, it is more preferable to use a different resin from the point of adhesiveness for the easy-adhesion layer formed on each surface of the base film. For example, it is preferable to use a polyester resin on the hard coat layer side and an acrylic resin on the resin layer side containing the organic dye.

Since the easy-adhesion layer generates interference fringes, it is necessary to devise measures to reduce them. For this purpose, the refractive index of the easy-adhesion layer is expressed by the following formula (11) (refractive index of the easy-adhesion layer) = {(refractive index of the base film) × (refractive index of the hard coat layer or the resin layer containing the organic dye). } ^1/2 ± 0.02 (11)
It is preferable from the viewpoint of reducing interference fringes. When the base film is polyester, the refractive index of the easy adhesion layer is preferably 1.53 to 1.63, and more preferably 1.57 to 1.61.

  When a base film is melt-extruded and then biaxially stretched to form a film, an easy-adhesion layer is preferably applied on both sides in the previous stage of the transverse stretching process of the film-forming process and formed simultaneously with the film formation. Used. In that case, the above-described resin is preferably applied as an aqueous emulsion paint, and the thickness of the easy-adhesion layer is preferably 0.03 to 0.20 μm.

  The antireflection film of the present invention is prepared by laminating a hard coat layer and an antireflection layer on one side of a base film to produce an antireflection film first, and then contains an organic dye on the opposite side of the base film It is preferable to laminate a resin layer. By doing so, it is possible to expose the organic dye to ultraviolet rays used when forming the hard coat layer and the antireflection layer.

  In this invention, a hard-coat layer means that hardness is higher than a base film. In practice, the hard coat layer of the present invention preferably has a pencil hardness of 2H or more.

  The hard coat layer is not particularly limited, and examples thereof include a composition containing a (meth) acrylate compound. Specifically, methyl (meth) acrylate, n-butyl (meth) acrylate, polyester (meth) Monofunctional acrylate compounds such as acrylates, lauryl (meth) acrylates, hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates, and polyfunctional (meth) acrylates having two or more (meth) acryloyl groups in the molecule A compound is particularly preferred in the present invention since the solvent resistance and the like are improved. Specific examples of polyfunctional (meth) acrylates include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like. These monomers may be used alone or in combination of two or more. Furthermore, fine particles such as silica and reactive silicon compounds such as tetraethoxysilane may be included. Among these, from the viewpoint of productivity and hardness, a composition containing an ultraviolet curable polyfunctional (meth) acrylate is preferably used.

  In the hard coat layer of the present invention, various additives can be blended as necessary. For example, stabilizers such as antioxidants, light stabilizers, ultraviolet absorbers, surfactants, leveling agents, antistatic agents, and the like can be used.

  The use of a leveling agent is preferable because it smoothes the hard coat layer to be formed. For example, there are silicone leveling agents, acrylic leveling agents, fluorine leveling agents and the like, and silicone leveling agents are particularly effective when added in a small amount. As the silicone leveling agent, it is preferable to apply an acrylic leveling agent that does not inhibit the adhesion with the antireflection layer on the hard coat layer. As such a leveling agent, “ARUFON-UP1000 series, UH2000 series, UC3000 series (trade name): manufactured by Toagosei Co., Ltd.” and the like can be preferably used. The leveling agent is preferably added in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the hard coat composition.

  The thickness of the hard coat layer is usually preferably 0.1 μm to 30 μm, more preferably 1 μm to 15 μm. When the thickness of the hard coat layer is less than 0.1 μm, it is too thin even if it is sufficiently cured, so that the surface hardness is not sufficient and the surface tends to be damaged. On the other hand, when the thickness of the hard coat layer exceeds 30 μm, the cured film tends to be cracked due to stress such as bending.

  The antireflection film of the present invention is obtained by laminating an antireflection layer composed of two layers of a high refractive index layer and a low refractive index layer on a hard coat layer.

  As a constituent component of the high refractive index layer of the present invention, it is preferable that metal compound particles are dispersed in a resin composition in order to impart antistatic properties to the antireflection film surface. A (meth) acrylate compound is used for the resin component. The (meth) acrylate compound is preferably radically polymerized by irradiation with actinic rays to improve the solvent resistance and hardness of the formed film. Furthermore, the (meth) acryloyl group has two or more polyfunctional (meth) The acrylate compound is particularly preferred in the present invention because of its improved solvent resistance. For example, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, ethylene-modified trimethylolpropane tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanuric acid ester Trifunctional (meth) acrylates such as tri (meth) acrylate, pentafunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.

  As the resin component, in order to improve the dispersibility of the metal compound particles, a (meth) acrylate compound having an acidic functional group such as a carboxyl group, a phosphate group, or a sulfonate group can be used. Specifically, examples of the acidic functional group-containing monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, and mono (2- (meta ) (Acryloyloxyethyl) acid phosphate, diphenyl-2- (meth) acryloyloxyethyl phosphate, and other phosphoric acid (meth) acrylic acid esters, 2-sulfoester (meth) acrylates, and the like. In addition, (meth) acrylate compounds having a bond with polarity such as an amide bond, a urethane bond, and an ether bond can be used.

  As the metal compound particles used here, various conductive metal oxide particles are preferably used. Particularly preferred are tin-containing antimony oxide particles (ATO), zinc-containing antimony oxide particles, tin-containing indium oxide particles (ITO), zinc oxide / aluminum oxide particles, and antimony oxide particles. More preferably, tin-containing indium oxide particles (ITO) are used.

  As the conductive metal compound particles constituting the conductivity, particles having an average primary particle diameter (sphere equivalent diameter measured by the BET method) of 0.5 μm or less are preferably used. More preferably, those having a particle size of 0.001 to 0.3 μm, and more preferably 0.005 to 0.2 μm are used. When the average particle diameter exceeds this range, the transparency of the coating film (high refractive index layer) produced is lowered. When the average particle diameter is less than this range, the metal compound particles tend to aggregate and the resulting coating film (high refractive index layer) The haze value increases. In either case, it becomes difficult to obtain a desired haze value.

  In the present invention, a conductive polymer such as polypyrrole, polythiophene, and polyaniline, an organometallic compound such as a metal alcoholate and a chelate compound, for the purpose of further improving the conductivity effect, as a component of the high refractive index layer, Further, it can be contained.

  In forming the high refractive index layer in the present invention, an initiator may be used to advance the curing of the applied resin component. As the initiator, the applied binder component initiates or accelerates polymerization and / or crosslinking reaction by radical reaction, anion reaction, cation reaction, etc., and conventionally known thioxanthone derivatives, azo compounds, diazo compounds, Various photopolymerization initiators such as aromatic carbonyl compounds, dialkylaminobenzoic acid esters, peroxides, acridine derivatives, phenazine derivatives and quinoxaline derivatives can be used. The amount of the photopolymerization initiator is usually preferably added in the range of 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the resin component. In such a preferred range, photopolymerization is sufficiently fast and light irradiation for a short time may be sufficient to satisfy hardness and scratch resistance, while the coating film has functions such as conductivity, abrasion resistance, and weather resistance. There is no decline.

  Further, when the high refractive index layer is formed in the present invention, an amine compound may be coexisted with the photopolymerization initiator in order to prevent the sensitivity of the initiator from being lowered due to oxygen inhibition. Furthermore, you may contain various additives, such as a polymerization inhibitor, a curing catalyst, antioxidant, a dispersing agent, a leveling agent, a silane coupling agent, as needed. In addition, for the purpose of improving the surface hardness, alkyl silicates and hydrolysates thereof, colloidal silica, dry silica, wet silica, titanium oxide and other inorganic particles, colloidally dispersed silica fine particles, and the like may be further included. it can.

  In the present invention, the mixing ratio of the constituent components of the high refractive index layer is preferably such that the mass ratio [(A) / (B)] of the resin component and the metal compound particles is 10/90 to 30/70, Preferably it is 15 / 85-25 / 75. When the metal compound particles are within such a preferable range, the obtained film has sufficient transparency and good electrical conductivity, and on the other hand, various physical and chemical strengths of the obtained film do not deteriorate.

In order to provide a desired level of antistatic properties by the high refractive index layer of the present invention, it is preferable to control the addition amount so that the surface resistance value of the layer is 1 × 10 ¹¹ Ω / □ or less. Is preferably controlled to be 1 × 10 ¹⁰ Ω / □ or less.

  The high refractive index layer in the present invention is a layer having a total light transmittance of preferably 40% or more, more preferably 50% or more, from the viewpoint of sharpness and transparency.

  In the present invention, the high refractive index layer can be formed by adjusting a coating liquid preferably dispersed with a solvent, applying the coating liquid on the hard coat layer, and then drying and curing.

  The solvent used in the formation of the high refractive index layer of the present invention is formulated to improve the coating or printing workability and to improve the dispersibility of the metal compound particles and to dissolve the resin component. For example, conventionally known various organic solvents can be used. In particular, in the present invention, an organic solvent having a boiling point of 60 to 180 ° C. is preferred from the viewpoint of viscosity stability and drying property of the composition, and among them, the organic solvent having an oxygen atom has an affinity for metal compound particles. It is preferable because it is good. Specific examples of the organic solvent include methanol, ethanol, isopropyl alcohol, n-butanol, tert-butanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, propylene glycol monomethyl ether, cyclohexanone, and acetic acid. Preferable examples include butyl, isopropylacetone, methyl ethyl ketone, methyl isobutyl ketone, diacetylacetone, acetylacetone and the like. These may be used alone or in combination of two or more.

