JP2006268031A - Antireflection film, polarizing plate, and image display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film having low reflectance and excellent scratch resistance and contamination resistance, and to provide a polarizing plate and an image display apparatus using the film. <P>SOLUTION: The antireflection film has a low refractive index layer comprising a cured film of a fluoropolymer as the outermost layer on a transparent supporting body, wherein the fluoropolymer is a copolymer containing a polysiloxane structure in a main chain and comprising a repeating unit of a fluoro-vinyl monomer, a repeating unit having a (meth)acryloyl group, and a repeating unit having a hydroxyl group. The content of the repeating unit having a (meth)acryloyl group in the copolymer is 30 to 70 mol% of the whole repeating units except for a polysiloxane moiety. The content of the repeating unit having a hydroxyl group is 5 to 40 mol% of the whole repeating units except the polysiloxane moiety. The low refractive index layer contains inorganic fine particles having an average particle size of 30 to 100% of the layer thickness. A polarizing plate and an image display apparatus using the antireflection film are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection film, a polarizing plate using the antireflection film, and an image display device.

  In general, the antireflection film is used in a display device such as a cathode ray tube display (CRT), a plasma display (PDP), an electroluminescence display (ELD), or a liquid crystal display (LCD), and a contrast reduction or image due to reflection of external light. In order to prevent reflection of light, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

  Such an antireflection film can be generally produced by forming a low refractive index layer having an appropriate film thickness and a lower refractive index than the support on the support. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. Further, since the antireflection film is used on the outermost surface of the display, high scratch resistance is required. In order to realize high scratch resistance in a thin film having a thickness of about 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  To lower the refractive index of the material, there are means of (1) introducing fluorine atoms and (2) lowering the density (introducing voids). The low refractive index and high scratch resistance are both difficult problems.

  As a method for increasing the film strength to some extent, there is a method using a fluorine-containing sol-gel film as described in Patent Documents 1 and 2, but (1) a long time is required for curing, and the production load is large. (2) There is no resistance to saponification liquid (alkali treatment liquid), and when the saponification treatment is performed on the triacetyl cellulose (TAC) surface, a great restriction such as being impossible after film formation of the antireflection film occurs.

  On the other hand, Patent Documents 3 to 5 describe means for reducing the coefficient of friction on the coating surface and improving the scratch resistance by introducing a polysiloxane structure into the fluorine-containing polymer. This means is effective to some extent for improving scratch resistance, but sufficient scratch resistance cannot be obtained only by this method for a film having an essential film strength and interfacial adhesion.

  In Patent Document 6, by using a fluorine-containing polymer and inorganic fine particles in combination, the film strength and interfacial adhesion are improved and scratch resistance is improved without being restricted by long-time thermal curing or saponification treatment. Means for making it described.

JP 2002-265866 A JP 2002-317152 A JP-A-11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A International Publication No. 04/017105 Pamphlet

However, in the antireflection film described in Patent Document 6, the inorganic fine particles are not sufficiently dispersed in the fluorine-containing polymer matrix, and there are cases where the inorganic fine particles are coarsely and densely formed in the film, resulting in an increase in haze. This problem is particularly problematic with a low reflection film having a smooth surface that does not have antiglare properties.
An object of the present invention is to provide an antireflection film having sufficient antireflection properties and improved scratch resistance. Furthermore, it is providing the polarizing plate and display apparatus using such an antireflection film.

As a result of intensive studies, the present inventor can maintain a small haze while maintaining high film strength, interfacial adhesion and scratch resistance by dispersing inorganic fine particles in a binder comprising a fluorine-containing polymer having a specific structure. I found.
According to the present invention, an antireflection film, a polarizing plate and an image display device having the following constitution are provided, and the above object is achieved.
1. An antireflection film having a low refractive index layer made of a cured film of a fluorine-containing polymer as an outermost layer on a transparent support,
The fluoropolymer has a polysiloxane structure in the main chain and a repeating unit composed of a fluorine-containing vinyl monomer, a repeating unit having a (meth) acryloyl group in the side chain,
A copolymer comprising a repeating unit having a hydroxyl group in the side chain,
The content of the repeating unit having a (meth) acryloyl group in the side chain in the copolymer is 30 to 70 mol% of all repeating units other than the polysiloxane moiety,
The content of the repeating unit having a hydroxyl group in the side chain in the copolymer is 5 to 40 mol% of all repeating units other than the polysiloxane moiety,
The antireflective film characterized in that the low refractive index layer contains at least one inorganic fine particle having an average particle size in the range of 30% to 100% of the thickness of the low refractive index layer.
2. 2. The antireflection film as described in 1 above, wherein the copolymer is a copolymer represented by the following general formula 1.

[In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, and m represents 0 or 1. X represents a hydrogen atom or a methyl group. A represents a repeating unit having a hydroxyl group in the side chain, and B represents a repeating unit composed of any vinyl monomer. A and B may be composed of a single component or a plurality of components. Y represents a constituent component containing a polysiloxane structure in the main chain. x, y, z1, and Z2 represent mol% of each repeating unit based on all repeating units other than Y, and 30 ≦ x ≦ 60, 30 ≦ y ≦ 70, 5 ≦ z1 ≦ 40, 0 ≦ A value satisfying z2 ≦ 35 is represented. However, x + y + z1 + Z2 = 100 (mol%). a represents mass% of the component Y in the copolymer. ]

3. 3. The antireflection film as described in 2 above, wherein the copolymer represented by the general formula 1 is a copolymer represented by the following general formula 2.

  In General Formula 2, X, Y, x, y, and a each have the same meaning as in General Formula 1. B represents a repeating unit from an arbitrary vinyl monomer, and may be composed of a single component or a plurality of components. z1 and z2 represent mol% of each repeating unit based on all repeating units other than Y, and represent values satisfying 5 ≦ z1 ≦ 40 and 0 ≦ z2 ≦ 35. However, x + y + z1 + z2 = 100 (mol%). n represents an integer satisfying 2 ≦ n ≦ 10.

4). 4. The antireflection film as described in 3 above, wherein the copolymer represented by the general formula 2 satisfies 40 ≦ x ≦ 60, 40 ≦ y ≦ 60, 5 ≦ z1 ≦ 40, and z2 = 0.

5. 5. The antireflection film as described in any one of 1 to 4 above, wherein the polysiloxane structure contained in the main chain is a structure represented by the following general formula 3.

In General Formula 3, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or a cyano group, and R ^{5 to} R ¹⁰ each independently represent hydrogen. Represents an atom, an alkyl group, a haloalkyl group or a phenyl group; p and q each independently represent an integer of 1 to 10. m and n each independently represents an integer of 0 to 10, and r represents an integer of 10 to 1000.
6). 6. The antireflection film as described in any one of 1 to 5 above, which has at least one hard coat layer between the transparent support and the low refractive index layer.
7). The antireflection film as described in any one of 1 to 6 above, wherein the inorganic fine particles are silica fine particles.
8). 8. The antireflection according to any one of 1 to 7, wherein the low refractive index layer further contains at least one silica fine particle having a particle diameter of less than 25% of the thickness of the low refractive index layer. the film.
9. 7 or 8 above, wherein at least one of the silica fine particles contained in the low refractive index layer is hollow silica fine particles, and the refractive index of the silica fine particles is 1.17 to 1.40. The antireflection film as described in 1.
10. At least one hard coat layer is a light diffusing layer, and the light diffusing layer is in the range of 0.01 to 0.2% with respect to the light intensity at an output angle of 0 ° of the scattered light profile of the goniophotometer. 10. The antireflection film as described in any one of 6 to 9 above, which has a scattered light intensity of 0 °.
11. There is at least one high refractive index layer between the transparent support and the low refractive index layer, and the high refractive index layer is mainly composed of titanium dioxide and at least one element selected from cobalt, aluminum, and zirconium. 11. The antireflection film as described in any one of 1 to 10 above, which is a constituent layer having a refractive index of 1.55 to 2.40, containing inorganic fine particles containing. 12 The polarizing plate which has a polarizing film and the protective film provided in the both sides of this polarizing film WHEREIN: At least one of this protective film is an antireflection film in any one of said 1-11.
13. Among the protective films, the film other than the antireflection film is an optical compensation film having an optically anisotropic layer, and the optically anisotropic layer has a negative birefringence composed of a compound having a discotic structural unit. The disc surface of the discotic structural unit is inclined with respect to the surface protective film surface, and the angle formed by the disc surface of the discotic structural unit and the surface protective film surface is optical anisotropy. 13. The polarizing plate as described in 12 above, wherein the polarizing plate changes in the layer depth method.
14 14. An image display device, wherein the antireflection film described in 1 to 11 or the polarizing plate described in 12 or 13 is disposed on an image display surface.
15. 14. A TN, STN, VA, IPS, or OCB mode transmissive, reflective, or transflective liquid crystal display device having at least one polarizing plate described in 12 or 13 above.

  The antireflection film of the present invention is excellent in scratch resistance while having sufficient antireflection properties. Further, the display device provided with the antireflection film of the present invention and the display device provided with the polarizing plate using the antireflection film of the present invention have little reflection of external light and reflection of the background, and extremely high visibility. .

A basic configuration of an antireflection film suitable as an embodiment of the present invention will be described with reference to the drawings.
The cross-sectional view schematically shown in FIG. 1 (a) is an example of the antireflection film of the present invention. The antireflection film 1 comprises a transparent support 2, a hard coat layer 3, a high refractive layer 4, and a low refractive index. It has a layer structure in the order of the rate layer 5. The refractive index of the high refractive index layer 4 is preferably in the range of 1.50 to 2.00, and the refractive index of the low refractive index layer 5 is preferably in the range of 1.35 to 1.49. In the present invention, the hard coat layer may be provided separately from the high refractive layer as described above, or may be provided as a high refractive index hard coat layer having the function of the high refractive layer. Further, the hard coat layer may be a single layer or may be composed of a plurality of layers, for example, 2 to 4 layers. Further, the hard coat layer may be omitted. Accordingly, the hard coat layer shown in FIG. 1 is not essential, but it is preferable that any of these hard coat layers is applied to impart film strength. The low refractive index layer is coated on the outermost layer.

