JP2005181519A - Antireflection film, polarizing plate and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection film to be manufactured easily and inexpensively and having sufficient antireflection performance, flaw resistance and further anticontamination property and dustproof property, and a polarizing plate and an image display device using such a superior antireflection film. <P>SOLUTION: The antireflection film has a hard coat layer, where mat particles are dispersed on binder and which is set so that the difference of a refractive index between the mat particles and the binder is 0.02-0.20; the particle diameters of the mat particles are 0.5-5.0μm; and the additive amount of the mat particles to the binder is 3-30 mass %; and a low refractive index layer whose refractive index is 1.30-1.49 on a transparent support body, and contains inorganic filler in all the layers except the support body. The polarizing plate and a liquid crystal or plasma display device which uses the antireflection film are provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

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

  In general, in an image display device such as a cathode ray tube display (CRT), a plasma display (PDP), or a liquid crystal display (LCD), optical interference is used to prevent a decrease in contrast due to reflection of external light or image reflection. An antireflective film that reduces the reflectivity using the above principle is disposed on the outermost surface of the display.

  So far, in an antireflection film having only a hard coat layer and a low refractive index layer on a transparent support, the low refractive index layer must be sufficiently lowered in order to reduce the reflectance. In order to make the average reflectance at 450 nm to 650 nm 1.6% or less in an antireflection film using triacetylcellulose as a support and a UV-cured coating of dipentaerythritol hexaacrylate as a hard coat layer, the refractive index is set to 1 Must be 40 or less. Examples of materials having a refractive index of 1.40 or less include magnesium fluoride and calcium fluoride for inorganic materials, and fluorine-containing compounds with a high fluorine content for organic materials, but these fluorine compounds are arranged on the outermost surface of the display because they have no cohesive force. As a film, the scratch resistance was insufficient. In addition, since the fluorine compound has a low charge train, it tends to be electrostatically charged and has poor dust resistance (dust resistance). Therefore, in order to have sufficient scratch resistance, a compound having a refractive index of 1.43 or more is necessary, and in order to ensure sufficient dust resistance, adjustment of a charged column or provision of an antistatic layer is desired. It was difficult to achieve both antifouling properties and optical properties determined by surface properties. Thus, it is difficult to satisfy all of the reduction in reflectance and scratch resistance, antifouling properties, and dustproof properties.

  In Patent Document 1, it is described that the reflectance is reduced by increasing the refractive index of the hard coat layer. However, since such a high refractive index hard coat layer has a large difference in refractive index with the support, color unevenness of the film occurs, and the wavelength dependence of the reflectance also greatly fluctuates.

Moreover, in patent document 2, although the anti-glare anti-reflective film excellent in gas barrier property, anti-glare property, and anti-reflective property is described, since the silicon oxide film by CVD is essential, compared with wet application | coating. Productivity is inferior.
JP 7-287102 A JP 7-333404 A

  An object of the present invention is to provide an antireflection film that can be produced easily and inexpensively and that has sufficient antireflection performance and scratch resistance, as well as antifouling and dustproof properties. Another object of the present invention is to provide a polarizing plate and an image display device using such an excellent antireflection film.