  The amount of the organic solvent may be blended in an arbitrary amount so that the composition has a viscosity with good workability according to the application means and the printing means, but the solid content concentration of the composition is usually 60% by mass. Hereinafter, it is preferable that the amount is 50% by mass or less. As the preparation of the composition for forming a photocurable conductive film of the present invention, any method can be adopted. Usually, a metal compound particle is added to a solution in which a resin component is dissolved in an organic solvent, and a paint shaker is added. Alternatively, a method of dispersing by a dispersing machine such as a ball mill, a sand mill, a three roll, an attritor, a homomixer, etc., and then adding a photopolymerization initiator and dissolving uniformly is suitable.

  In the antireflection film of the present invention, the low refractive index layer preferably has a refractive index as described above in order to reduce the minimum reflectance, and for this purpose, silica fine particles having cavities in the interior described later are used as a matrix material. It is preferable that the dispersed paint is cured. A preferred example of the matrix material is a resin composition having fluorine in order to suppress the refractive index of the low refractive index layer to be low and to impart antifouling properties, fingerprint wiping properties, and the like.

  In the antireflection film of the present invention, in order to make the low refractive index layer more preferable, it is obtained by coating a coating composition comprising silica fine particles having cavities therein, a siloxane compound, a curing agent, and a solvent. It is preferable that the refractive index be reduced because the refractive index can be lowered and the surface reflectance can be lowered.

Further, in the low refractive index layer of the present invention, the siloxane compound as the matrix material and the silica fine particles are preferably bonded tightly in order to improve the surface hardness and to have excellent scratch resistance. It is preferable that the siloxane compound is reacted with the surface of the silica fine particles and bonded in advance at the stage of the coating composition before coating.
The coating composition for that purpose can be obtained by hydrolyzing the silane compound in a solvent with an acid catalyst in the presence of silica fine particles to form a silanol compound and then subjecting the silanol compound to a condensation reaction. As the silanol compound, one or more silane compounds selected from silane compounds represented by the following general formulas (1) to (5) are preferable.

  The obtained paint contains a siloxane compound that is a condensate of these silane compounds. Moreover, although these silane compounds were hydrolyzed, you may contain the silanol compound which is not condensed.

R ¹ Si (OR ⁶ ) ₃ (1)
R ¹ represents a fluoroalkyl group having 3 to 17 fluorine atoms. The number of fluorine in R ¹ is preferably 6-8. When the number of fluorine atoms per molecule is large, the hardness of the obtained film tends to decrease. The number of carbon atoms of R ¹ is preferably 3 to 10 because the scratch resistance of the obtained film can be increased. A carbon number of 3 is particularly preferred.

R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, and may be the same or different. R ⁶ is more preferably a methyl group or an ethyl group.

  Use of the trifunctional silane compound represented by the general formula (1) is preferable because the refractive index of the resulting film can be lowered.

R ² Si (OR ⁷ ) ₃ (2)
R ² represents a group selected from a vinyl group, an allyl group, an alkenyl group, an acrylic group, a methacryl group, a methacryloxy group, a cyano group, an epoxy group, a glycidoxy group, an amino group, and a substituted product thereof. R ² having 2 to 10 carbon atoms is preferred because it can increase the scratch resistance of the resulting coating.

R ⁷ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxyethyl group, or an acetyl group, and may be the same or different. R ⁷ is more preferably a methyl group or an ethyl group.

  Use of the trifunctional silane compound represented by the general formula (2) is preferable because the hardness of the resulting coating can be improved.

R ³ Si (OR ⁸ ) ₃ (3)
R ³ represents a group selected from hydrogen, an alkyl group, an aryl group, and substituents thereof. The number of carbon atoms of R ³ is preferably 1 to 6 because the scratch resistance of the resulting film can be increased. If R ³ exceeds 6 carbon atoms, the hardness of the resulting coating tends to decrease.

R ⁸ represents a methyl group, an ethyl group, a propyl group, or a butyl group, and may be the same or different. R ⁸ is more preferably a methyl group or an ethyl group.

  Use of the trifunctional silane compound represented by the general formula (3) is preferable because the hardness of the resulting coating can be improved.

R ⁴ R ⁵ Si (OR ⁹ ) ₂ (4)
R ⁴ and R ⁵ each represent a group selected from hydrogen, an alkyl group, a fluoroalkyl group, an aryl group, an alkenyl group, a methacryloxy group, an epoxy group, a glycidoxy group, an amino group, and a substituent thereof. May be the same or different. As C4 of R < ⁴ >, R < ⁵ >, since 1-6 can improve the abrasion resistance of the obtained film, it is preferable.

R ⁹ represents a methyl group, an ethyl group, a propyl group, an isopropyl group or an acetyl group, and may be the same or different. R ⁹ is more preferably a methyl group or an ethyl group.

  The use of a bifunctional silane compound represented by the general formula (4) is preferable because the flexibility of the resulting film can be improved.

Si (OR ¹⁰ ) ₄ (5)
R ¹⁰ represents a methyl group or an ethyl group, and may be the same or different.

  It is preferable to use a tetrafunctional silane compound represented by the general formula (5) because the hardness of the resulting film can be improved.

  These silane compounds represented by the general formulas (1) to (5) may be used alone or in combination of two or more.

  The content of the siloxane compound is preferably 20% by mass to 70% by mass, and particularly preferably 30% by mass to 60% by mass with respect to the total amount of the film when the film is formed. It is preferable to contain a siloxane compound within this range because the refractive index of the coating can be lowered and the hardness of the coating can be increased. Therefore, the content of the siloxane compound in the coating is preferably in the above range with respect to all components except the solvent.

  Among these, in order to reduce the refractive index, the fluorine-containing silane compound represented by the general formula (1) is used as an essential component, and the silane compound represented by the general formulas (2) to (5) is selected. It is preferable to use a combination of one or more silane compounds. The amount of the silane compound represented by the general formula (1) is preferably 20% by mass to 80% by mass, and particularly preferably 30% by mass to 60% by mass with respect to the total amount of the silane compound. When the amount of the silane compound is less than 20% by mass, the reduction in the refractive index may be insufficient. On the other hand, when the amount of the silane compound exceeds 80% by mass, the hardness of the film may be lowered.

  Specific examples of the silane compounds represented by the general formulas (1) to (5) are shown below.

  Examples of the trifunctional silane compound represented by the general formula (1) include trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoromethyltriacetoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyl. Triethoxysilane, trifluoropropyltriacetoxysilane, trifluoroacetoxyethyltrimethoxysilane, trifluoroacetoxyethyltriethoxysilane, trifluoroacetoxyethyltriacetoxysilane, perfluoropropylethyltrimethoxysilane, perfluoropropylethyltriethoxysilane , Perfluoropropylethyltriacetoxysilane, perfluoropentylethyltrimethoxysilane, perfluoropentylethyltriethoxy Silane, perfluoropentylethyltriacetoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, tridecafluorooctyltripropoxysilane, tridecafluorooctyltriisopropoxysilane, heptadecafluorodecyltrimethoxysilane , Heptadecafluorodecyltriethoxysilane, and the like. Of these, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, trifluoropropyltrimethoxysilane, and trifluoropropyltriethoxysilane are preferred from the viewpoint of the hardness of the resulting coating.

  Examples of the trifunctional silane compound represented by the general formula (2) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, glycidoxymethyltrimethoxysilane, Glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α- Glycidoxypro Rutrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropyltripropoxy silane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycid Xylbutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycid Xibutyltrimethoxy , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltri Methoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, β- (3,4-epoxycyclohexyl) propyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) pro Examples include pyrtriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane. Of these, vinyltrialkoxysilane and 3-methacryloxypropyltrialkoxysilane are preferred from the viewpoint of the hardness of the resulting coating.

  Examples of the trifunctional silane compound represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane, 3-glycidoxysipropyltrimethoxy Silane, and the like. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable from the viewpoint of the hardness of the obtained film.

  Examples of the bifunctional silane compound represented by the general formula (4) include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, and methylvinyldimethoxy. Silane, methylvinyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, glycidoxymethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxy Silane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Methyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, β-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldi Ethoxysilane, trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxysilane, trifluoropropylmethyldiacetoxysilane, trifluoropropylethyldimethoxysilane, trifluoropropylethyldiethoxysilane, trifluoropropylethyldiacetoxysilane, tri Fluoropropylvinyldimethoxysilane, trifluoropropylvinyldiethoxysilane, trifluoropropylvinyldiacetoxysilane, heptadecafluorodecylme Examples include tildimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, cyclohexylmethyldimethoxysilane, 3-methacryloxypropyldimethoxysilane, and octadecylmethyldimethoxysilane. Of these, dimethyl dialkoxysilane is preferably used for the purpose of imparting flexibility to the resulting coating.

  Examples of the tetrafunctional silane compound represented by the general formula (5) include tetramethoxysilane and tetraethoxysilane.