The cross-sectional view schematically shown in FIG. 1B is an example of the antireflection film of the present invention. The antireflection film 1 includes a transparent support 2, a hard coat layer 3, a medium refractive index 7, and a high refractive index. It has a layer structure in the order of the layer 8 and the low refractive index layer (outermost layer) 5.
The transparent support 2, the medium refractive index layer 7, the high refractive index layer 8, and the low refractive index layer 5 have refractive indexes that satisfy the following relationship.
Refractive index of high refractive index layer> refractive index of medium refractive index layer> refractive index of transparent support> refractive index of low refractive index layer In the layer structure as shown in FIG. As described above, the intermediate refractive index layer satisfies the following formula (I), the high refractive index layer satisfies the following formula (II), and the low refractive index layer satisfies the following formula (III). It is preferable at the point which can produce the antireflection film which has prevention performance.

Formula (I)
(Hλ / 4) × 0.7 <n ₁ d ₁ <(hλ / 4) × 1.3
In the formula (I), h is a positive integer (generally 1, 2 or 3), n ₁ is the refractive index of the medium refractive index layer, and d ₁ is the layer thickness (nm) of the medium refractive index layer. It is. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

Formula (II)
(Iλ / 4) × 0.7 <n ₂ d ₂ <(iλ / 4) × 1.3
In formula (II), i is a positive integer (generally 1, 2 or 3), n ₂ is the refractive index of the high refractive index layer, and d ₂ is the layer thickness (nm) of the high refractive index layer. It is. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

Formula (III)
(Jλ / 4) × 0.7 <n ₃ d ₃ <(jλ / 4) × 1.3
In formula (III), j is a positive odd number (generally 1), n ₃ is the refractive index of the low refractive index layer, and d ₃ is the layer thickness (nm) of the low refractive index layer. λ is the wavelength (nm) of visible light, and is a value in the range of 380 to 680 nm.

In the layer configuration as shown in FIG. 1B, the medium refractive index layer satisfies the following mathematical formula (IV), the high refractive index layer satisfies the following mathematical formula (V), and the low refractive index layer satisfies the following mathematical formula (VI). Is particularly preferred.
In the following formula, λ is 500 nm, h is 1, i is 2, and j is 1.
Formula (IV)
(Hλ / 4) × 0.80 <n ₁ d ₁ <(hλ / 4) × 1.00
Formula (V)
(Iλ / 4) × 0.75 <n ₂ d ₂ <(iλ / 4) × 0.95
Formula (VI)
(Jλ / 4) × 0.95 <n ₃ d ₃ <(jλ / 4) × 1.05

  The high refractive index, medium refractive index, and low refractive index described here refer to the relative refractive index between layers. Moreover, in FIG.1 (b), the high refractive index layer is used as a light interference layer, and the antireflection film which has the very outstanding antireflection performance can be produced.

[Low refractive index layer]
The refractive index of the low refractive index layer of the antireflection film of the present invention is preferably in the range of 1.20 to 1.49, more preferably in the range of 1.30 to 1.44.
Further, the low refractive index layer preferably satisfies the following formula (VII) from the viewpoint of reducing the reflectance.
Formula (VII)
(Mλ / 4) × 0.7 <n ₃ d ₃ <(mλ / 4) × 1.3
In the formula, m is a positive odd number, n ₃ is the refractive index of the low refractive index layer, and d ₃ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (VII) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (VII) exists in the said wavelength range.

The material for forming the low refractive index layer will be described below.
The low refractive index layer contains a fluorine-containing polymer as a low refractive index binder. The fluorine-containing polymer has a polysiloxane structure in the main chain, and must include a repeating unit composed of a fluorine-containing vinyl monomer, a repeating unit having a (meth) acryloyl group in the side chain, and a repeating unit having a hydroxyl group in the side chain. It is a copolymer as a constituent component.
The content of the (meth) acryloyl group-containing repeating unit in the copolymer is in the range of 30 to 70 mol% of all repeating units other than the polysiloxane moiety, and the copolymer weight of the repeating unit having a hydroxyl group in the side chain. Content in coalescence is the range of 5-40 mol% among all the repeating units other than a polysiloxane site | part.
The copolymer-derived component preferably occupies 80% by mass or more, and particularly preferably 90% by mass or more of the solid content of the film.

(Copolymer containing polysiloxane structure)
The copolymer used for the low refractive index layer contains a polysiloxane structure in the main chain. There is no particular limitation on the method for introducing the polysiloxane structure into the main chain. A method using a polymer-type initiator such as Kogyo Co., Ltd.), a polymerization initiator, a reactive group derived from a chain transfer agent (for example, a mercapto group, a carboxyl group, a hydroxyl group, etc.) is introduced into the polymer end, Examples thereof include a method of reacting with terminal or both-terminal reactive group (eg, epoxy group, isocyanate group, etc.)-Containing polysiloxane, a method of copolymerizing a cyclic siloxane oligomer such as hexamethylcyclotrisiloxane by anionic ring-opening polymerization, and the like. Among them, a method using an initiator having a polysiloxane structure is easy and preferable.

As the polysiloxane structure introduced into the copolymer of the present invention, the structure represented by the general formula 3 is particularly preferable.
In General Formula 3, R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 5 carbon atoms. Examples include a methyl group and an ethyl group), an aryl group ( The number of carbon atoms is preferably 6 to 10. Examples include phenyl group and naphthyl group.), Alkoxycarbonyl group (preferably having 2 to 5 carbon atoms. Examples include methoxycarbonyl group and ethoxycarbonyl group), or cyano. Represents an alkyl group and a cyano group, and a methyl group and a cyano group are particularly preferable.

R ^{5 to} R ¹⁰ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 5. Examples include a methyl group and an ethyl group), and a haloalkyl group (a fluorinated alkyl group having 1 to 5 carbon atoms). (Examples include a trifluoromethyl group and a pentafluoroethyl group.) Or a phenyl group, preferably a methyl group or a phenyl group, and particularly preferably a methyl group.

  p and q each independently represent an integer of 1 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. m and n each independently represents an integer of 0 to 10, preferably an integer of 1 to 6, and particularly preferably an integer of 2 to 4. r represents an integer of 10 to 1000, preferably an integer of 20 to 500, and particularly preferably an integer of 50 to 200.

  The polysiloxane structure is preferably introduced in the range of 0.01 to 20% by mass in the copolymer of the present invention, more preferably in the range of 0.05 to 10% by mass, Especially preferably, it is a case where it introduce | transduces in 0.5-5 mass%.

  By introducing the polysiloxane structure, the film is imparted with antifouling property and dustproof property, and the film surface is provided with slipperiness, which is advantageous for scratch resistance.

Fluorine-containing vinyl monomers include fluoroolefins (eg, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (eg, biscoat) 6FM (trade name, manufactured by Osaka Organic Chemical Co., Ltd.), M-2020 (trade name, manufactured by Daikin), etc., and fully or partially fluorinated vinyl ethers, etc. are preferable, but perfluoroolefins are preferable, and refractive index, dissolution From the viewpoints of properties, transparency, availability, etc., hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorine-containing vinyl monomers can lower the refractive index but lowers the film strength.
The fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. Is the case.

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

  If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. In the present invention, those in which the (meth) acryloyl group-containing repeating unit is introduced in the range of 30 to 70 mol% are useful, and it is particularly preferable to occupy 40 to 60 mol%.

  In addition to the repeating unit from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, the copolymer has a repeating group having a hydroxyl group in the side chain in order to have affinity for inorganic fine particles. It is essential to contain units. The repeating unit having a hydroxyl group may be one type or two or more different repeating units, and those introduced in a range of 5 to 40 mol% of the copolymerized units in total are useful. It is preferably introduced in the range of 35 mol%.

  In order to introduce a repeating unit having a hydroxyl group in the side chain into the copolymer, a monomer having a hydroxyl group in the side chain may be copolymerized. As the monomer having a hydroxyl group in the side chain, many monomers are known and are not particularly limited. For example, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene Examples include glycol vinyl ether and 4- (hydroxymethyl) cyclohexyl methyl vinyl ether.

In the copolymer used for the low refractive index layer, in addition to the repeating unit from the above fluorine-containing vinyl monomer, the repeating unit having a (meth) acryloyl group in the side chain, and the repeating unit having a hydroxyl group in the side chain, to the substrate Other vinyl monomers can be suitably copolymerized from various viewpoints such as adhesion of the polymer, Tg of the polymer (contributing to film hardness), solubility in a solvent, transparency, and dust / stain resistance. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 40 mol% in total in the copolymer, and more preferably in the range of 0 to 30 mol%. The range of 0 to 20 mol% is particularly preferable.
The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic) Acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tertbutylacrylamide, N-cyclohexylacrylamide, etc.), methacrylamides (N, N-dimethylmethacrylic) Amide), acrylonitrile and the like.

As a preferred form of the copolymer used in the present invention, the general formula 1 is mentioned. In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O-**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, -CONH- (CH ₂ ) ₃ -O-**, * -CH ₂ CH (OH) CH ₂ -O-**, * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* represents the connecting site on the polymer main chain side, and ** represents the connecting site on the (meth) acryloyl group side. And the like.
m represents 0 or 1.
X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In general formula 1, A represents a repeating unit containing a hydroxyl group. B represents a repeating unit from any vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Adhesion to a substrate, Tg of a polymer (in terms of film hardness) Can be selected from various viewpoints such as solubility in solvents, transparency, slipperiness, dustproof / antifouling properties, etc., even if it is composed of one or more vinyl monomers depending on the purpose good.

Preferred examples of A include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, 8-hydroxyoctyl vinyl ether, diethylene glycol vinyl ether, triethylene glycol vinyl ether, 4- (hydroxymethyl) cyclohexyl methyl vinyl ether and the like.
Preferred examples of B include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, glycidyl vinyl ether and allyl vinyl ether, and vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate. , (Meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane, styrene, p Examples include styrene derivatives such as hydroxymethylstyrene, unsaturated carboxylic acids such as crotonic acid, maleic acid and itaconic acid, and derivatives thereof. Kill, but is preferably vinyl ether derivatives and vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, z1, and z2 represent mol% of each repeating unit based on all repeating units other than Y, and 30 ≦ x ≦ 60, 30 ≦ y ≦ 70, 5 ≦ z1 ≦ 40, 0 ≦ A value satisfying z2 ≦ 35 is represented. Preferably, 35≤x≤55, 30≤y≤60, 5≤z1≤35, 0≤z2≤35, particularly preferably 40≤x≤55, 40≤y≤55, 5≤z1≤. 35, 0 ≦ z2 ≦ 35.

  Y represents a constituent component containing a polysiloxane component in the main chain, and a preferable example includes a structure derived from the above-described polysiloxane structure-containing initiator.

  a represents mass% of the Y component, preferably 0.01 ≦ a ≦ 20, more preferably 0.05 ≦ a ≦ 10, and particularly preferably 0.5 ≦ a ≦ 5. It is.