According to the present invention, an antireflection film, a polarizing plate and a liquid crystal or plasma display device having the following constitution are provided, and the above object is achieved.
1. On the transparent support, mat particles are dispersed in a binder, the difference in refractive index between the mat particles and the binder is 0.02 to 0.20, the particle size of the mat particles is 0.5 to 5.0 μm, A hard coat layer in which the addition amount of the mat particles to the binder is 3 to 30% by mass, and a low refractive index layer having a refractive index of 1.30 to 1.49, and all layers except for the transparent support are An antireflection film comprising an inorganic filler.
2. 2. The antireflection film as described in 1 above, wherein the hard coat layer has two or more kinds of mat particles having different refractive indexes.
3. 3. The antireflection film as described in 2 above, wherein a difference in refractive index between the two or more kinds of mat particles is from 0.02 to 0.10.
4). 4. The antireflection film as described in any one of 1 to 3 above, wherein the inorganic filler has an average particle size of 0.001 to 0.2 μm.
5). 5. The antireflection film as described in any one of 1 to 4 above, wherein the hard coat layer contains an inorganic filler, and the refractive index of the hard coat layer is 1.50 to 2.00.
6). The inorganic filler contained in the hard coat layer is an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon, and the content thereof is the total amount of the hard coat layer. The antireflection film as described in any one of 1 to 5 above, which is 10 to 90% of the mass.
7. The antireflection film as described in any one of 1 to 6 above, wherein the surface resistance value (SR (Ω / □)) measured at 25 ° C. and 60% RH is Log SR ≦ 11.0.
8). 8. The antireflection film as described in any one of 1 to 7 above, which contains a conductive inorganic filler in the lower layer of the hard coat layer.
9. The conductive inorganic filler contained in the lower layer of the hard coat layer is an oxide or nitride of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony, and its content Is 30 to 70% of the total mass of the layer, The antireflection film as described in any one of 1 to 8 above.
10. 10. The antiglare antireflection film as described in any one of 1 to 9 above, wherein Ra and JIS defined in JIS-B0601 are 0.12 to 0.30 and 1.0 to 2.9, respectively.
11. The low refractive index layer is composed of a fluorine-containing compound and an inorganic filler that are crosslinked by heating or irradiation with ionizing radiation, and has a dynamic friction coefficient of 0.03 to 0.15 on the layer surface and a contact angle with water of 90 to 120 °. The antireflection film as described in any one of 1 to 10 above.
12 The inorganic filler contained in the low refractive index layer is silica, hollow silica or magnesium fluoride, and the content thereof is 15 to 40% of the total mass of the low refractive index layer. The antireflection film according to any one of the above.
13. 13. The antireflection film as described in any one of 1 to 12 above, which has a haze of 3.0 to 70.0% and an average reflectance of 450 to 650 nm of 1.8% or less.
14 14. The antireflection film as described in any one of 1 to 13 above, wherein the material of the transparent support is triacetyl cellulose, polyethylene terephthalate, or polyethylene naphthalate.
15. 15. A polarizing plate, wherein the antireflection film according to any one of 1 to 14 is used for at least one of two protective films of a polarizing film in a polarizing plate.
16. 15. An image display device comprising the antireflection film according to any one of 1 to 14 as an outermost layer of a display.
17. 16. An image display device, wherein the polarizing plate according to 15 is used so that an antireflection film as a protective layer of the polarizing plate is an outermost layer of the display.

  The antireflection film of the present invention is excellent in scratch resistance, antifouling properties, dustproof properties, and adhesiveness 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.
1 is an example of the antireflection film of the present invention. The antireflection film 1 includes a transparent support 2, a hard coat lower layer 3, a hard coat layer 4, and a low refractive index layer 5. The layer structure is as follows. Matt particles 6 are dispersed in the hard coat layer 4, the refractive index of the hard coat layer is preferably in the range of 1.50 to 2.00, and the refractive index of the low refractive index layer 5 is 1.30. It is preferable to be in the range of ˜1.49. In the present invention, the hard coat lower layer is a layer containing an inorganic filler, and is preferably a conductive layer. The hard coat layer may be a hard coat layer having an antiglare property, a hard coat layer having no antiglare property, or a single layer, or a plurality of layers, for example, 2 to 4 layers. Good. The low refractive index layer is coated on the outermost layer.
In the present specification, the description “numerical value A” to “numerical value B” represents the meaning of “numerical value A to numerical value B”.

  As the solvent composition of the coating liquid used for forming the antireflection film of the present invention, it is preferable to use a ketone solvent, which may be either alone or mixed, and when mixed, the content of the ketone solvent is the coating composition. It is preferable that it is 10 mass% or more of the total solvent contained in a thing. Preferably it is 30 mass% or more, More preferably, it is 60 mass% or more.