  The number average particle diameter of the silica fine particles used in the present invention is preferably 1 nm to 200 nm, and particularly preferably the number average particle diameter is 1 nm to 70 nm. When the number average particle diameter is less than 1 nm, the bonding with the matrix material becomes insufficient, and the hardness of the coating film may be lowered. On the other hand, if the number average particle diameter exceeds 200 nm, the generation of voids between particles caused by introducing a large amount of particles is reduced, and the effect of lowering the refractive index may not be sufficiently exhibited.

  Here, the average particle diameter of the silica fine particles can be measured by a number average particle diameter using various particle counters. It is preferable to measure the particle diameter of the silica fine particles before being added to the paint. Moreover, after the coating is formed, a method of measuring the particle diameter of the silica fine particles in the coating using an electron scanning microscope or a transmission electron microscope is preferable.

  The number average particle diameter of the silica fine particles is preferably smaller than the film thickness of the coating film to be formed. When the film thickness is exceeded, silica fine particles are exposed on the surface of the film, and not only the antireflection property is impaired, but also the surface hardness and stain resistance of the film are lowered.

  The silica fine particles used in the present invention are preferably silica fine particles having a silanol group on the surface in order to easily react with the matrix siloxane compound.

  As the silica fine particles used in the present invention, silica fine particles having cavities inside are preferable in order to reduce the refractive index of the coating. Silica fine particles having no cavity inside generally have a refractive index lowering effect because the refractive index of the particles themselves is 1.45 to 1.50. On the other hand, since the silica fine particles having cavities inside have a refractive index of 1.20 to 1.40, the effect of lowering the refractive index by introduction is large.

  Examples of the silica fine particles having cavities therein include silica fine particles having cavities surrounded by an outer shell, and porous silica fine particles having a large number of cavities. Among these, when the hardness of the coating is taken into consideration, porous silica fine particles having high strength of the particles themselves are preferable. The refractive index of the fine particles is 1.20 to 1.40, more preferably 1.20 to 1.35. Further, the number average particle diameter of the silica fine particles having cavities therein is preferably 5 nm to 100 nm. The refractive index of the silica fine particles can be measured by the method disclosed in paragraph [0034] of JP-A-2001-233611. Silica fine particles having cavities therein are produced, for example, by the method described in paragraphs [0033] to [0046] of JP-A-2001-233611 and the method described in paragraph [0043] of Japanese Patent No. 3272111. can do. A commercially available product can also be used.

  The content of the silica fine particles is preferably 30% by mass to 80% by mass, and particularly preferably 40% by mass to 70% by mass with respect to the total amount of the film when the film is formed. Therefore, it is preferable that the content of the silica fine particles in the coating is in the above-mentioned range with respect to all components except the solvent. When silica fine particles are contained in the coating within this range, not only the refractive index can be lowered, but also the hardness of the coating can be increased. When the content of the silica fine particles is less than 30% by mass, the refractive index lowering effect due to the voids between the particles is reduced. On the other hand, when the content of the silica fine particles exceeds 80% by mass, many island phenomena occur in the coating film, the hardness of the coating film decreases, and the refractive index becomes uneven depending on the location, which is not preferable.

  In the hydrolysis reaction, the acid catalyst and water are preferably added in a solvent over 1 to 180 minutes, and then reacted at room temperature to 80 ° C. for 1 to 180 minutes. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed. The reaction temperature is more preferably 40 to 70 ° C. Moreover, after obtaining a silanol compound by a hydrolysis reaction, it is preferable that the reaction solution is heated as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to perform a condensation reaction. In order to increase the degree of polymerization of the siloxane compound, it is possible to reheat or add a base catalyst.

  Examples of the acid catalyst used in the hydrolysis reaction include acid catalysts such as hydrochloric acid, acetic acid, formic acid, nitric acid, oxalic acid, hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, polyvalent carboxylic acid or anhydrides thereof, and ion exchange resins. In particular, an acidic aqueous solution using formic acid, acetic acid or phosphoric acid is preferred. A preferable addition amount of these acid catalysts is preferably 0.05% by mass to 10% by mass, particularly preferably 0.1% by mass to 5% by mass, based on the total amount of silane compounds used in the hydrolysis reaction. %. If the amount of the acid catalyst is less than 0.05% by mass, the hydrolysis reaction may not proceed sufficiently. On the other hand, if the amount of the acid catalyst exceeds 10% by mass, the hydrolysis reaction may run away.

  The solvent is not particularly limited, but is determined in consideration of the stability, wettability, volatility, etc. of the coating composition. The solvent can be used not only as one type but also as a mixture of two or more types. Specific examples of the solvent include, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl- Alcohols such as 3-methoxy-1-butanol and diacetone alcohol; glycols such as ethylene glycol and propylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, Ethers such as lenglycol diethyl ether, ethylene glycol dibutyl ether and diethyl ether; ketones such as methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone and 2-heptanone; dimethylformamide Amides such as dimethylacetamide; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, lactic acid Acetates such as methyl, ethyl lactate and butyl lactate; toluene, xylene, hexane, In addition to the aromatic or aliphatic hydrocarbons such as cyclohexane, .gamma.-butyrolactone, N- methyl-2-pyrrolidone, dimethyl sulfoxide and the like.

  The amount of the solvent used during the hydrolysis reaction is preferably in the range of 50% by mass to 500% by mass, particularly preferably in the range of 80% by mass to 200% by mass, based on the total amount of silane compounds. When the amount of the solvent is less than 50% by mass, the reaction may run away and gel may occur. On the other hand, if the amount of the solvent exceeds 500% by mass, hydrolysis may not proceed.

  Moreover, as water used for a hydrolysis reaction, ion-exchange water is preferable. The amount of water can be arbitrarily selected, but it is preferably used in the range of 1.0 to 4.0 mol with respect to 1 mol of the silane compound.

  Examples of the curing agent used in the present invention include various curing agents or three-dimensional crosslinking agents that accelerate the curing of the coating composition or facilitate the curing. Specific examples of the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, melamine resins, polyfunctional acrylic resins, urea resins, and the like. One kind or two or more kinds may be added. Of these, metal chelate compounds are preferably used in view of the stability of the curing agent and the processability of the obtained film. Examples of the metal chelate compound used include a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound, and a magnesium chelate compound. Among these, for the purpose of lowering the refractive index, an aluminum chelate compound and / or a magnesium chelate compound having a low refractive index is preferable. These metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane; β-keto acid esters such as ethyl acetoacetate and ethyl benzoylacetate. Preferable specific examples of the metal chelate compound include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris ( Examples include aluminum chelate compounds such as acetylacetonate), and magnesium chelate compounds such as ethyl acetoacetate magnesium monoisopropylate, magnesium bis (ethylacetoacetate), alkyl acetoacetate magnesium monosopropylate, and magnesium bis (acetylacetonate). . Of these, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), magnesium bis (acetylacetonate), and magnesium bis (ethylacetoacetate) are preferable. In view of storage stability and availability, aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate) are particularly preferred. The amount of the curing agent added is preferably 0.1% by mass to 10% by mass, and particularly preferably 1% by mass to 6% by mass with respect to the total amount of silane compounds in the coating composition. Here, the total amount of the silane compound means an amount including all of the silane compound, its hydrolyzate and its condensate. When the content is less than 0.1% by mass, the hardness of the resulting coating is lowered. On the other hand, if the content exceeds 10% by mass, curing is sufficient and the hardness of the resulting coating is improved, but the refractive index is also increased, which is not preferable.

  In the coating composition, it is preferable to use a mixture of a solvent having a boiling point of 100 to 180 ° C. under atmospheric pressure and a solvent having a boiling point of less than 100 under atmospheric pressure. By including a solvent having a boiling point of 100 to 180 ° C. under atmospheric pressure, the coating property of the coating liquid is improved, and a film having a flat surface can be obtained. In addition, by including a solvent having a boiling point of less than 100 under atmospheric pressure, the solvent is effectively volatilized at the time of film formation, and a film having high hardness can be obtained. That is, a film having a flat surface and high hardness can be obtained.

  Specific examples of the solvent having a boiling point of 100 to 180 ° C. under atmospheric pressure include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether. , Ethers such as propylene glycol mono-t-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, butyl acetate, isobutyl acetate, 3 -Methoxybutyl acetate, 3-methyl-3- Toxibutyl acetate, acetates such as methyl lactate, ethyl lactate and butyl lactate, ketones such as acetylacetone, methylpropylketone, methylbutylketone, methylisobutylketone, cyclopentanone and 2-heptanone, butanol, isobutylalcohol, pentano- , 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxy-1-butanol, alcohols such as diacetone alcohol, and aromatic hydrocarbons such as toluene and xylene Can be mentioned. These may be used alone or in combination. Among these, examples of particularly preferable solvents are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diacetone alcohol and the like.

  Examples of the solvent having a boiling point of less than 100 ° C. under atmospheric pressure include methanol, ethanol, isopropanol, t-butanol, methyl ethyl ketone, and the like. These may be used alone or in combination.

  The total solvent content in the coating composition of the present invention is preferably in the range of 1300% by mass to 9900% by mass, particularly preferably in the range of 1500% by mass to 6000% by mass with respect to the total silane compound content. . If the total solvent content is less than 1300% by mass or more than 9900% by mass, it becomes difficult to form a film having a predetermined film thickness.