As a particularly preferred form of the copolymer used in the present invention, the above general formula 2 can be mentioned. In the general formula 2, X, Y and B have the same meaning as in the general formula 1, and the preferred range is also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a repeating unit from any vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example shown in the said General formula 1 is applicable.
z1 and z2 represent the mol% of each repeating unit based on all repeating units other than Y, and represent values satisfying 5 ≦ z1 ≦ 40 and 0 ≦ z2 ≦ 35. It is preferable that 5 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 5 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5. Preferably, 40 ≦ x ≦ 60, 40 ≦ y ≦ 60, 5 ≦ z1 ≦ 40, and z2 = 0.

  For example, the copolymer represented by the general formula 1 or 2 is synthesized by the above-described method, into a copolymer of hexafluoropropylene and hydroxyalkyl vinyl ether having a polysiloxane structure in the main chain by any of the above-described methods ( It can be synthesized by introducing a (meth) acryloyl group.

  In the general formula 1 or 2, it means that the mode of bonding of the copolymer (block copolymer, random copolymer, graft copolymer, etc.) is limited to any one unless otherwise specified. is not.

  Although the preferable example of the copolymer useful by this invention is shown below, this invention is not limited to these.

  In the formula, 50 / y / z represents a molar ratio, a represents mass%, and VPS-1001 represents a component derived from a polysiloxane-containing macroazo initiator (VPS1001 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. The same).

  In the formula, 50 / y / z indicates a molar ratio, and a indicates mass%. VPS-1001 indicates a component derived from a polysiloxane-containing macroazo initiator (VPS1001 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. (the same applies hereinafter).

  In the formula, x / y / z2 represents a molar ratio, and a represents mass% in the copolymer. VPS-0501 represents a component derived from a polysiloxane-containing macroazo initiator (VPS0501: trade name) manufactured by Wako Pure Chemical Industries.

  In the formula, x / y / z1 / z2 each represents a molar ratio, and a represents mass%.

  In the formula, x / y / z1 represents a molar ratio, and a represents mass%.

  In the formula, the ratio of the components of the vinyl monomer (50/40/10) indicates a molar ratio, a indicates mass%, and r indicates the number of dimethylsiloxane units.

  The copolymer preferably has a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography in the range of 5,000 to 500,000, and more preferably in the range of 5,000 to 300,000. preferable.

  The copolymer is synthesized by synthesizing a precursor of a hydroxyl group-containing polymer by various polymerization methods, for example, solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, emulsion polymerization, and the like. Can be carried out by introducing a (meth) acryloyl group. The polymerization reaction can be carried out by any operation such as batch, semi-continuous or continuous.

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

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

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

The reaction pressure can be selected as appropriate, but it is usually 1-100 kg / cm ² , particularly about 1-30 kg / cm ² . The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

(Multifunctional ionizing radiation curable compound)
In the low refractive index layer of the present invention, in addition to the fluoropolymer of the present invention,
It is preferable to use an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer. The functional group for ionizing radiation curing is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Particularly preferably, a compound containing two or more (meth) acryloyl groups in one molecule described below can be used.

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

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

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

  For the purpose of lowering the refractive index, it is preferable to use a monomer containing a fluorine atom in the molecule. As a specific example, for example, a compound described in JP-A-2005-248142 is used. Can do.

(Inorganic fine particles)
Next, the inorganic fine particles contained in the low refractive index layer of the present invention will be described below.
The average particle size of the inorganic fine particles is in the range of 30% to 100% of the thickness of the low refractive index layer, more preferably 35% to 80%, still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the inorganic fine particles is preferably 30 nm or more and 100 nm or less, more preferably 35 nm or more and 80 nm or less, and still more preferably 40 nm or more and 60 nm or less.
If the particle size of the inorganic fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The average particle size of the inorganic fine particles can be measured with a Coulter counter.

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

Since the inorganic fine particles are contained in the low refractive index layer, a low refractive index is desirable. Examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. What has been described above for silica fine particles also applies to other inorganic particles.

In order to reduce the refractive index of the particles, pores can be introduced on the surface or inside of the particles. Porous particles and hollow particles can be used. In order to further reduce the increase in the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles, and the hollow silica fine particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17. -1.35, more preferably 1.17-1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x represented by the following formula (VIII) is preferably 10 to 60%, more preferably 20 to 60. %, Most preferably 30-60%.
(Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, the low refractive index is less than 1.17. Rate particles do not hold.
The refractive index of these hollow silica particles can be measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

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

  A method for producing hollow fine particles is described, for example, in JP-A-2001-233611. Moreover, the manufacturing method of porous particle | grains is described in each gazette, such as Unexamined-Japanese-Patent No. 2003-327424, 2003-335515, 2003-226516, 2003-238140, etc., for example.

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

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

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

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

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
Although there is no special restriction | limiting in the usage-amount of these surface treating agents, 1-100 mass parts is preferable with respect to an inorganic particle, More preferably, it is 1-50 mass parts, Most preferably, it is 2-30 mass parts.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO2004 / 017105.

(Organosilane compound)
At least one of the hard coat layer and the low refractive index layer constituting the antireflection film of the present invention is at least one of an organosilane compound, a hydrolyzate thereof, and a partial condensate in the coating solution forming the layer. It is preferable from the viewpoint of scratch resistance that it contains a so-called sol component (hereinafter referred to as such). The sol component may be a mixture of two or more of an organosilane compound, a hydrolyzate thereof, and a partial condensate.
In particular, the low refractive index layer preferably contains the sol component in order to achieve both antireflection performance and scratch resistance, and the hard coat layer is an inorganic material dispersed in the self-layer and / or other adjacent layers. It is desirable to contain the sol component for the purpose of increasing the film strength of the system by interfacial bonding with oxide particles and thereby improving the scratch resistance. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product, which becomes a binder for the layer. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably one represented by the following general formula 4.
Formula _{^{4: (R 10) m -Si}} (X) 4-m
In the above general formula 4, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Specifically, methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl, etc. Is mentioned. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

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

When there are a plurality of R ¹⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group, and among them, an organosilane compound having a vinyl polymerizable substituent represented by the following general formula 5 is preferable.

In the general formula 5, R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferred, and * -COO-** is particularly preferred. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

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

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula 4, and is preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in formula 4, preferably a halogen atom, a hydroxyl group, or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, or 1 to 3 carbon atoms. Are more preferable, and a methoxy group is particularly preferable.

  Two or more compounds of the general formulas 4 and 5 may be used in combination. Specific examples of the compounds represented by the general formulas 4 and 5 are shown below, but are not limited thereto.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable.

  The hydrolysis reaction and / or condensation reaction of organosilane is generally performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples thereof include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium; metal chelate compounds having a metal such as Zr, Ti or Al as a central metal. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant (pKa value (25 ° C.)) of 4.5 or less in water, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

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

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

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 90%, preferably in the range of 20% to 70%.

0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, in the presence or absence of the above solvent, and in the presence of a catalyst. It is carried out by stirring at 25 to 100 ° C.
The hydrolysis / condensation reaction is carried out by using an alcohol represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ Is an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms), and a compound represented by Zr, Ti or It is preferably carried out by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal selected from Al as a central metal.

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

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

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. If it is less than 0.01% by mass, the condensation reaction of the organosilane compound is slow, and the durability of the coating film may be deteriorated. On the other hand, if it exceeds 50% by mass, the hydrolyzate and / or partial condensate of the organosilane compound And the storage stability of the composition containing the metal chelate compound may be deteriorated, which is not preferable.

  In addition to the composition containing the hydrolyzate and / or partial condensate of the organosilane compound and the metal chelate compound in the coating solution for the hard coat layer to the low refractive index layer, a β-diketone compound and / or a β-ketoester compound Is preferably added. This will be further described below.

As the β-diketone compound and / or β-ketoester compound, it is preferable to use a β-diketone compound and / or a β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ , which form each layer. It can act as a stability improver for the composition. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved.
R ⁴ and R ⁵ constituting the β- diketone compound and / or β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane -Dione, 5-methyl-hexane-dione and the like can be mentioned. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

The content of the hydrolyzate and / or partial condensate of the organosilane compound is preferably small for a surface layer that is a relatively thin film and large for a lower layer that is a thick film. In the case of a surface layer such as a low refractive index layer, 0.1 to 50% by mass of the total solid content of the containing layer (addition layer) is preferable, 0.5 to 20% by mass is more preferable, and 1 to 10% by mass is preferable. Most preferred.
The amount added to the layers other than the low refractive index layer is preferably 0.001 to 50 mass%, more preferably 0.01 to 20 mass%, and more preferably 0.05 to 10 mass% of the total solid content of the containing layer (addition layer). More preferably, it is 0.1 to 5% by mass.
In the present invention, first, a composition containing a hydrolyzate and / or partial condensate of the organosilane compound and a metal chelate compound is prepared, and a liquid in which a β-diketone compound and / or a β-ketoester compound is added thereto is prepared. It is preferable to coat by coating it in at least one coating solution of a hard coat layer or a low refractive index layer.

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

(Inorganic filler)
In the antireflection film of the present invention, an inorganic filler is preferably added to each layer on the transparent support. The inorganic filler added to each layer may be the same or different, and the type and amount added are preferably adjusted appropriately according to the required performance of each layer, such as refractive index, film strength, film thickness, and coatability. .
As already described, the inorganic filler used in the low refractive index layer preferably contains silica fine particles.

The shape of the inorganic filler used in the present invention is not particularly limited, and for example, any of a spherical shape, a plate shape, a fiber shape, a rod shape, an indeterminate shape, a hollow shape, and the like are preferably used. Good and more preferable. Further, the kind of the inorganic filler is not particularly limited, but an amorphous one is preferably used, and a metal oxide, nitride, sulfide or halide is preferably used. Is particularly preferred. As metal atoms, Na, K, Mg, Ca, Ba, Al, Zn, Fe, Cu, Ti, Sn, In, W, Y, Sb, Mn, Ga, V, Nb, Ta, Ag, Si, B Bi, Mo, Ce, Cd, Be, Pb, Zr, Ni and the like. In order to obtain a transparent cured film, the average particle diameter of the inorganic filler is preferably set to a value within the range of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm, and still more preferably. 0.001 to 0.06 μm. Here, the average particle diameter of the particles is measured by a Coulter counter.
Although the usage method of the inorganic filler in this invention is not restrict | limited in particular, For example, it can use in a dry state or can also be used in the state disperse | distributed to water or the organic solvent.