  The coating solvent may contain a solvent other than the ketone solvent. For example, as a solvent having a boiling point of 100 ° C. or lower, hexane (boiling point 68.7 ° C., hereinafter “° C.” is omitted), heptane (98.4), cyclohexane (80.7), benzene (80.1), etc. Hydrocarbons such as dichloromethane (39.8), chloroform (61.2), carbon tetrachloride (76.8), 1,2-dichloroethane (83.5), trichloroethylene (87.2), etc. Hydrogens, diethyl ether (34.6), diisopropyl ether (68.5), dipropyl ether (90.5), ethers such as tetrahydrofuran (66), ethyl formate (54.2), methyl acetate (57. 8), esters such as ethyl acetate (77.1) and isopropyl acetate (89), acetone (56.1), 2-butanone (= methyl ethyl ketone, 9.6), alcohols such as methanol (64.5), ethanol (78.3), 2-propanol (82.4), 1-propanol (97.2), acetonitrile (81.6) ), Cyano compounds such as propionitrile (97.4), carbon disulfide (46.2), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

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

In the antireflection film of the present invention, the layer components of each layer are diluted with the solvent having the above-mentioned composition to prepare a coating solution for those layers. The solid content concentration is preferably adjusted as appropriate in consideration of the viscosity of the coating solution and the specific gravity of the layer material, but is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass.
These solvents may have the same composition or may be different.

[Hard coat layer]
The hard coat layer of the present invention will be described below.
The hard coat layer is formed from a binder for imparting hard coat properties, mat particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.
The binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. Moreover, it is preferable that these binder polymers have a crosslinked structure.
As the binder polymer having a saturated hydrocarbon chain as a main chain, a polymer of an ethylenically unsaturated monomer is preferable. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to further increase the refractive index of the hard coat layer, the monomer structure contains at least one kind of atom selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom. It is preferable.

  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 above, acrylate and / or methacrylate are described as (meth) acrylate.

  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 these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
Accordingly, a coating liquid containing a monomer having an ethylenically unsaturated group, a photo radical initiator or a thermal radical initiator, mat particles, and an inorganic filler is prepared, and the coating liquid is applied on a transparent support and then ionizing radiation or heat is applied. It can be cured by a polymerization reaction to form an antireflection film.

As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of the benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takashiro, publisher; Technical Information Association, Inc., published in 1991), which is useful 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. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

The polymer having a polyether as the main chain is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.
Accordingly, a coating liquid containing a polyfunctional epoxy compound, a photoacid generator or a thermal acid generator, matte particles and an inorganic filler is prepared, and the coating liquid is applied onto a transparent support and then subjected to a polymerization reaction by ionizing radiation or heat. Curing can form an antireflection film.

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.

In the hard coat layer, for the purpose of imparting light diffusibility and / or antiglare property, mat particles having a mean particle size of 0.5 to 5.0 μm, preferably 1.5 to 3.5 μm, larger than the filler particles, For example, inorganic compound particles or resin particles are contained. If the refractive index difference between the matte particles and the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusing effect cannot be obtained, so 0.02 to 0.20 is preferable, and 0.04 to Particularly preferred is 0.10. If the addition amount of the mat particles to the binder is too large, the film becomes cloudy if it is too large, and if it is too small, a sufficient light diffusion effect cannot be obtained. A percentage is particularly preferred.
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 refractive index of the matte particles is preferably 1.40 to 1.65, and particularly preferably 1.50 to 1.60.
As the shape of the mat particle, either a true sphere or an indefinite shape can be used.

  Further, two or more different kinds of mat particles may be used in combination. When two or more kinds of mat particles are used, the difference in refractive index is preferably 0.02 or more and 0.10 or less in order to effectively exert the refractive index control by mixing the two, and 0.03 or more. Is particularly preferably 0.07 or less. Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an antireflection film is attached to a high-definition display of 133 ppi or higher, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a refractive index different from that of the binder.