  Here, the total amount of the silane compound means an amount including all of the silane compound, its hydrolyzate and its condensate.

  In the antireflection film of the present invention, a hard coat layer is first formed on one surface of a base film, then a high refractive index layer is formed on the layer, and then a low refractive index layer is formed on the layer. To do. As the coating method of each paint, micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, flow coating method, etc. can be preferably used. Gravure coating is preferably used. Next, after coating, each film is formed by heating, drying and curing with active rays such as heat or ultraviolet rays.

  In a more preferred embodiment of the antireflection film of the present invention, an antireflective film is obtained by laminating a resin layer containing an organic dye on the opposite side of the surface of the base film on which the hard coat layer and antireflection layer are laminated. It is more preferable to combine the function and the function of shielding near infrared rays and / or shielding visible light having an ineffective wavelength in the emission spectrum.

  The resin layer containing such an organic dye is preferably a laminated film made of a composition in which an organic dye having near infrared absorption ability is dispersed in a transparent polymer resin binder. In this case, the antireflection film of the present invention preferably satisfies the conditions that the transmittance at a wavelength of 850 nm is 15% or less and the transmittance from a wavelength of 950 nm to 1150 nm is 10% or less. Further, the transmittance at a wavelength of 850 nm is more preferably 11% or less, and the transmittance at a wavelength from 950 nm to 1150 nm is more preferably 7% or less.

  As such a near-infrared absorbing dye, a diimonium compound as disclosed in Japanese Patent Publication No. 43-25335 is preferable, and specifically, “KAYASORB” manufactured by Nippon Kayaku Co., Ltd. is used as the title. “IRG-022”, “IRG-023”, “IRG-050”, “IRG-068”, “CIR-1081”, “CIR-1085”, “FD-RH” manufactured by Nippon Carlit.

Such a diimonium-based compound has a wide effective absorption wavelength region in the near infrared region with a wavelength of 850 to 1250 nm, and an organic dye in the resin layer per unit area in order to reduce the transmittance at a wavelength of 950 to 1150 nm to 10% or less. Is preferably 0.1 to 0.5 g / m ^2, and more preferably 0.2 to 0.4 g / m ² . If the content is below this range, the near-infrared shielding ability may be inferior, and if the content exceeds this range, the total light transmittance may be insufficient and the image may become dark.

  As the near-infrared absorbing dye in the present invention, only the diimonium compound may be used. However, in order to make the transmittance at a wavelength of 850 nm alone 15% or less, it is necessary to increase the content, The light transmittance may be insufficient. Therefore, in the present invention, it is preferable to use one or more near infrared absorbing dyes having an absorption maximum wavelength in the wavelength range of 800 nm to 900 nm together with the diimonium compound. Specifically, phthalocyanine compounds or naphthalocyanine compounds, cyanine compounds, dithiol nickel complex compounds having one or more substituents of halogen groups such as primary and / or secondary amino groups, alkoxy groups and fluorine Etc. Of these, fluorine-containing phthalocyanine compounds are preferably used from the viewpoint of light resistance and heat and humidity resistance. Specific examples include “IR-1”, “IR-10”, “IR-12”, “IR-14” and the like, which are named “EEX Color” manufactured by Nippon Shokubai Co., Ltd.

  Further, although cyanine compounds have difficulty in light resistance, as an improved dye, a dye obtained by coupling a cyanine compound and a quencher in advance to be integrated is preferably used in the present invention. By integrating, the light resistance of the cyanine compound can be improved and a high extinction coefficient characteristic of the cyanine dye can be obtained, so that the amount of the dye used can be reduced. As the quencher, bis (1,2-dithiophenolate) copper tetra-n-butylammonium salt is preferable because it does not impair the light resistance of the diimonium compound. Specific examples of the integrated dye of the cyanine compound and the quencher include “SD50-E04N” and “SD50-E05N” manufactured by Sumitomo Seika Co., Ltd. and “TZ-111” manufactured by Asahi Denka Kogyo Co., Ltd. , “TZ-114”, “TZ-118” and the like.

The content in the resin layer per unit area of the near-infrared absorbing dye compound having an absorption maximum wavelength in the wavelength range of 800 nm to 900 nm is determined according to the extinction coefficient of the dye used and the content of the diimonium compound. In order to set the transmittance at 850 nm to 15% or less, the content is preferably 0.01 to 0.3 g / m ² , particularly when an integrated dye of a cyanine compound and a quencher is used. Is preferably 0.01 to 0.1 g / m ² . If the content is below this range, the near-infrared shielding ability may be inferior, and if the content exceeds this range, the total light transmittance may be insufficient and the image may become dark.

  Another preferred embodiment of the resin layer containing such an organic dye is a laminate comprising a composition in which an organic dye that selectively absorbs visible light having a specific wavelength in the range of 550 to 610 nm is dispersed in a transparent polymer resin binder. In this case, the antireflection film of the present invention preferably has a main absorption peak in the range of 550 to 610 nm. More preferably, the half width of the main absorption peak is 50 nm or less, and the main absorption wavelength is preferably an ineffective wavelength in the emission spectrum of the image display apparatus to which it is applied.

  For example, in the case of a plasma display, a dye that selectively absorbs orange light around 590 nm accompanying emission of neon gas sealed in a panel is preferably used. In this case, a dye having a main absorption peak in the wavelength range of 585 to 595 nm is preferable, the transmittance at a wavelength of 590 nm is 50% or less, more preferably 35% or less, and the total light transmittance is 55% or more, more preferably It is preferable that it is 60% or more. The transmittance at a wavelength of 590 nm is preferably low, but if it is too low, the total light transmittance is also low, so it is preferably 15% or more.

  In the case of a cathode ray tube (CRT), a surface electric field display (SED), or the like, a dye that selectively absorbs yellow light around 575 nm is preferably used. In this case, a dye having a main absorption peak in the wavelength range of 565 to 585 nm is preferable, and the transmittance at a wavelength of 575 nm is preferably 40% or more and 80% or less, more preferably 50% or more and 70% or less. The light transmittance is preferably 70% or more, more preferably 75% or more. The transmittance at a wavelength of 575 nm is preferably low, but if it is too low, the total light transmittance is also low, which is not preferable.

  The organic dye that selectively absorbs a specific wavelength used in the present invention is, for example, a porphyrazine compound (also known as a tetraazaporphyrin compound) or a cyanine compound as disclosed in JP-A-2002-129052, It is preferably used from the viewpoint of solubility in organic solvents and extinction coefficient. Specific examples include TAP series such as “TAP-2”, “TAP-5”, “TAP-12”, and “TAP-45” manufactured by Yamada Chemical Co., Ltd., “Asahi Denka Kogyo Co., Ltd.” TY-100 "," TY-102 "," TY-171 "and the like.

The content of the organic dye in the resin layer per unit area is determined from the required value of transmittance (or absorbance) at a specific wavelength to be shielded and the extinction coefficient of the organic dye to be used. a .15g / ^{m 2,} more and more preferably, 0.01~0.10g / ^{m 2.}

  Furthermore, as another preferred embodiment of the resin layer containing such an organic dye, both an organic dye that absorbs visible light having a specific wavelength in the range of 550 to 610 nm and the near-infrared absorbing dye are used in combination. The functions of infrared absorption and visible light selective wavelength absorption may be combined.

  The resin used in the resin layer containing the organic pigment according to the present invention is preferably a transparent polymer resin binder, is substantially colorless and transparent with no visible light absorption, polyester-based resin, (meth) acrylic resin, (Meth) acrylic urethane resins, polycarbonate resins and the like are preferably used, and (meth) acrylic resins are particularly preferable.

  The (meth) acrylic resin used in the present invention includes methyl (meth) acrylate, ethyl (meth) acrylate, n- or isopropyl (meth) acrylate, n- or sec- or tert-butyl (meth) acrylate, pentyl ( (Meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Selected from decyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid, itaconic acid, maleic anhydride, glycidyl (meth) acrylate, fluorine-containing (meth) acrylate, and styrene Those obtained by copolymerizing several unsaturated monomer is preferred. Furthermore, in order to improve the light resistance of organic dyes, unsaturated monomers having a hindered amine which is an ultraviolet light-stable group (for example, Adeka Stub LA-82, LA-87, etc. manufactured by Asahi Denka Kogyo Co., Ltd.), benzotriazole series , Benzophenone-based, triazine-based unsaturated monomers having a copolymerized unsaturated monomer, or hindered amine additives (for example, Sanol LS-765, LS-2626 manufactured by Sankyo Lifetech Co., Ltd.) ) Or an ultraviolet absorber is preferably added to the polymerized resin.

  The (meth) acrylic resin used in the resin layer containing the organic pigment according to the present invention preferably has a glass transition point of 80 ° C. or higher, more preferably 100 ° C. or higher from the viewpoint of heat resistance. It is not limited. In order to reduce the influence of moisture on the organic dye, the hygroscopicity of the resin is preferably 2% or less.

  Furthermore, the (meth) acrylic resin used in the present invention may be crosslinked to improve the solvent resistance. In this case, a crosslinking agent such as aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, or melamine is suitable. Used for. Further, a silane coupling agent may be added in order to improve the adhesion with the easy adhesion layer. Examples of the silane coupling agent include an alkoxysilane compound having an unsaturated group or an epoxy group.