In the present invention, for the purpose of suppressing aggregation and sedimentation of the inorganic filler, it is also preferable to use a dispersion stabilizer in combination with the coating solution for forming each layer. As the dispersion stabilizer, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivative, polyamide, phosphate ester, polyether, surfactant, silane coupling agent, titanium coupling agent and the like can be used. In particular, a silane coupling agent is preferable because the film after curing is strong. Although the addition amount of the silane coupling agent as a dispersion stabilizer is not particularly limited, for example, the value is preferably 1 part by mass or more with respect to 100 parts by mass of the inorganic filler. Also, the method of adding the dispersion stabilizer is not particularly limited, but a hydrolyzed one can be added, or a dispersion stabilizer silane coupling agent and an inorganic filler are mixed. Later, a method of further hydrolysis and condensation can be employed, but the latter is more preferred.
Inorganic fillers suitable for other layers will be described later.

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

  For the purpose of imparting properties such as antifouling properties, water resistance, chemical resistance, and slipping properties, known silicone-based or fluorine-based antifouling agents, slipping agents, and the like can be appropriately added. When these additives are added, it is preferably added in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass of the total solid content of the low n layer. Particularly preferably 0.1 to 5% by mass.

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

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

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

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

  The composition for forming a low refractive index layer used in the present invention usually takes the form of a liquid and contains the above-mentioned fluorine-containing copolymer and inorganic fine particles as constituent components, and various additives and a polymerization initiator as appropriate in accordance with necessity. It is prepared by dissolving in At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

The polymerization initiator is appropriately selected according to the type of the curing reactive group.
For example, when the fluorine-containing copolymer has an unsaturated double bond (acryloyl group, methacryloyl group, etc.) capable of radical polymerization, it is preferable to add a radical polymerization initiator.
The radical polymerization initiator may be in any form of generating radicals by the action of heat or generating radicals by the action of light.
As the compound that initiates radical polymerization by the action of heat, organic or inorganic peroxides, organic azo, diazo compounds, and the like can be used.
Specifically, benzoyl peroxide, halogen benzoyl peroxide, lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, butyl hydroperoxide as organic peroxides, hydrogen peroxide, peroxides as inorganic peroxides. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

When a compound that initiates radical polymerization by the action of light is used, the coating is cured by irradiation with active energy rays.
Examples of such radical photopolymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds , Disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, and coumarins. Examples of acetophenones include 2,2-diethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxy-dimethyl-p-isopropylphenyl ketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Sensitizing dyes can also be preferably used in combination with these photoradical polymerization initiators.

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

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

Specific examples of the active halogens include Wakabayashi et al. “Bull Chem. Soc Japan Vol. 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M. P. Hutto “Journal of Heterocyclic Chemistry”, Vol. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring. Specific examples include S-triazine and oxathiazole compounds such as 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl). -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Trihalomethyl-5- (p-methoxyphenyl) -1,3,4-oxadiazole. Specifically, p.14 to p30 in JP-A-58-15503, p6-p10 in JP-A-55-77742, and p287 in JP-B-60-27673. 1-No. 8, p443-p444 No. of JP-A-60-239736 1-No. 17, No. 4,701,399. Compounds such as 1-19 are particularly preferred.
Examples of inorganic complexes include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

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

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

In the present invention, in order to advance the curing of the low refractive index layer, a compound having a high molecular weight and hardly volatilizing from the coating film is preferable, and for example, an oligomer type polymerization initiator is preferable. The oligomer type radiation polymerization initiator is not particularly limited as long as it has a site that generates a photo radical upon irradiation. In order to suppress volatilization, the molecular weight of the polymerization initiator is preferably 250 or more and 10,000 or less, more preferably 300 or more and 10,000 or less. More preferably, the mass average molecular weight is 400 to 10,000. A mass average molecular weight of 400 or more is preferable because of low volatility, and 10,000 or less is preferable because the resulting cured coating film has sufficient hardness. Specific examples of the oligomer type radiation polymerization initiator include oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the following general formula (6). .
General formula (6):

In the general formula ( 6 ), R ⁵¹ represents a monovalent group, preferably a monovalent organic group, and q represents an integer of 2 to 45.

As a commercially available product of the oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone] represented by the general formula ( 6 ), trade name “Ezacure KIP150” manufactured by Fratelli Lamberti Co., Ltd. (CAS-No. 163702-01-0, q = 4-6), “Ezacure KIP65LT” (a mixture of “Ezacure KIP150” and tripropylene glycol diacrylate), “Ezacure KIP100F” (“Ezacure KIP150” and 2- Hydroxy-2-methyl-1-phenylpropan-1-one), “Ezacure KT37”, “Ezacure KT55” (above, “Ezacure KIP150” and a mixture of methylbenzophenone derivatives), “Ezacure KTO46” (“Ezacure KIP150”) ”, Methylbenzo A mixture of an enone derivative and 2,4,6-trimethylbenzoyldiphenylphosphine oxide), “Ezacure KIP75 / B” (a mixture of “Ezacure KIP150” and 2,2-dimethoxy-1,2-diphenylethane-1-one), etc. Can be mentioned.

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

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

  The amount of the compound that initiates radical polymerization by the action of heat or light may be any amount that can initiate the polymerization of the carbon-carbon double bond, but generally the total amount in the low refractive index layer forming composition is not limited. 0.1-15 mass% is preferable with respect to solid content, More preferably, it is 0.5-10 mass%, Most preferably, it is a case of 2-5 mass%.

  When the cross-linking reactive site of the polymer has a group capable of cationic polymerization (epoxy group, oxetanyl group, oxazolyl group, vinyloxy group, etc.), it is preferable to add a polymerization initiator that generates an acid catalyst by light.

Various examples of compounds that generate an acid by the action of light are described in, for example, “Organic Materials for Imaging” p187-198, JP-A-10-282644, edited by the Society for Organic Electronics Materials (Bunshin Publishing). These known compounds can be used. Specifically, RSO ₃ ^- (R is an alkyl group, an aryl ^{_{group), AsF 6 -, SbF 6}} -, PF 6 -, BF 4 - diazonium salt and the counter ion or the like, ammonium salts, phosphonium salts, Various onium salts such as iodonium salts, sulfonium salts, selenonium salts, arsonium salts, organic halides such as oxadiazole derivatives and S-triazine derivatives substituted with trihalomethyl groups, o-nitrobenzyl esters of organic acids, benzoin esters, Examples thereof include iminoesters and disulfone compounds, preferably onium salts, particularly preferably sulfonium salts and iodonium salts.

  A sensitizing dye can also be preferably used in combination with a compound that generates an acid by the action of light. In the present invention, the addition amount of the compound that accelerates the curing reaction by the action of light is preferably 0.1 to 15% by mass, more preferably 0.5%, based on the total solid content in the low refractive index layer forming composition. -10 mass%, particularly preferably 2-5 mass%.

The example of the preferable layer structure of the antireflection film of this invention is shown below. In the following configuration, the base film functions as a support.
・ Base film / low refractive index layer,
・ Base film / Antistatic layer / Low refractive index layer,
・ Base film / hard coat layer / high refractive index layer / low refractive index layer,
・ Base film / hard coat layer / antistatic layer / high refractive index layer / low refractive index layer,
Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations.
The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, ATO, ITO), and can be provided by coating or atmospheric pressure plasma treatment.
Although the above example shows a configuration example of a so-called anti-glare film having no anti-glare property, it can also be applied to an anti-glare anti-reflection film. In this case, it is possible to impart antiglare properties to any of the above layers.

[High / Medium Refractive Index Layer]
Next, materials for forming the high / medium refractive index layer / hard coat layer will be described below.
The refractive index of the high / medium refractive index layer is preferably in the range of 1.50 to 2.40, more preferably in the range of 1.50 to 1.80. The high / medium refractive layer contains at least a film-forming binder, and can further contain an inorganic filler in order to increase the refractive index of the layer and to reduce curing shrinkage.

The material for forming the high / medium refractive index layer of the present invention will be described below.
(Film-forming binder)
In the present invention, it is possible to use a compound having an ethylenically unsaturated group as a main film-forming binder component of a film-forming composition for forming each layer such as a high / medium refractive index layer. Is preferable in terms of productivity and coating film productivity. The main film-forming binder refers to one that accounts for 10% by mass or more of the film-forming components excluding inorganic fine particles. Preferably, they are 20 mass% or more and 100 mass% or less, More preferably, they are 30 mass% or more and 95 mass% or less.
A polymer having a saturated hydrocarbon chain or a polyether chain as a main chain is preferable, and a polymer having a saturated hydrocarbon chain as a main chain is more preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to obtain a high refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polymer Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds , Fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are also described in the latest UV curing technology (P-359, publisher: Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.

Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 907) manufactured by Nippon Ciba-Geigy Co., Ltd.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

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

In the present invention, a polymer having a polyether as a main chain can also be used. A ring-opening polymer of a polyfunctional epoxy compound is preferred. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

(Inorganic filler for high and medium refractive index layers)
The high refractive index layer includes an oxide of at least one metal selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in order to increase the refractive index of the layer and to reduce cure shrinkage. It is preferable that an inorganic filler having an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less is contained.
Specific examples of the inorganic filler used for the high refractive index layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ .
TiO ₂ and ZrO ₂ are particularly preferable in terms of increasing the refractive index. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the high refractive index layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.
In addition, since such a filler has a particle size sufficiently smaller than the wavelength of light, scattering does not occur, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of the binder and inorganic filler of the high refractive index layer is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

  The antireflective film is preferably provided with a medium refractive index layer having a refractive index lower than that of the high refractive index layer and higher than that of the support. The medium refractive index layer is a high refractive index used for the high refractive index layer. It can be formed in the same manner as the high refractive index layer by adjusting the amount of the filler and the high refractive index monomer used.

(Light diffusion layer)
The light diffusing layer is formed for the purpose of contributing to the film light scattering due to internal scattering, or light scattering due to surface scattering and antiglare properties, and preferably hard coat properties for improving the scratch resistance of the film.

As a method for forming light diffusibility, a method of laminating a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, as described in JP-A-2000-206317, etc. A method of forming by curing shrinkage of an ionizing radiation curable resin due to a difference in the amount of ionizing radiation, and as described in JP-A No. 2000-338310, when the weight ratio of a good solvent to a translucent resin decreases by drying. A method of solidifying the light-sensitive fine particles and the translucent resin while gelling to form unevenness on the coating film surface, a method of imparting surface unevenness by external pressure as described in JP-A-2000-275404, etc. These known methods can be used.
The light diffusing layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting light diffusibility, and a solvent as essential components. It is preferable that irregularities on the surface be formed by the protrusions of the protrusions themselves or protrusions formed by an aggregate of a plurality of particles.
The light diffusion layer formed by the dispersion of the matte particles is composed of a binder and light-transmitting particles dispersed in the binder. The light diffusion layer having antiglare properties preferably has both antiglare properties and hard coat properties.