  The (meth) acrylic resin used in the resin layer containing the organic dye according to the present invention is preferably soluble in an organic solvent, particularly methyl ethyl ketone, methyl butyl ketone, cyclohexanone, acetone, acetonitrile, ethyl acetate, butyl acetate, Those which are soluble in toluene, xylene and the like are preferable, and these are used alone or as a mixed solvent of two or more. The viscosity of the (meth) acrylic resin is 50 to 5000 mPa.s in consideration of workability when preparing a paint by preparing an organic dye compound. It is preferable that it is s, and it is preferable that the solid content density | concentration of (meth) acrylic-type resin is 10-50 mass%.

  Commercially available products of such (meth) acrylic resin binders include “Dianar BR-80” manufactured by Mitsubishi Rayon Co., Ltd., “Hals Hybrid IR-G205” manufactured by Nippon Shokubai Co., Ltd., “Foret” manufactured by Soken Chemical Co., Ltd. GS-1000 "etc. are mentioned as a suitable example.

  The above-mentioned organic coloring matter can be either a dye or a pigment, but it is preferable to use a dye in consideration of transparency and visible light transmittance. In the case of using a dye, one that dissolves in an organic solvent in which the polymer resin binder is soluble is preferable. Examples of the organic solvent include methyl ethyl ketone, methyl butyl ketone, cyclohexanone, acetone, acetonitrile, ethyl acetate, butyl acetate, toluene, xylene and the like. The aforementioned organic dye is used after being dissolved in such an organic solvent and then mixed with a polymer resin binder solution or an organic solvent to form a paint. Furthermore, it is also preferable to mix | blend a ultraviolet absorber, a ultraviolet stabilizer, antioxidant, a leveling agent, an antifoamer, etc. with a coating material.

  Such paint is applied on the easy-adhesion layer of the base film by a coating method such as three reverse coaters, forward rotation or reverse gravure coater, comma coater, die coater, etc., and heated to dry to form a resin layer To do.

  The thickness of the resin layer containing the organic dye of the present invention is not particularly limited, but is preferably 1 to 30 μm, and more preferably 3 to 15 μm is applicable to the film of the (meth) acrylic resin binder. From the point of view, it is more preferable.

  In order to bond the optical film of the present invention with other optical filter elements such as semi-tempered glass, electromagnetic wave shielding film, or antistatic film, an adhesive layer is laminated on the resin layer, and further until the bonding process. In order to prevent adhesion with other surfaces, it is preferable that a release film is laminated.

  The pressure-sensitive adhesive layer in the present invention is not particularly limited as long as two objects are bonded by the pressure-sensitive adhesive action. As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, rubber-based, vinyl polymerization-based, condensation polymerization-based, thermosetting resin-based, silicone-based, and the like can be used. Among these, examples of the rubber-based adhesive include butadiene-styrene copolymer system (SBR), butadiene-acrylonitrile copolymer system (NBR), chloroprene polymer system, and isobutylene-isoprene copolymer system (butyl rubber). it can. Examples of the vinyl polymerization-based pressure-sensitive adhesive include acrylic resin-based, styrene resin-based, vinyl acetate-ethylene copolymer system, and vinyl chloride-vinyl acetate copolymer system. Examples of the condensation polymerization pressure-sensitive adhesive include a polyester resin system. Examples of the thermosetting resin adhesive include epoxy resin, urethane resin, formalin resin, and the like. These resins may be used alone or in combination of two or more.

  Furthermore, the above-mentioned organic dye may be contained in the adhesive layer, whereby the resin layer can be omitted.

  The pressure-sensitive adhesive layer in the present invention preferably has a film peel strength at 90 degrees in the range of 5 to 25 N / 25 mm when an optical film is bonded to a blue plate glass plate previously degreased with alcohol or the like, and more preferably 10 to 20 N. A range of / 25 mm is preferred. If it is lower than this, the adhesive strength is weak and it is easy to peel off. On the contrary, if it is strong, the resin tends to be hard, which is not preferable.

  The thickness of the adhesive layer is preferably 10 to 50 μm, and more preferably 20 to 30 μm.

  Further, the adhesive layer is bonded to the release film in consideration of workability until it is actually bonded to the semi-tempered glass or the electromagnetic wave shielding film. As the release film, a film in which a release agent such as silicone is coated on a film substrate such as polyester is suitably used.

  The peel strength at 90 degrees with the adhesive layer of the release film is preferably in the range of 10 to 100 mN / 25 mm, and more preferably in the range of 30 to 70 mN / 25 mm. Specific examples of the release film include “Therapel” manufactured by Toray Film Processing Co., Ltd.

  The adhesive layer is applied to the release surface of the release film by a coating method such as a three reverse coater, a normal rotation or reverse gravure coater, a comma coater, or a die coater, and is dried in an oven to form a film. A method of laminating by laminating with a resin layer containing an organic dye is preferred, but it is not limited to this method.

  The antireflection film of the present invention has a low surface reflectance and a flatter reflection spectrum. Further, the antireflection film of a more preferred embodiment of the present invention is excellent in surface scratch resistance, and at the same time, absorbs light having an ineffective wavelength for an image display device in the range of 550 to 610 nm. Has correction ability. The antireflection film of the present invention is bonded to a functional film such as an electromagnetic wave shielding film, an antistatic film, an antiglare film, a gas barrier film, etc., so that a cathode ray tube (CRT), plasma display panel (PDP), surface electrolytic display It is suitably used for an optical filter of an image display device such as (SED), and is attached to the image display surface and / or the surface of its front plate via an adhesive layer or an adhesive layer to form an image display device. it can.

  Next, as an example using the antireflection film of the present invention, an optical filter for surface electric field display (SED) (hereinafter simply referred to as an optical filter) will be described. FIG. 2 is a schematic cross-sectional view showing an example of the optical filter, but is not limited thereto.

In the case of a display that emits light by colliding electrons with a glass surface coated with a fluorescent material, such as CRT or SED, the image display surface has a static dissipative property in order to prevent electrostatic charge on the image display surface. It is required to be granted. Here, the electrostatic diffusibility is not conductive enough to shield the electrostatic field, but does not cause severe ESD (Electro-Static Discharge) when a charged object comes into contact with it, and it is charged. Is required to have a surface resistivity of 10 ⁵ to 10 ⁹ Ω / □. Therefore, the optical filter is provided with an adhesive 12 for bonding to the panel 13 (including a release film before being bonded to the panel), an antistatic layer 11 and a base film 10 in this order to prevent antistatic. The layer 11 is arranged at a position close to the panel 13. If it is disposed at a position away from the panel 13 (for example, a position through the base film 10), it is not preferable because sufficient electrostatic diffusibility cannot be obtained. Such surface resistivity is measured based on JIS K6911 (1995 edition), or a high resistivity meter Hi-Lester UP (model number: MCP-HT450, manufactured by Dia Instruments, measurement range: 10 ⁴ to 10 ¹³ Ω) is used. Thus, it can be measured and determined by the Mitsubishi Chemical Method (MCC method).

  The antistatic layer 11 is preferably highly transparent, and the total light transmittance is preferably 85% or more, more preferably 92% or more, and particularly preferably 95% or more. The total light transmittance is measured based on JIS K7361-1: (1997 edition), and for example, an antistatic layer using a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) as a JIS-compliant measuring instrument. 11 is measured, and the total light transmittance of the antistatic layer 11 is determined by dividing the total light transmittance of the base film 10 formed with 11 by the total light transmittance of the base film 10 measured in advance.

  Further, the haze of the antistatic layer 11 is preferably 1% or less, more preferably 0.7% or less, and particularly preferably 0.4% or less. The haze is measured based on JIS K7136 (2000 version). For example, the antistatic layer 11 is formed using a turbidimeter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) as in the case of measuring the total light transmittance. The haze of the base film 10 is measured, and the haze of the base film 10 that has been measured in advance is subtracted to determine the haze of the antistatic layer 8.

  The antistatic layer 11 is not particularly limited as long as it has the above-described surface resistivity, total light transmittance, and haze, but is preferably a layer in which conductive particles are dispersed. Examples of the conductive particles include metal fine particles such as silver and copper, metal oxide particles such as antimony-doped tin oxide (ATO), tin-containing indium oxide (ITO), and zinc oxide, carbon black, carbon nanotube, and carbon nanofiber. Of carbon particles. Among these, carbon nanotubes are preferably used because they are excellent in conductivity and can exhibit antistatic properties in a smaller amount.

  The hard coat layer 4 is formed on the surface side of the base film 5 of the optical filter, and the antireflection layer 9 of the present invention is formed thereon. Further, an antifouling layer or a protective film may be provided on the surface layer of the antireflection layer 9.

  Further, in order to improve the contrast of the image and the color purity, the resin layer 6 containing the organic dye having the main absorption peak in the wavelength range of 565 to 585 nm is opposite to the antireflection layer 9 of the base film 5. Although formed on the surface, the resin layer 6 may be formed on the surface opposite to the antistatic layer 11 of the base film 10. The position of the resin layer 6 containing the organic dye in the optical filter is not particularly limited. However, the resin layer 6 contains the organic dye in order to prevent deterioration of the dye due to ultraviolet rays contained in external light (for example, sunlight). It is preferable that an ultraviolet absorbing layer is disposed on the surface side of the resin layer 6. Such an ultraviolet absorbing function is usually preferably imparted to the base film 5 or to the adhesive 7.