As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either spherical or irregular.

  The particle size distribution of the matte particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

  The internal haze and surface haze of the present invention can be achieved by adjusting the refractive index of the translucent resin in accordance with the refractive index of each translucent particle selected from these particles. Specifically, a translucent resin (having a refractive index after curing of 1.55 to 1.70) mainly composed of a tri- or higher functional (meth) acrylate monomer preferably used in the light diffusion layer of the present invention, A combination of translucent particles and / or benzoguanamine particles composed of a crosslinked poly (meth) acrylate polymer having a styrene content of 50 to 100% by mass is preferred, and in particular, the translucent resin and styrene content of 50 to 100% by mass. A combination with translucent particles (having a refractive index of 1.54 to 1.59) made of a crosslinked poly (styrene-acrylate) copolymer is particularly preferred.

The translucent particles are preferably blended in the formed light diffusion layer so as to be contained in an amount of 3 to 30% by mass in the total solid content of the light diffusion layer. More preferably, it is 5-20 mass%. When it is less than 3% by mass, the antiglare property is insufficient, and when it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.
Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

Further, the absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.04 or less. The absolute value of the difference between the refractive index of the translucent resin and the refractive index of the translucent particles is preferably 0.001 to 0.030, more preferably 0.001 to 0.020, and still more preferably 0.001. ~ 0.015. When this difference exceeds 0.040, problems such as film character blur, a decrease in dark room contrast, and white turbidity of the surface occur.
Here, the refractive index of the translucent resin can be quantitatively evaluated by directly measuring the refractive index with an Abbe refractometer or by measuring a spectral reflection spectrum or a spectral ellipsometry. The refractive index of the light-transmitting particles is measured by measuring the turbidity by equally dispersing the light-transmitting particles in the solvent in which the refractive index is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes. It is measured by measuring the refractive index of the solvent when the turbidity is minimized with an Abbe refractometer.

  Two or more kinds of mat particles having different particle diameters may be used in combination. It is possible to impart anti-glare properties with mat particles having a larger particle size and to impart other optical characteristics with mat particles having a smaller particle size. For example, when an anti-glare antireflection film is attached to a high-definition display of 133 ppi or higher, a problem in display image quality called “glare” may occur. “Glitter” is derived from the fact that pixels are enlarged or reduced due to unevenness present on the surface of the antiglare and antireflection antireflection film, resulting in loss of luminance uniformity, but particles smaller than mat particles that impart antiglare properties. It can be greatly improved by using mat particles having a diameter different from that of the binder.

  The film thickness of the light diffusion layer is preferably 1 to 10 μm, more preferably 1.2 to 8 μm. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

  On the other hand, the center line average roughness (Ra) of the light diffusion layer is preferably in the range of 0.05 to 0.40 μm. If it exceeds 0.40 μm, problems such as glare and whitening of the surface when external light is reflected occur. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

  The strength of the light diffusion layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in the pencil hardness test.

(Hard coat layer)
The film of the present invention can be provided with a hard coat layer in addition to the antiglare layer in order to impart the physical strength of the film.
Preferably, a low refractive index layer is provided thereon, and more preferably, an intermediate refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to constitute an antireflection film.
The hard coat layer may be composed of two or more layers.

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, since there is at least one low refractive index layer on the hard coat layer, if the refractive index is too small, the antireflection property is lowered, and if it is too large, the color of the reflected light tends to be strong. is there.

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

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

  The hard coat layer contains matte particles having an average particle diameter of 1.0 to 10.0 μm, preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles, for the purpose of imparting internal scattering properties. May be.

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

  In order to maintain the sharpness of the image, it is preferable to adjust the clarity of the transmitted image in addition to adjusting the uneven shape of the surface. The clearness of the transmitted image of the clear antireflection film is preferably 60% or more. The transmitted image clarity is generally an index indicating the degree of blurring of an image reflected through a film, and the larger this value, the clearer and better the image viewed through the film. The transmitted image definition is preferably 70% or more, and more preferably 80% or more.

In order to provide the viewing angle expansion function, it is important to adjust the intensity distribution (scattered light profile) of the scattered light measured by the goniophotometer of the light diffusion layer. For example, in the case of a liquid crystal display, the viewing angle characteristics are improved as the light emitted from the backlight is diffused by the antireflection film installed on the surface of the polarizing plate on the viewing side. However, if it is diffused too much, backscattering will increase and the front luminance will decrease, or the scattering will be too great and the image clarity will deteriorate. Therefore, it is necessary to control the scattered light intensity distribution of the hard coat layer within a certain range. In order to achieve the desired visual characteristics, the scattered light intensity at an output angle of 30 °, which correlates with the effect of improving the viewing angle in particular, is 0.01% to 0.2% with respect to the light intensity at the output angle of 0 ° of the scattered light profile. %, 0.02% to 0.15% is more preferable, and 0.02% to 0.1% is most preferable.
The scattered light profile can be measured using an automatic goniophotometer GP-5 manufactured by Murakami Color Research Laboratory Co., Ltd. for an antireflection film provided with a hard coat layer.

As a method of imparting internal scattering properties to the hard coat layer or a method of imparting a desired scattering profile, a light transmitting material having a refractive index different from that of the binder in a binder (including the above-described inorganic particles capable of adjusting the refractive index) is used. It is preferable to contain conductive particles. The refractive index difference between the binder and the translucent particles is preferably 0.02 to 0.20. The difference in refractive index within the above range causes an appropriate light diffusion effect and does not cause the entire film to be whitened due to an excessive light diffusion effect. The refractive index difference is more preferably 0.03 to 0.15, and most preferably 0.04 to 0.13.
The combination of the binder and the translucent particles can be appropriately selected for the purpose of adjusting the refractive index difference.

  The particle diameter of the translucent particles is preferably 0.5 μm to 5 μm. If the particle size is in the above range, the light diffusion effect is moderate, the backscattering is small, the light utilization efficiency is sufficient, the surface irregularities are small, and white blurring and glare phenomenon hardly occur. The particle size of the translucent particles is preferably 0.7 μm to 4.5 μm, and most preferably 1.0 μm to 4.0 μm.

The translucent particles may be organic particles or inorganic particles. As the particle size is not more varied, the scattering characteristics are less varied and the design of the haze value is facilitated. As the translucent fine particles, plastic beads are preferable, and those having particularly high transparency and a difference in refractive index from the binder as described above are preferable.
Organic particles include polymethyl methacrylate beads (refractive index 1.49), acrylic-styrene copolymer beads (refractive index 1.54), melamine beads (refractive index 1.57), polycarbonate beads (refractive index 1.57). ), Styrene beads (refractive index 1.60), cross-linked polystyrene beads (refractive index 1.61), polyvinyl chloride beads (refractive index 1.60), benzoguanamine-melamine formaldehyde beads (refractive index 1.68), etc. It is done.
As the inorganic particles, silica beads (refractive index 1.44), alumina beads (refractive index 1.63), and the like are used.

  As described above, the particle size of the translucent particles may be appropriately selected from 0.5 to 5 μm, and may be used by mixing two or more kinds. It is good to contain a mass part.

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

[Other layers]
The antireflection film may further be provided with a hard coat layer, a moisture proof layer, an antistatic layer, an undercoat layer or a protective layer. The hard coat layer is provided for imparting scratch resistance to the transparent support. The hard coat layer also has a function of strengthening the adhesion between the transparent support and the layer thereon. The hard coat layer can be formed using an acrylic polymer, a urethane polymer, an epoxy polymer, a silicon polymer, or a silica compound. A pigment may be added to the hard coat layer. The acrylic polymer is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicon-based polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Two or more kinds of polymers may be used in combination. As the silica compound, colloidal silica is preferably used. The strength of the hard coat layer is preferably a pencil hardness of 1 kg load, preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher. On the transparent support, in addition to the hard coat layer, an adhesive layer, a shield layer, a sliding layer and an antistatic layer may be provided. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Support]
As the transparent support used in the antireflection film of the present invention, it is preferable to use a plastic film. Examples of polymers forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene). Naphthalate), polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon Corporation), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. In addition, the cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and the process for producing the same are disclosed in the JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; The cellulose acylate described herein can also be preferably used in the present invention.

[Coating film forming method]
The antireflection film of the present invention can be formed by the following method, but is not limited to this method.
First, a coating solution containing components for forming each layer is prepared. The coating solution is applied onto a transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (see US Pat. No. 2,681,294). Heat and dry. Of these coating methods, a gravure coating method is preferable because a coating solution with a small coating amount such as each layer of the low refractive index layer can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method has a high film thickness uniformity and is more preferable.
In addition, a coating solution with a small coating amount can be applied with high film thickness uniformity even by using a die coating method. Further, since the die coating method is a pre-measuring method, film thickness control is relatively easy, and the solvent in the coating part Is preferred because of less transpiration. As a method for applying a thin layer coating solution having a wet film thickness of several tens of microns or less to a plastic film using a specific slot die or a coating method, for example, Japanese Patent Application Laid-Open Nos. 2003-200097, 2003-211052, and 2003 No. 230862, No. 2003-236434, No. 2003-236451, No. 2003-245595, No. 2003-251260, No. 2003-260400, No. 2003-260402, No. 2003-275562, No. 2004-141806 The methods described in the above publications are also preferable. Two or more layers may be applied simultaneously. The method of simultaneous application is described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

  The antireflection film formed as described above preferably has a haze value of 10% or less, more preferably 5% or less, still more preferably 3% or less, and an average reflectance of 450 nm to 650 nm. Is preferably 3.0% or less, more preferably 2.5% or less. When the antireflection film has a haze value and an average reflectance in the above range, antireflection properties can be obtained without accompanying deterioration of the transmission image.

[Saponification]
When the antireflection film is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support of the antireflection film is triacetylcellulose, since triacetylcellulose is used as a protective film for protecting the polarizing layer of the polarizing plate, it is preferable in terms of cost to use the antireflection film as it is for the protective film. .

When an anti-reflection film is placed on the outermost surface of the display by providing an adhesive layer on one side, or when used as it is as a protective film for a polarizing plate, a fluorine-containing film is used on the transparent support to ensure sufficient adhesion. It is preferable to perform a saponification treatment after forming the outermost layer mainly composed of a polymer. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the polarizing film and the antireflection film when adhered to the polarizing film, and this prevents point defects caused by dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the saponification treatment is performed up to the surface of the low refractive index layer, the surface is alkali-hydrolyzed and the film deteriorates. The point that it becomes dirty when the liquid remains can be a problem. In that case, although it becomes a special process, (2) is excellent.
(1) After forming the low refractive index layer on the transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the formation of the low refractive index layer on the transparent support, an alkaline liquid is applied to the surface of the antireflection film opposite to the surface on which the low refractive index layer is formed, followed by heating, washing with water and / or Alternatively, only the back surface of the film is saponified by neutralization.

In the present invention, the conditions described below are standard saponification conditions. In general, a polarizing plate in a state of being saponified and processed into a polarizing plate by a continuous treatment in the polarizing plate manufacturing process is also referred to as “reflection after saponification” of the present invention. It is defined as “a polarizing plate having a prevention film”.
Saponification standard conditions It is assumed that the antireflection film is treated and dried in the following steps.
(1) Alkaline bath 1.5 mol / L sodium hydroxide aqueous solution 55 ° C.-120 seconds (2) First washing bath Tap water 60 seconds (3) Neutralization bath 0.05 mol / L sulfuric acid 30 ° C.-20 seconds (4) Second washing bath Tap water 60 seconds (5) Dry 120 ° C
60 seconds

[Polarizer]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The antireflection film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.
As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, with a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the moving direction of the film at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 degrees. It can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 degrees are preferably used from the viewpoint of productivity.

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

[Optical compensation film]
In addition, the polarizing plate of the present invention preferably has a form in which one of the protective films is the antireflection film of the present invention and the other is an optical compensation film having an optically anisotropic layer.
The optically anisotropic layer is preferably designed so as to compensate for the liquid crystal compound molecules in the liquid crystal cell in the black display of the liquid crystal display device. The alignment state of the liquid crystal compound molecules in the liquid crystal cell in black display varies depending on the mode of the liquid crystal display device. Regarding the alignment state of the liquid crystal compound molecules in this liquid crystal cell, IDW'00, FMC7-2, p. 411-414.
The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 0.7 to 5 μm. However, depending on the mode of the liquid crystal cell, it may be thick (3 to 10 μm) in order to obtain high optical anisotropy.

(Liquid crystal compound)
The liquid crystal compound used in the optically anisotropic layer may be a rod-like liquid crystal or a discotic liquid crystal, and these are high molecular liquid crystals or low molecular liquid crystals, and those in which low molecular liquid crystals are crosslinked and no longer exhibit liquid crystallinity. Including. Most preferred is a discotic liquid crystal.

Preferable examples of the rod-like liquid crystal include those described in JP 2000-304932A.
Examples of discotic liquid crystals (compounds having a discotic structural unit) include C.I. Destrade et al., Mol. Cryst. 71, 111 (1981), benzene derivatives described in C.I. Destrade et al., Mol. Cryst. 122, 141 (1985), Physicslett, A, 78, 82 (1990); Kohne et al., Angew. Chem. 96, page 70 (1984) and the cyclohexane derivatives described in J. Am. M.M. Lehn et al. Chem. Commun. , 1794 (1985), J. Am. Zhang et al., J. Am. Chem. Soc. 116, 2655 (1994), and azacrown and phenylacetylene macrocycles. The discotic liquid crystal generally has a structure in which these are used as a mother nucleus at the center of a molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group, etc. are radially substituted as the linear chain. Show. However, the molecule itself is not limited to the above description as long as the molecule itself has negative uniaxiality and can give a certain orientation. Further, in the present invention, the term “formed from a discotic compound” does not require that the final substance is the above-mentioned compound. For example, a low molecular discotic liquid crystal has a group that reacts with heat, light, or the like. As a result, it may be polymerized or cross-linked by reaction with heat, light, etc., resulting in high molecular weight and loss of liquid crystallinity. Preferred examples of the discotic liquid crystal include those described in JP-A-8-50206.

  The optically anisotropic layer is generally formed by applying a solution obtained by dissolving a discotic compound and other compounds (eg, plasticizer, surfactant, polymer, etc.) in a solvent onto the alignment film, drying, and then discotic nematic. It is obtained by heating to the phase formation temperature and then cooling while maintaining the orientation state (discotic nematic phase). Alternatively, the optically anisotropic layer is formed by applying a solution obtained by dissolving a discotic compound and another compound (for example, a polymerizable monomer, a photopolymerization initiator) in a solvent onto the alignment film, drying, and then discotic It is obtained by heating to the nematic phase formation temperature, polymerizing (by irradiation with UV light or the like), and further cooling.

(Alignment film)
The alignment film is usually used because it has the function of defining the alignment direction of the liquid crystal molecules. However, if the alignment state is fixed after aligning the liquid crystalline compound, the alignment film plays its role. It is not necessarily essential as a component of the invention. For example, it is possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizer.

  The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.

The alignment film is preferably formed by polymer rubbing treatment. In principle, the polymer used for the alignment film has a molecular structure having a function of aligning liquid crystal molecules.
In the present invention, in addition to the function of aligning liquid crystal molecules, a crosslinkable function having a function of aligning a side chain having a crosslinkable functional group (eg, a double bond) to the main chain or aligning liquid crystal molecules. It is preferred to introduce the group into the side chain.
As the polymer used for the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.

Examples of the polymer include, for example, a methacrylate copolymer, a styrene copolymer, a polyolefin, a polyvinyl alcohol and a modified polyvinyl alcohol described in JP-A-8-338913, paragraph [0022], and poly (N-methylolacrylamide). , Polyester, polyimide, vinyl acetate copolymer, carboxymethyl cellulose, polycarbonate and the like. Most preferred are polyvinyl alcohol and modified polyvinyl alcohol.
Specific examples of the alignment film forming composition such as the modified polyvinyl alcohol compound and the crosslinking agent include those described in JP-A Nos. 2000-155216 and 2002-62426.
The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

[Image display device]
The image display device of the present invention is characterized in that the antireflection film of the present invention described above or a polarizing plate having the antireflection film as a protective film is disposed on the image display surface. Thus, the antireflection film of the present invention or the polarizing plate having the antireflection film as a protective film can be applied to an image display device such as a liquid crystal display device (LCD) or an organic EL display. The image display device of the present invention is preferably applied to a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, and OCB modes. This will be further described below.
Any conventionally known liquid crystal display device can be used. For example, Tatsuo Uchida, “Reflective Color LCD General Technology” [CMC, 1999], “New Development of Flat Panel Display” [Toray Research Center, Research Division, 1996], “Liquid Crystal Related Markets” And the future prospects (first volume), (second volume) "[Fuji Chimera Research Institute, Inc., published in 2003], and the like.

  Specifically, for example, a transmissive type or a reflective type such as twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), etc. It can be preferably used for a liquid crystal display device of a type or a transflective type.

  In addition, the antireflection film of the present invention has a good contrast and a wide viewing angle even when the size of the attached display image of the liquid crystal display device is 17 inches or more, and prevents hue change and transfer of external light. Is preferable.

[TN mode liquid crystal display]
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and many publications are cited. The alignment state in the liquid crystal cell in the TN mode black display is an alignment state in which the rod-like liquid crystalline molecules rise at the center of the cell and the rod-like liquid crystalline molecules lie in the vicinity of the cell substrate.

[OCB mode liquid crystal display]
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. Since the liquid crystal display device using the bend alignment mode liquid crystal cell is aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the devices disclosed in the specifications of US Pat. Nos. 4,583,825 and 5,410,422 are provided. The bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode.
Similarly to the TN mode, the liquid crystal cell in the OCB mode is in a black display, and the alignment state in the liquid crystal cell is such that the rod-like liquid crystal molecules rise in the center of the cell and the rod-like liquid crystal molecules lie in the vicinity of the cell substrate. .

[VA mode liquid crystal display]
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). (2) In addition to the liquid crystal cell [SID97, Digest of Tech. Papers 28 (1997) 845], (3) Liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied. [Preliminary collections 58-59 (1998) of the Japanese Liquid Crystal Discussion Group] and (4) SURVAVAL mode liquid crystal cells (presented at LCD International 98).

[IPS mode liquid crystal display]
In the IPS mode liquid crystal cell, the liquid crystal molecules are always rotated in a horizontal plane with respect to the substrate. In the direction the liquid crystal molecules change direction. The light transmittance can be changed by arranging the polarizing plates sandwiching the liquid crystal cell at a predetermined angle. As the liquid crystal molecules, nematic liquid crystal having a positive dielectric anisotropy Δε is used. The thickness (gap) of the liquid crystal layer is more than 2.8 μm and less than 4.5 μm. This is because when the retardation Δn · d is more than 0.25 μm and less than 0.32 μm, a transmittance characteristic having almost no wavelength dependency within the visible light range can be obtained. By combining the polarizing plates, the maximum transmittance can be obtained when the liquid crystal molecules are rotated 45 ° from the rubbing direction to the electric field direction. The thickness (gap) of the liquid crystal layer is controlled by polymer beads. Of course, the same gap can be obtained with glass bead fiber or resin columnar spacers. The liquid crystal molecules are not particularly limited as long as they are nematic liquid crystals. When the value of the dielectric anisotropy Δε is large, the driving voltage can be reduced, and when the refractive index anisotropy Δn is small, the thickness (gap) of the liquid crystal layer can be increased, the liquid crystal sealing time is shortened, and the gap Variation can be reduced.

[Other LCD mode]
The STN mode liquid crystal display device can be provided with the polarizing plate of the present invention in the same manner as described above. The same applies to the ECB mode.

  Further, by combining with a λ / 4 plate, it can be used to reduce the reflected light from the surface and inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

[Example 1]
[Synthesis of fluorinated copolymer (P-3)]
In an autoclave with a stirrer made of stainless steel with an internal volume of 100 ml, ethyl acetate 40 ml, hydroxyethyl vinyl ether 14.7 g, dilauroyl peroxide 0.49 g, and polysiloxane structure-containing macroazo initiator (VPS-1001 (trade name) Wako Pure Chemical Industries, Ltd.) 0.98 g) was charged, and the system was degassed and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 8.6 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.9 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice with hexane to completely remove the residual monomer. After drying, 35 g of the following copolymer (a-1) of 1/1 (molar ratio) of hexafluoropropylene / hydroxyethyl vinyl ether having 2.3% by mass of polydimethylsiloxane structure introduced into the main chain was obtained. The obtained polymer had a refractive index of 1.407.
Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of a fluorinated copolymer (P-3). The number average molecular weight of the obtained polymer was 35,000, and the refractive index was 1.422.