  Since the antireflection film of the present invention has a low surface reflectance and a flatter reflection spectrum, it can be applied to an optical filter so that the luminous reflectance is low and the color of the reflected color is close to neutral. An optical filter with good contrast can be provided.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

1. Characteristic Evaluation Method (1) Measurement of Refractive Index of Low Refractive Index Layer A low refractive index paint of any of paints A to D described later is applied to a silicon wafer with a spin coater so that the film thickness becomes 0.1 μm. Applied. Then, using an inert oven INH-21CD (manufactured by Koyo Thermo System Co., Ltd.), the film was obtained by heat curing at 130 ° C. for 1 minute. About the formed film, the refractive index in 633 nm was measured with the phase difference measuring apparatus (Nikon Co., Ltd. product: NPDM-1000).

(2) Thickness measurement of high refractive index layer and low refractive index layer The cross section of the antireflection layer of the prepared antireflection film was observed at an acceleration voltage of 100 kV using a transmission electron microscope (H-7100FA type manufactured by Hitachi). Sample preparation used the ultrathin section method. Observation at a magnification of 100,000 times or 200,000 times, the thickness of each layer is measured, and then the ratio d _H / d _L between the thickness d _H of the high refractive index layer and the thickness d _L of the low refractive index layer Asked.

(3) 5 ° absolute reflectance measurement No. 320-400 water resistant sand on the surface opposite to the measurement surface (surface on which the antireflection layer is provided) so that the 60 ° C. gloss (JIS Z 8741) is 10 or less. After uniformly roughening with paper, a black paint was applied and colored so that the visible light transmittance was 5% or less. Using a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation, the absolute reflection spectrum in the wavelength region of 380 nm to 780 nm is measured at an incident angle of 5 degrees from the measurement surface, and the lowest in the wavelength region of 400 nm to 700 nm. The reflectance and its wavelength, the highest reflectance and its wavelength, and the difference between the highest reflectance and the lowest reflectance were determined. When the measured reflection spectrum has undulations, the respective reflectances were obtained from curves connecting intermediate points between undulation peaks (maximum points) and valleys (minimum points).

(4) Scratch resistance; steel wool hardness evaluation Scratch resistance was determined by applying a load of 250 g to # 0000 steel wool and rubbing 10 times at a stroke width of 10 cm and a speed of 30 mm / sec. Was visually observed, and the scratching was evaluated in the following five stages. 5th grade: No scratches. Fourth grade: 1 to 5 scratches. 3rd grade: 6 to 10 scratches. Second grade: 11 or more scratches. First grade: Countless scratches on the entire surface.

(5) Transmittance measurement The transmission spectrum of the antireflection film was measured in the wavelength range of 380 to 1200 nm with a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation. As the near infrared shielding property, a transmittance of 850 nm and a maximum transmittance in a range of 950 to 1150 nm were determined. Furthermore, when the transmission spectrum has a main absorption peak in the visible light region, the main absorption peak wavelength, the transmittance at that wavelength, and the half width of the main absorption peak were determined.

(6) Total light transmittance Measurement was performed using a direct reading haze computer (NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd.

(7) Pencil hardness Measured according to JIS K-5400 using HEIDON (manufactured by Shinto Kagaku Co., Ltd.).

2. Adjustment of low refractive index paint (Paint A)
95.2 parts by mass of methyltrimethoxysilane and 65.4 parts by mass of trifluoropropyltrimethoxysilane were dissolved in 300 parts by mass of propylene glycol monomethyl ether and 100 parts by mass of isopropanol. In this solution, a silica fine particle dispersion having a cavity inside the outer shell having a number average particle diameter of 50 nm (isopropanol dispersion type, solid content concentration 20.5%, manufactured by Catalyst Kasei Kogyo Co., Ltd.) 297.9 parts by mass, water 54 masses And 1.8 parts by mass of formic acid were added dropwise with stirring so that the reaction temperature did not exceed 30 ° C. After the dropwise addition, the obtained solution was heated at a bath temperature of 40 ° C. for 2 hours, and then the solution was heated at a bath temperature of 85 ° C. for 2 hours, the internal temperature was raised to 80 ° C. and heated for 1.5 hours, The polymer solution A was obtained.
In the obtained polymer solution A, 4.8 parts by mass of aluminum tris (acetyl acetate) (trade name: Aluminum Chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.) as an aluminum-based curing agent is added to 125 parts by mass of methanol. The dissolved material was added, 1500 parts by mass of isopropanol and 250 parts by mass of propylene glycol monomethyl ether were added, and the mixture was stirred at room temperature for 2 hours to prepare paint A.
A coating film of the paint A was formed on a silicon wafer, and the refractive index determined by the above method was 1.36.

(Paint B)
109.0 parts by mass of methyltrimethoxysilane, 56.8 parts by mass of heptadecafluorodecyltrimethoxysilane, and 15.2 parts by mass of tetramethoxysilane were dissolved in 300 parts by mass of propylene glycol monoethyl ether. In this solution, a sol of silica fine particles dispersed in isopropanol having a number average particle diameter of 20 nm and having cavities (solid content: 8.5%) (trade name: SOC-NPA-4MA, manufactured by Sumitomo Osaka Cement Co., Ltd.) 890 parts by mass, 60 parts by mass of water and 2 parts by mass of acetic acid were added dropwise with stirring so that the reaction temperature did not exceed 30 ° C. After the dropwise addition, the resulting solution is heated at a bath temperature of 30 ° C. for 3 hours, then the solution is heated at a bath temperature of 85 ° C. for 2 hours, the internal temperature is raised to 80 ° C., heated for 2 hours, and then cooled to room temperature. As a result, a polymer solution B was obtained. In the obtained polymer solution B, 4.8 parts by mass of aluminum tris (acetyl acetate) (trade name: Aluminum Chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.) as an aluminum-based curing agent is added to 125 parts by mass of methanol. The dissolved material was added, 1500 parts by mass of isopropanol and 250 parts by mass of propylene glycol monomethyl ether were added, and the mixture was stirred at room temperature for 2 hours to prepare paint B.
A coating film of the paint B was formed on a silicon wafer, and the refractive index determined by the above-described method was 1.36.

(Paint C)
95.2 parts by mass of methyltrimethoxysilane and 65.4 parts by mass of trifluoropropyltrimethoxysilane were placed in a reaction vessel, and while stirring, 54 parts by mass of water and 1.8 parts by mass of formic acid exceeded 30 ° C. It was dripped so that there was no. After dripping, the obtained solution was heated at a bath temperature of 30 ° C. for 5 hours and then cooled to room temperature to obtain a silanol solution. In the obtained silanol solution, 297.9 parts by mass of a silica fine particle dispersion (isopropanol dispersion type, solid content concentration 20.5%, manufactured by Catalyst Kasei Kogyo Co., Ltd.) having cavities inside the outer shell and an aluminum curing agent, Aluminum tris (acetyl acetate) (trade name: Aluminum Chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.), 4.8 parts by mass dissolved in 125 parts by mass of methanol, and 1600 parts by mass of isopropanol and propylene were added. 550 parts by mass of glycol monomethyl ether was added and stirred at room temperature for 2 hours to prepare paint C.
A coating film of the paint C was formed on a silicon wafer, and the refractive index determined by the above method was 1.36.

(Paint D)
95.2 parts by mass of methyltrimethoxysilane and 65.4 parts by mass of trifluoropropyltrimethoxysilane were dissolved in 300 parts by mass of propylene glycol monomethyl ether and 100 parts by mass of isopropanol. To this solution, 54 parts by mass of water and 1.8 parts by mass of formic acid were added dropwise with stirring so that the reaction temperature did not exceed 30 ° C. After the dropwise addition, the obtained solution was heated at a bath temperature of 40 ° C. for 2 hours, and then the solution was heated at a bath temperature of 85 ° C. for 2 hours, the internal temperature was raised to 80 ° C. and heated for 1.5 hours, Until the polymer solution was obtained.
In the obtained polymer solution, 4.8 parts by mass of aluminum tris (acetyl acetate) (trade name: Aluminum Chelate A (W), manufactured by Kawaken Fine Chemical Co., Ltd.) as an aluminum-based curing agent is dissolved in 125 parts by mass of methanol. Then, 1500 parts by mass of isopropanol and 250 parts by mass of propylene glycol monomethyl ether were added and stirred at room temperature for 2 hours to obtain paint D.
A coating film of the paint D was formed on a silicon wafer, and the refractive index determined by the above method was 1.41.

(Paint E)
Diacrylic acid-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononylethylene glycol 40 parts by mass, dipentaerythritol 10 parts by mass of hexaacrylate, 10 parts by mass of poly (acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl), 300 parts by mass of silica fine particle dispersion having a cavity inside the outer shell (isopropanol dispersion type, solid content concentration 20%, manufactured by Catalyst Kasei Kogyo Co., Ltd.), photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals) 2 Part by mass and 840 parts by mass of trifluoroethanol were mixed to obtain paint E.
A coating film was formed by applying the coating material E on a silicon wafer and then irradiating with ultraviolet rays, and the refractive index determined by the above-described method was 1.38.