  Other fluorine-containing copolymers exemplified in this specification can be synthesized in the same manner.

[Synthesis of Comparative Compound a-2]
Into an autoclave with a stirrer made of stainless steel with a capacity of 100 ml, ethyl acetate 40 ml, hydroxyethyl vinyl ether 3.7 g, ethyl vinyl ether 12.0 g and dilauroyl peroxide 0.49 g, polysiloxane structure-containing macroazo initiator (VPS-1001 (trade name) 0.98 g (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and the system was deaerated while being cooled with dry ice-methanol and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.1 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 2.9 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of methanol, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from methanol to completely remove residual monomers. After drying, 35 g of a 50/40/10 (molar ratio) copolymer of hexafluoropropylene / ethyl vinyl ether / hydroxyethyl vinyl ether into which 2.3% by mass of the polydimethylsiloxane structure had been introduced was obtained. The obtained polymer had a refractive index of 1.387. Further, Comparative Compound a-2 was synthesized by allowing acrylic acid chloride to act on the copolymer in the same manner as in the synthesis of P-3. The refractive index of the obtained polymer was 1.415.

[Synthesis of Comparative Compound a-3]
The following comparative compound a-3 was synthesized in the same manner as the synthesis of P-3 except that no polysiloxane-containing macroazo initiator was added and 0.55 g of dilauroyl peroxide was added. The refractive index of the polymer was 1.421.

[Preparation of inorganic fine particles (C-1)]
360 g of tetraethoxysilane (TEOS, SiO ₂ concentration 28% by mass) and 530 g of methanol are mixed, and 100 g of ion-exchanged water and ammonia water (containing 28% ammonia) are added dropwise to the mixture at 25 ° C., followed by stirring for 24 hours. And matured. Heat treatment was performed at 180 ° C. for 4 hours in an autoclave, and the solvent was replaced with ethanol using an ultrafiltration membrane to prepare a dispersion of inorganic fine particles having a solid content concentration of 20% by mass. It was confirmed to be porous particles by observation with a transmission electron microscope.
A mixture obtained by adding 900 g of ion exchange water and 800 g of ethanol to 100.0 g of the porous particle dispersion thus obtained was heated to 30 ° C., and then tetraethoxysilane (SiO ₂ concentration: 28 mass). %) 360 g and 28% ammonia water 626 g were added, and a silica shell layer was formed on the particle surface with a hydrolyzed polycondensate of tetraethoxysilane. Next, after concentration with an evaporator to a solid content concentration of 5% by weight, ammonia water with a concentration of 15% by mass was added to adjust the pH to 10, followed by heat treatment at 180 ° C. for 4 hours in an autoclave, and the solvent was changed to ethanol using an ultrafiltration membrane. A dispersion of substituted inorganic fine particles (C-1) having a solid content concentration of 20% by mass was prepared.

As a result of calculating the particle size and refractive index of the inorganic fine particles from the obtained dispersion by the following method, the average particle size was 40 nm and the refractive index was 1.28.
(Particle size measurement)
The obtained dispersion was diluted and skimmed on a grid and observed with a transmission electron microscope. From the average of 1000 particles, the average particle size was determined.
(Measurement of refractive index)
According to the method described in JP-A-2002-79616, the refractive index of a film prepared by dispersing the obtained inorganic fine particles in an appropriate binder while changing the mixing ratio was measured. From these measurement results, the refractive index of the inorganic particles was calculated by extrapolating to 100% of the inorganic particles.

[Preparation of inorganic fine particles (C-2)]
A reaction mother liquor was prepared by mixing 90 g of silica sol having an average particle diameter of 5 nm and a SiO ₂ concentration of 20% by mass with 1710 g of ion-exchanged water, and heated to 95 ° C. The pH of this reaction mother liquor is 10.5. In the mother liquor, 24,900 g of 1.5% by mass sodium silicate aqueous solution as SiO ₂ and 0.5% by mass sodium aluminate aqueous solution 36, Al ₂ O ₃ , 800 g was added simultaneously. Meanwhile, the temperature of the reaction solution was maintained at 91 ° C. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a dispersion (A) of SiO ₂ · Al ₂ O ₃ core particles having a solid content concentration of 20% by mass. (First preparation step)
Next, 500 g of the core particle dispersion (A) is collected, 1,700 g of ion exchange water is added and heated to 98 ° C., and the sodium silicate aqueous solution is removed with a cation exchange resin while maintaining this temperature. A silica protective film was formed on the surface of the core particles by adding 2,100 g of a silicic acid solution (SiO ₂ concentration 3.5 mass%) obtained by alkali. The obtained dispersion of core particles having a silica protective film was washed with an ultrafiltration membrane to adjust the solid content concentration to 13% by mass, and then 1,125 g of ion-exchanged water was added to 500 g of the dispersion of core particles. Concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, and after dealumination treatment, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of ion-exchanged water. Then, a particle precursor dispersion was prepared. (Second preparation step)
A mixture of 1500 g of the particle precursor dispersion, 500 g of ion-exchanged water and 1,750 g of ethanol is heated to 30 ° C., and then 70 g of tetraethoxysilane (SiO ₂ 28% by mass) and 626 g of 28% ammonia water are added at a speed. Was added while controlling, and a silica outer shell layer was formed on the surface of the particle precursor with a hydrolyzed polycondensate of tetraethoxysilane to prepare particles having cavities inside the outer shell layer. Next, after concentration with an evaporator to a solid content concentration of 5% by mass, ammonia water with a concentration of 15% by mass was added to adjust the pH to 10, followed by heat treatment at 180 ° C. for 4 hours in an autoclave, and the solvent was changed to ethanol using an ultrafiltration membrane. A dispersion of substituted hollow silica fine particle sol (hole-containing inorganic fine particles) (C-2) having a solid content concentration of 20% by mass was prepared. (Third preparation step)
As a result of calculating the particle size and refractive index of the inorganic fine particles from the obtained dispersion by the method described above, the average particle size was 51 nm and the refractive index was 1.28.

[Preparation of inorganic oxide particles (C-3)]
A commercially available silica particle dispersion (IPA-ST-L, manufactured by Nissan Chemical Co., Ltd., silica solid content concentration of 30% by mass, solvent isopropyl alcohol) having a silica solid content concentration of 20 as a non-porous silica particle. Dilution with isopropyl alcohol was carried out so that it might become mass%. The refractive index of the silica fine particles was 1.46 as a result of calculation by the method described above.

[Preparation of dispersion (A-2)]
By vacuum distillation at a pressure of 20 kPa while adding isopropyl alcohol to 500 parts of the hollow silica fine particle sol (C-2) (silica concentration: 20% by mass, ethanol dispersion) so that the silica content is substantially constant. Solvent replacement was performed. 500 parts of the silica dispersion (silica concentration 20%) thus obtained was added to 30 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and diisopropoxyaluminum ethyl acetate ( After adding 1.5 parts of a trade name, Kerope EP-32, manufactured by Hope Pharmaceutical Co., Ltd. and mixing, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. While adding cyclohexanone to 500 g of this dispersion so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 20 kPa. There was no generation of foreign matter in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% by mass with cyclohexanone was 5 mPa · s at 25 ° C. When the residual amount of isopropyl alcohol in the obtained dispersion (A-6) was analyzed by gas chromatography, it was 1.5%.
The other inorganic fine particles (C-1) and (C-3) are treated according to the preparation of the dispersion (A-2) to prepare the corresponding dispersions (A-1) and (A-3). did.

[Preparation of sol solution a]
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate (trade name, Kellop EP -32, manufactured by Hope Pharmaceutical Co., Ltd.) and mixing, 30 parts of ion-exchanged water was added, and the mixture was reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all. Sol solution a was adjusted with methyl ethyl ketone so that the solid content was 29%.

[Preparation of coating solution for low refractive index layer (L-1 to 24)]
Each component shown in the following Table 1 is mixed, diluted with cyclohexane and methyl ethyl ketone so that the solid content concentration of the entire coating solution becomes 5 mass%, and the ratio of cyclohexane and methyl ethyl ketone is 10:90. 1-24) were prepared.
In the table, () represents the mass part of the solid content of each component. IRG907 represents Irgacure 907 (trade name) manufactured by Ciba Geigy Co., Ltd.

[Preparation of coating liquid A for hard coat layer]
Desolite Z7404 (zirconia fine particle-containing hard coat composition, manufactured by JSR Corporation) 100 parts by mass, DPHA (UV curable resin: manufactured by Nippon Kayaku Co., Ltd.) 31 parts by mass, KBM-5103 (silane coupling agent: Shin-Etsu) (Chemical Industry Co., Ltd.) 10 parts by mass, 29 parts by mass of methyl ethyl ketone, 13 parts by mass of methyl isobutyl ketone, and 5 parts by mass of cyclohexanone were put into a mixing tank and stirred to obtain a hard coat layer coating solution A.

[Preparation of antireflection film (207)]
As a support, a triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form, and the above coating liquid A for hard coat layer has a gravure pattern of 135 lines / inch and a depth of 60 μm. Using a micro gravure roll with a diameter of 50 mm and a doctor blade, the coating was carried out at a conveyance speed of 10 m / min, dried at 60 ° C. for 150 seconds, and then air-cooled metal halide lamp (Igraphics (160)) under a nitrogen purge. Co., Ltd.) was used to cure the coating layer by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² to form a hard coat layer and wound it. The hard coat film (207) was produced by adjusting the rotation speed of the gravure roll so that the thickness of the hard coat layer after curing was 4.0 μm. The refractive index of the hard coat layer after curing was 1.61.
On the hard coat film (207) thus obtained, the low refractive index layer coating solution (L-7) is used to adjust the thickness of the low refractive index layer to 90 nm to prevent reflection. A film (207) was produced. The low refractive index layer was dried at 60 ° C. for 1 minute, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.01% by volume or less. ), And the irradiation dose was 300 mW / cm ² and the irradiation dose was 240 mJ / cm ² . The refractive index of the low refractive index layer after curing was 1.45.

[Preparation of antireflection films (201) to (206) and (208) to (224)]
In the production of the antireflection film (207), the coating solution for low refractive index layer (L-7) was changed to (L-1) to (L-6), (L-8) to (L-24). Antireflection films (201) to (206) and (208) to (224) were produced in the same manner as the antireflection film (207) except that only the difference was observed.