3. Preparation of paint containing organic pigment (Paint-1)
As a near infrared absorbing dye, 14.5 parts by mass of “KAYASORB IRG-050” manufactured by Nippon Kayaku Co., Ltd. and 8 parts by mass of “EEX Color IR-10A” manufactured by Nippon Shokubai Co., Ltd. are added to 1000 parts by mass of methyl ethyl ketone. Stir and mix to dissolve. This solution was used as a transparent polymer resin binder solution, and stirred and mixed with 2000 parts by mass of “Hals Hybrid IR-G205” (solid content concentration 29% solution) manufactured by Nippon Shokubai Co., Ltd. to prepare Paint-1.

(Paint-2)
As a near-infrared absorbing dye, 14.5 parts by mass of “KAYASORB IRG-050” manufactured by Nippon Kayaku Co., Ltd., 8 parts by mass of “EEX Color IR-10A” manufactured by Nippon Shokubai Co., Ltd., and main absorption at 593 nm As an organic pigment having a peak, “TAP-2” manufactured by Yamada Chemical Co., Ltd. was dissolved by stirring and mixing 2,000 parts by mass with 2000 parts by mass of methyl ethyl ketone. This solution was used as a transparent polymer resin binder solution, and was stirred and mixed with 2000 parts by mass of “Hals Hybrid IR-G205” (solid content concentration 29% solution) manufactured by Nippon Shokubai Co., Ltd. to prepare Paint-2.

(Paint-3)
As an organic dye having a main absorption peak at 593 nm, 3.6 parts by mass of “TAP-2” manufactured by Yamada Chemical Co., Ltd. was stirred and mixed in 1000 parts by mass of methyl ethyl ketone and dissolved. This solution was used as a transparent polymer resin binder solution, and was stirred and mixed with 2000 parts by mass of “Hals Hybrid IR-G205” (solid content concentration 29% solution) manufactured by Nippon Shokubai Co., Ltd. to prepare Paint-3.

(Paint-4)
As an organic dye having a main absorption peak at 575 nm, “TAP-5” manufactured by Yamada Chemical Industry Co., Ltd. was dissolved by stirring and mixing 1.9 parts by mass with 1000 parts by mass of methyl ethyl ketone. This solution was used as a transparent polymer resin binder solution, and was stirred and mixed with 2000 parts by mass of “Harus Hybrid IR-G205” (solid content concentration 29% solution) manufactured by Nippon Shokubai Co., Ltd. to prepare Paint-4.

(Paint-5)
As an organic dye having a main absorption peak at 583 nm, 1.2 parts by weight of “TAP-45” manufactured by Yamada Chemical Co., Ltd. was stirred and mixed in 1000 parts by weight of methyl ethyl ketone and dissolved. This solution was used as a transparent polymer resin binder solution, and was stirred and mixed with 2000 parts by mass of “Hals Hybrid IR-G205” (solid content concentration 29% solution) manufactured by Nippon Shokubai Co., Ltd. to prepare Paint-5.

[Example 1]
Using a polyester film for optics ("Lumirror" U46 manufactured by Toray, thickness of 100 μm), a commercially available hard coat agent ("Desolite" Z7528 manufactured by JSR) diluted with isopropyl alcohol to a solid content concentration of 30% on an easily adhesive surface, After coating with a micro gravure coater and drying at 80 ° C. for 1 minute, it was cured by irradiation with ultraviolet light 1.0 J / cm ² to provide a hard coat layer having a thickness of 5 μm. The refractive index of the base film is 1.65, the refractive index of the easy adhesion layer is 1.58, the refractive index of the hard coat layer is 1.52, and (refractive index of the easy adhesion layer) = {(of the base film Refractive index) × (refractive index of hard coat layer)} ^1/2 ± 0.02 was satisfied, and there were few interference fringes. The pencil hardness of the hard coat layer was 2H.

Next, a commercially available high refractive index / antistatic coating (JSR “OPSTAR” TU4005) is diluted with isopropyl alcohol to a solid content concentration of 8% on the hard coat layer forming surface, and coated with a micro gravure coater at 120 ° C. And dried for 1 minute, and then cured by irradiating with 1.0 J / cm ² of ultraviolet rays to form a high refractive index layer having a refractive index of 1.65 and a thickness of 135 nm on the hard coat layer.

  Next, the above-described low refractive index paint A was applied to the high refractive index layer forming surface as a low refractive index layer with a micro gravure coater. Subsequently, it was dried and cured at 130 ° C. for 1 minute to form a low refractive index layer having a refractive index of 1.36 and a thickness of 90 nm on the high refractive index layer.

  The properties of the produced antireflection film are shown in Tables 1 and 2 and FIG. The minimum reflectance is as low as 0.2%, the maximum reflectance is also 1.5%, and the difference between the maximum reflectance and the minimum reflectance is also 1.3%. Reflection characteristics with neutral color in the reflection spectrum were obtained. In addition, the scratch resistance is at a practical level of 4th grade.

[Examples 2 to 8]
An antireflection film was produced in the same manner as in Example 1 except that the thickness of the high refractive index layer and the thickness of the low refractive index layer were changed to those shown in Table 1.

The characteristics of the produced antireflection film are shown in Tables 1 and 2. As the ratio d _H / d _L between the thickness of the high refractive index layer and the thickness of the low refractive index layer is decreased, and the thickness of the high refractive index layer and the thickness of the low refractive index layer is decreased, the minimum reflectance becomes lower. However, the maximum reflectivity increases, and the difference between the maximum reflectivity and the minimum reflectivity increases, but in this range the minimum reflectivity is 0.6% or less, and the maximum reflectivity and reflectivity are also high. The difference was 2.5% or less, and a flat reflection spectrum and neutral reflection characteristics were obtained. In addition, the scratch resistance is at a practical level of 4th grade.

[Example 9]
An antireflection film was produced in the same manner as in Example 2 except that the low refractive index paint was changed from the paint A to the paint B. The characteristics of the produced antireflection film are shown in Tables 1 and 2. The lowest reflectance was as low as 0.1%, and the highest reflectance was 1.6%. A reflection characteristic with a neutral color in a flat reflection spectrum was obtained. However, the scratch resistance was slightly inferior to that of Example 3 and Example 2.

[Example 10]
An antireflection film was produced in the same manner as in Example 2 except that the low refractive index paint was changed from the paint A to the paint C. The characteristics of the produced antireflection film are shown in Tables 1 and 2. As in Example 2, a reflection characteristic having a low minimum reflectance, a flat reflection spectrum, and neutral color was obtained. However, the scratch resistance was as low as 1 to 2 and was insufficient. This is presumably because the bond between the silica fine particles having cavities inside the low refractive index layer and the siloxane compound as the matrix is weak.

[Example 11]
An antireflection film was produced in the same manner as in Example 1 except that the low refractive index paint was changed from the paint A to the paint D. The characteristics of the produced antireflection film are shown in Tables 1 and 2. Although a flat reflection spectrum and neutral reflection characteristics were obtained, the minimum reflectance exceeded 0.6%, and the antireflection performance was insufficient. Further, the scratch resistance was as low as first grade and was insufficient.

[Example 12]
An antireflection film was produced in the same manner as in Example 1 except that an optical polyester film (Toray “Lumirror” QT77, thickness 100 μm) having different easily adhesive layers on both sides was used as the base film. The characteristics of the produced antireflection film are shown in Tables 1 and 2. Since the easy-adhesion layer on the opposite side of the antireflection layer-forming surface of the base film is different, the minimum reflectance is slightly higher than in Example 1 due to its influence, but as in Example 1, the minimum reflectance is low, Reflective properties with a flat reflection spectrum and neutral color are obtained. In addition, the scratch resistance is at a practical level of 4th grade.

[Example 13]
In Example 1, the low refractive index coating E described above as a low refractive index layer was applied to the high refractive index layer forming surface with a micro gravure coater, dried at 120 ° C. for 1 minute, and then irradiated with ultraviolet rays 1.0 J / cm ² . And cured to form a low refractive index layer having a refractive index of 1.38 and a thickness of 90 nm. The characteristics of the produced antireflection film are shown in Tables 1 and 2. The minimum reflectivity is as low as 0.3%, and the maximum reflectivity is 1.7%, and the difference between the maximum reflectivity and the minimum reflectivity is 1.4%, and the minimum reflectivity is low and flat. Reflection characteristics with neutral color in the reflection spectrum were obtained. However, the scratch resistance was grade 3 and slightly inferior to Example 1.

[Comparative Example 1]
An antireflection film was produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was changed to 91 nm and the thickness of the low refractive index layer was changed to 110 nm. The properties of the produced antireflection film are shown in Tables 1 and 2 and FIG. Although the minimum reflectivity was as low as 0.2%, the maximum reflectivity was as high as 3.8%, resulting in a so-called V-shaped reflection spectrum, which was a film with a particularly blue-ish glare.

[Comparative Example 2]
An antireflection film was produced in the same manner as in Example 1 except that the thickness of the high refractive index layer was changed to 160 nm and the thickness of the low refractive index layer was changed to 80 nm. The characteristics of the produced antireflection film are shown in Tables 1 and 2. The difference between the maximum reflectance and the minimum reflectance was 0.6%, which was a very flat reflection spectrum, but the minimum reflectance was as high as 0.8%, and the antireflection performance was insufficient.

[Example 14]
After attaching “Sanitekt” (thickness 50 μm) manufactured by Sanei Kaken as a protective film to the antireflection surface of the antireflection film produced in Example 12, the die coater was applied to the base film surface opposite to the antireflection layer. The coating material-1 containing an organic pigment | dye was applied using, and it dried at 120 degreeC, the 10-micrometer-thick resin layer was formed, and the antireflection film was produced. Table 3 shows the transmittance of the produced antireflection film. The near-infrared absorbing dye had sufficient near-infrared shielding performance, and the total light transmittance was sufficiently high at 76.1%.

[Example 15]
An antireflection film was produced in the same manner as in Example 14 except that the paint containing the organic dye was changed to Paint-2. Table 3 shows the transmittance of the produced antireflection film. The near-infrared absorbing dye has sufficient near-infrared shielding performance, and the wavelength-selective absorbing dye having a main absorption peak at 593 nm has sufficient shielding ability for orange light which is an ineffective wavelength, and further has a total light transmittance. Was also sufficiently high at 60.2%.

[Example 16]
An antireflection film was produced in the same manner as in Example 14 except that the paint containing the organic dye was changed to Paint-3. Table 3 shows the transmittance of the produced antireflection film. The wavelength selective absorption dye having a main absorption peak at 593 nm has a sufficient shielding ability for orange light which is an ineffective wavelength, and the total light transmittance is also sufficiently high at 70.2%.

[Example 17]
An antireflection film was produced in the same manner as in Example 14 except that the paint containing the organic dye was changed to Paint-4. Table 3 shows the transmittance of the produced antireflection film. The wavelength selective absorption dye having a main absorption peak at 575 nm has a sufficient shielding ability for yellow light, which is an ineffective wavelength, and the total light transmittance is sufficiently high at 81.1%.

[Examples 18 to 19]
In Example 17, the thickness of the resin layer containing an organic dye was changed as shown in Table 3 to prepare an antireflection film. Table 3 shows the transmittance of the produced antireflection film. The wavelength selective absorption dye having a main absorption peak at 575 nm has a sufficient shielding ability for yellow light which is an ineffective wavelength, and the total light transmittance is sufficiently high.

[Example 20]
An antireflection film was produced in the same manner as in Example 14 except that the paint containing the organic dye was changed to Paint-5. Table 3 shows the transmittance of the produced antireflection film. The wavelength selective absorption dye having a sharp main absorption peak with a narrow half-value width at 583 nm has a sufficient shielding ability for yellow light which is an ineffective wavelength, and the total light transmittance is sufficiently high at 83.8%. It was.

[Example 21]
Antistatic paint consisting of 1 part by mass of bent-walled carbon nanotube (Toray “TOCANA S1”), 1 part by mass of polyvinylpyrrolidone and 1600 parts by mass of isopropyl alcohol is applied to an optical polyester film (“Lumirror” U34, Toray, thickness 188 μm). ) Was applied with a microgravure coater and then dried at 100 ° C. for 1 minute to form an antistatic layer having an average antistatic layer thickness of 5 nm and a carbon nanotube content of 3 mg / m ² . The surface resistivity of this film was 2 × 10 ⁷ Ω / □, the total light transmittance of the antistatic layer was 96%, and the haze was 0.3%. Furthermore, on the antistatic layer, an acrylic adhesive (“SK Dyne 1811L” manufactured by Soken Chemical Co., Ltd.) was bonded to a release film formed with a thickness of 25 μm.

  Next, an acrylic pressure-sensitive adhesive (“SK Dyne 1811L” manufactured by Soken Chemical Co., Ltd.) is formed to a thickness of 25 μm on the resin layer containing the organic pigment of the film produced in Example 20, and then the antistatic Laminated with the base film side of the film.

  This laminated film is laminated on a glass plate, and the 5 ° absolute reflection spectrum is measured by the method described above. The luminous regular reflectance obtained from the measurement is 0.79%, and an optical filter excellent in antireflection performance is obtained. It was.

  Since the antireflection film of the present invention has a low surface reflectance and a flatter reflection spectrum, the color is neutral. Moreover, since the antireflection film of a more preferred embodiment of the present invention has excellent surface scratch resistance, it is suitably used for the display surface of an image display device. Further, the anti-reflection film and the electromagnetic wave shielding film of the present invention are combined with a near-infrared shielding function and / or a color tone correction function by shielding light having an ineffective wavelength for an image display device in the range of 550 to 610 nm. , Image display devices such as cathode ray tube (CRT), plasma display panel (PDP), surface electrolysis display (SED), etc. by bonding with other functional films such as antistatic film, antiglare film, and gas barrier film The optical filter can be provided at low cost, and is suitably used for an image display device by being attached to the surface of the image display surface and / or its front plate via an adhesive layer or an adhesive layer.

It is the figure which represented typically the cross section of the antireflection film of the preferable aspect of this invention. It is the figure which represented typically the cross section of an example of the optical filter using the antireflection film of the preferable aspect of this invention. It is a figure showing the 5 degree absolute reflection spectrum of the antireflection film shown in Example 1 and Comparative Example 1 of the present invention.

Explanation of symbols

1 Protective film (f)
2 Low refractive index layer (e)
3 High refractive index layer (d)
4 Hard coat layer (b)
5 Base film (a)
6 Resin layer containing organic dye (g)
7 Adhesive layer (h)
8 Release film (i)
9 Antireflection layer (c)
DESCRIPTION OF SYMBOLS 10 Base film 11 Antistatic layer 12 Adhesive layer 13 Panel

Claims (13)

One surface of the substrate film, the hard coat layer, high refractive index layer, a low refractive index layer is a reflection preventing film formed in this order, a thickness d _H of the high refractive index layer of the antireflective layer is 105~160nm The thickness d _L of the low refractive index layer is in the range of 75 to 110 nm, and the ratio d _H / d _L of the thickness d _H of the high refractive index layer and the thickness d _L of the low refractive index layer is 1. An antireflection film in the range of 0 to 1.9. Product _d H · _{n H} a thickness _{d H} and a refractive index _{n H} of the high refractive index layer is 165～276Nm, and the product _d L · _{n L} of the refractive index _{n L} and thickness _{d L} of the low refractive index layer is 96 to The antireflection film according to claim 1, which is in a range of 163 nm.   The antireflection film according to claim 1 or 2, wherein the low refractive index layer comprises a coating obtained by curing a paint containing silica fine particles having cavities therein.   The antireflection film according to claim 3, wherein the coating material forming the low refractive index layer is a coating material further containing a siloxane compound and a curing agent. The antireflection film according to claim 4, wherein the siloxane compound is a hydrolyzate and / or condensate of one or more silane compounds selected from the following general formulas (1) to (5).
R ¹ Si (OR ⁶ ) ₃ (1)
(R ¹ represents a fluoroalkyl group having 3 to 17 fluorine atoms. R ⁶ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, which may be the same or different.)
R ² Si (OR ⁷ ) ₃ (2)
(R ² represents a group selected from vinyl group, allyl group, alkenyl group, acrylic group, methacryl group, methacryloxy group, cyano group, epoxy group, glycidoxy group, amino group, and substituted products thereof. R ⁷ Represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxyethyl group, or an acetyl group, which may be the same or different.
R ³ Si (OR ⁸ ) ₃ (3)
(R ³ represents a group selected from hydrogen, an alkyl group, an aryl group, and a substituent thereof. R ⁸ represents a methyl group, an ethyl group, a propyl group, or a butyl group, and each is the same or different. Is also good.)
R ⁴ R ⁵ Si (OR ⁹ ) ₂ (4)
(R ⁴ and R ⁵ each represents a group selected from hydrogen, an alkyl group, a fluoroalkyl group, an aryl group, an alkenyl group, a methacryloxy group, an epoxy group, a glycidoxy group, an amino group, and a substituent thereof. Each may be the same or different, and R ⁹ represents a methyl group, an ethyl group, a propyl group, an isopropyl group, or an acetyl group, and each may be the same or different.)
Si (OR ¹⁰ ) ₄ (5)
(R ¹⁰ represents a methyl group or an ethyl group, and may be the same or different.)   The antireflection film according to claim 4 or 5, wherein the curing agent is an aluminum chelate compound and / or a magnesium chelate compound.   A resin layer containing at least one organic dye is laminated on the surface opposite to the surface on which the hard coat layer, high refractive index layer, and low refractive index layer of the base film are laminated. The antireflection film according to any one of 6.   The antireflection film according to claim 7, wherein the transmittance at a wavelength of 850 nm is 15% or less, and the transmittance at a wavelength of 950 nm to 1150 nm is 10% or less.   The antireflection film according to claim 7 or 8, which has a main absorption peak in a wavelength range of 550 to 610 nm.   The antireflection film according to claim 9, wherein the half width of the main absorption peak is 50 nm or less.   The optical filter which provided the antireflection film in any one of Claims 1-10 in the surface layer. The resin layer containing an organic dye having a main absorption peak in a wavelength range of 565 to 585 nm, and an antistatic layer having a surface resistivity of 10 ⁵ Ω / □ or more and 10 ⁹ Ω / □ or less. Optical filter.   An image display device comprising the optical filter according to claim 11.

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