[Saponification treatment of antireflection film]
The obtained antireflection film was treated and dried under the following saponification standard conditions.
(1) Alkaline bath 1.5 mol / L sodium hydroxide aqueous solution 55 ° C.-120 seconds (2) First washing bath Tap water 60 seconds (3) Neutralization bath 0.05 mol / L sulfuric acid 30 ° C.-20 seconds (4) Second washing bath Tap water 60 seconds (5) Dry 120 ° C
60 seconds

[Performance evaluation of coated film]
The following performance evaluation was implemented about the antireflection film sample (201)-(224) obtained in this way.

(1) Average reflectance Using a spectrophotometer (manufactured by JASCO Corporation), the spectral reflectance at an incident angle of 5 ° was measured in a wavelength region of 380 to 780 nm. The mirror surface average reflectance of 450-650 nm was used for the result.

(2) Pencil Hardness Evaluation After the antireflection film was conditioned at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, a pencil hardness evaluation described in JIS K 5400 was performed.

(3) Scratch resistance test The film surface was rubbed 10 times under a load of 200 g using steel wool # 0000, and then the level of scratching was confirmed. The determination was in accordance with the following criteria.
Not scratched at all: ◎
Slightly scratched: ○
Fine scratches stand out: △
Scratch is remarkable: ×

(4) Fingerprint and magic adhesion evaluation As an index of surface contamination resistance, the optical material was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 60% RH, and then the fingerprint was attached to the sample surface and then cleaned. The state when wiped with a cloth was observed, and the fingerprint and magic adhesion were evaluated as follows.
Fingerprints can be wiped off completely: ◎
Some fingerprints are visible: ○
Fingerprints can hardly be wiped off: ×
The obtained results are shown in Table 2.

(5) Evaluation of white haze As an index for evaluating the uneven density of the inorganic fine particles in the low refractive layer, the sample is placed on a black paper, and diffused white light is applied from 50 cm directly above the sample. The state was observed and evaluated as follows.
Uniform observation without unevenness: ○
White scattering unevenness is observed in a part of the sample: Δ
White scattering unevenness is observed on one side of the sample: ×

  As is clear from this example, the antireflection film samples (207) to (209), (213) to (215), and (219) to (221) of the present invention do not satisfy the requirements of the present invention. Compared with examples (201) to (206), (210) to (212), (216) to (218), and (222) to (224), scratch resistance is excellent, and no white haze is generated. It can be seen that the film has excellent antifouling properties and suitable antireflection performance as an antireflection film. In particular, it can be seen that (207) to (209) and (213) to (215) using hollow silica fine particles and porous silica fine particles have lower reflectance and are excellent.

[Example 2]
[Preparation of dispersion (A-4)]
Dispersion (A-2) was prepared except that 10 parts of trimethylmethoxysilane was used instead of 30 parts of acryloyloxypropyltrimethoxysilane and the heating temperature was changed to 50 ° C. for 24 hours. A dispersion (A-4) was prepared in the same manner as described above.

[Preparation of Dispersion (A-5)]
In the preparation of the dispersion liquid (A-2), the dispersion liquid was the same as the dispersion liquid (A-2) except that 15 parts of 30 parts of acryloyloxypropyltrimethoxysilane were changed to tridecafluorooctyltrimethoxysilane. (A-5) was prepared.

[Preparation of coating liquid B for hard coat layer]
"PET-30" 50.0g
"Irgacure 184" 2.0g
"SX-350" (30%) 1.2g
Crosslinked acrylic-styrene particles (30%) 10.0 g
"KBM-5103" 10.0g
Fluorine-based surface conditioner (FP-1) 0.075 g
Toluene 38.5g
Cyclohexanone 5.0g

  The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution B.

The compounds used are shown below.
“PET-30”: a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate {manufactured by Nippon Kayaku Co., Ltd.}
“Irgacure 184”: Polymerization initiator {Ciba Specialty Chemicals Co., Ltd.}
“SX-350”: Cross-linked polystyrene particles having an average particle size of 3.5 μm {refractive index 1.60, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser}.
Cross-linked acrylic-styrene particles: average particle size 3.5 μm {refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion. Use after dispersion for 20 minutes at 10,000 rpm in a Polytron disperser}.
“KBM-5103”: acryloyloxypropyltrimethoxysilane {manufactured by Shin-Etsu Chemical Co., Ltd.}.

  Fluorine-based surface improver (FP-1)

[Preparation of coating solution for low refractive index layer (L-301 to 310)]
Each component shown in the following Table 3 is mixed, diluted with cyclohexanone and methyl ethyl ketone so that the solid content concentration of the entire coating solution becomes 10%, and the ratio of cyclohexanone and methyl ethyl ketone becomes 10:90, and the coating solution (L-301 -310) were prepared.

In the table, () represents the mass part of the solid content of each component.
The compounds used are shown below.
Polymerization initiators: IRG184 (Irgacure 184 (Ciba Specialty Chemicals Co., Ltd., molecular weight 204)), IRG907 (Irgacure 907 (Ciba Specialty Chemicals Co., Ltd., molecular weight 279)), IRG369 (Irgacure 369 (Ciba)・ Specialty Chemicals Co., Ltd., molecular weight 367)), IRGOXE01 (Irgacure OXE01 (Ciba Specialty Chemicals Co., Ltd., molecular weight 451)), KIP150 (Ezacure KIP150, Fratelli Lamberti Co., Ltd., Oligo (2) -Hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) n = 4-6, average molecular weight about 1000)
RMS-33 (photo-curing silicone (manufactured by Gelest Co., Ltd.))
DPHA (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate {manufactured by Nippon Kayaku Co., Ltd.})

[Preparation of Antireflection Film Sample 301]
An 80 μm-thick triacetyl cellulose film “TAC-TD80U” {manufactured by Fuji Photo Film Co., Ltd.} is unwound in a roll form, and the above hard coat layer coating solution B is directly applied to the number of lines 180 / in. Using a gravure pattern with a depth of 40 μm and a micro gravure roll with a diameter of 50 mm and a doctor blade, it was applied at a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further purged with nitrogen Using an “air-cooled metal halide lamp” {manufactured by iGraphics Co., Ltd.} having a lower oxygen concentration of 0.1% by volume of 160 W / cm, it is applied by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ^2. The layer was cured to form a 6 μm thick layer and wound up. The surface roughness of the light diffusion layer (HC-1) thus obtained was Ra = 0.14 μm, Rz = 1.40 μm, Sm = 80 μm, the surface haze was 8%, and the internal haze was 14 %Met.

On the light diffusion layer thus obtained, the low refractive index layer coating liquid L-301 is used, and the low refractive index layer film thickness is adjusted to 95 nm, whereby the antireflection film sample 301 is prepared. Produced. The coating solution was applied after mixing each component for 2 hours. The low refractive index layer was dried at 110 ° C. for 10 minutes. While purging, a 240 W / cm “air-cooled metal halide lamp” {manufactured by Eye Graphics Co., Ltd.) was used to obtain an irradiation amount of 120 mW / cm ² and an irradiation amount of 120 mJ / cm ² .

[Preparation of antireflection films 302 to 311]
In the production of the antireflection film (101), it is the same as the antireflection film 301 except that (L-302) to (L-310) are used instead of the low refractive index layer coating liquid (L-301). Thus, antireflection films 302 to 310 were produced.

[Evaluation of antireflection film]
The antireflection film thus obtained was subjected to the same saponification treatment as in Example 1 and evaluated according to Example 1. In order to evaluate the stability of the coating solution over time, the evaluation of Shiromoya is based on the coating (FR) applied 2 hours after the preparation of the coating solution for the low refractive index layer. Application was performed (2 W) and compared.
The evaluation results are shown in Table 4.

The following can be understood from this example.
The sample of the present invention has a low reflectivity, excellent pencil hardness and scratch resistance, and is free from white haze (FR) and excellent coated surface. In particular, when the molecular weight of the polymerization initiator is increased, scratch resistance is improved, and generation of white haze after storage of the coating solution is suppressed. Moreover, it turns out that the scratch resistance is improved in the sample which used photocurable silicone together.

Example 3
<Preparation of polarizing plate with antireflection film>
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. A saponification-treated antireflection film of Example 2 was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive so that the support (triacetylcellulose) side of the antireflection film was the polarizing film side. . A viewing angle widening film “wide view film SA12B” {manufactured by Fuji Photo Film Co., Ltd.}, which is an optical compensation film having an optically anisotropic layer, is saponified, and the other side of the polarizing film using a polyvinyl alcohol-based adhesive. Pasted on the side. In this way, a polarizing plate was produced. As a result of performing the evaluation according to Example 2 in this polarizing plate state, the same effect was obtained by using the low refractive index layer of the present invention. The antireflection film of the present invention has a light scattering property of 0.013 with a scattered light intensity of 30 ° with respect to a light intensity of 0 ° of the outgoing angle of the scattered light profile of a goniophotometer. It was effective.

Example 4
It was confirmed that the TN, IPS, VA, and OCB mode transmission type liquid crystal display devices equipped with the produced polarizing plate of the present invention were excellent in visibility, scratch resistance, and coated surface condition.

Example 5
When the antireflection film sample of Example 2 was bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained.

(A) And (b) is a cross-sectional schematic diagram which shows the laminated constitution of the antireflection film which concerns on this embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat layer 4,8 High refractive index layer 5 Low refractive index layer 7 Middle refractive index layer

Claims (4)

An antireflection film having a low refractive index layer made of a cured film of a fluorine-containing polymer as an outermost layer on a transparent support,
The fluoropolymer includes a repeating unit comprising a polysiloxane structure in the main chain and comprising a fluorine-containing vinyl monomer, a repeating unit having a (meth) acryloyl group in the side chain, and a repeating unit having a hydroxyl group in the side chain; The content of the repeating unit having a (meth) acryloyl group in the side chain in the copolymer is 30 to 70 mol% of all repeating units other than the polysiloxane moiety, The content of the repeating unit having a hydroxyl group in the side chain in the copolymer is 5 to 40 mol% of all repeating units other than the polysiloxane moiety, and
The antireflective film characterized in that the low refractive index layer contains at least one inorganic fine particle having an average particle size in the range of 30% to 100% of the thickness of the low refractive index layer.   2. The antireflection film according to claim 1, wherein the inorganic fine particles are hollow silica fine particles, and the refractive index of the silica fine particles is 1.17 to 1.40.   3. A polarizing plate comprising a polarizing film and protective films provided on both sides of the polarizing film, wherein at least one of the protective films is the antireflection film according to claim 1 or 2.   An image display device, wherein the antireflection film according to claim 1 or 2 or the polarizing plate according to claim 3 is disposed on an image display surface.

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