  Furthermore, the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

The mat particles are contained in the hard coat layer so that the amount of the mat particles in the formed hard coat layer is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .
The particle size distribution of the mat particles is measured by a Coulter counter method, and the measured distribution is converted into a particle number distribution.

The hard coat layer has at least one selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, in addition to the above mat particles, in order to increase the refractive index of the layer and to reduce cure shrinkage. It consists of one kind of metal oxide, and the average particle diameter is preferably in the range of 0.001 μm to 0.2 μm, more preferably 0.001 to 0.1 μm, and particularly preferably 0.001 to 0.06 μm. An inorganic filler is contained.
In order to increase the refractive index difference between the mat particles and the binder, it is also preferable to use a silicon oxide in order to keep the refractive index of the hard coat layer using the high refractive index mat particles low. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used for the hard coat 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 from the viewpoint 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 hard coat layer, more preferably 20 to 80%, and particularly preferably 30 to 70%. By setting the inorganic filler content in the above range, it is possible to achieve both improvement in coating film strength as typified by pencil strength, improvement in interlayer adhesion, and reduction in curling due to curing shrinkage.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The refractive index of the hard coat layer of the present invention is preferably 1.50 to 2.00, more preferably 1.57 to 1.90. 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 choose can be easily known by preliminary experiments. By setting it as the said range, it becomes possible to make preferable low reflectance and film | membrane intensity | strength compatible.

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

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

  The film thickness of the hard coat layer is preferably 1 to 10 μm, more preferably 1.2 to 6 μm.

The hard coat of the present invention preferably contains a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”) from the viewpoint of coatability. The fluoroaliphatic group-containing copolymer is preferably a copolymer having a perfluoroalkyl group having 4 or more carbon atoms or a fluoroalkyl group having a CF ₂ H-group having 4 or more carbon atoms in the side chain.
Among them, an acrylic resin, a methacrylic resin, and a copolymer thereof containing a repeating unit (polymerization unit) corresponding to the monomer (i) below and / or a repeating unit (polymerization unit) corresponding to the monomer (ii) below. Copolymers with possible vinyl monomers are useful. Examples of such monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 can be used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

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

In the general formula A, R ¹ represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, more preferably an oxygen atom or —N (R ¹² ) —, and still more preferably an oxygen atom. R ¹² represents a hydrogen atom or an optionally substituted alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. R _f represents —CF ₃ or —CF ₂ H.
M in the general formula A represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1.
N in the general formula A represents an integer of 1 to 17, more preferably 4 to 11, and still more preferably 6 to 7. R _f is preferably —CF ₂ H.
Further, two or more kinds of polymer units derived from the fluoroaliphatic group-containing monomer represented by the general formula A may be contained in the fluorine-based polymer as a constituent component.

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

In the above general formula B, R ¹³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, more preferably an oxygen atom or —N (R ¹⁵ ) —, and still more preferably an oxygen atom. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ¹⁴ is a linear, branched or cyclic alkyl group having 1 to 60 carbon atoms which may have a substituent, or an aromatic group which may have a substituent (for example, a phenyl group or a naphthyl group). ). The alkyl group may include a poly (alkyleneoxy) group. A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkyl group containing a poly (alkyleneoxy) group having 5 to 40 carbon atoms, or an aromatic group having 6 to 18 carbon atoms is more preferable. Alkyl groups including 8 linear, branched, or cyclic alkyl groups and poly (alkyleneoxy) groups having 5 to 30 carbon atoms are highly preferred. The poly (alkyleneoxy) group will be described below.

Poly (alkyleneoxy) groups can be represented by (OR) x, R is an alkylene group having 2 to 4 carbon atoms, such as _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH (CH ₃ ) CH ₂ — or —CH (CH ₃ ) CH (CH ₃ ) — is preferred. x represents 2-30, 2-20 are preferable and 4-15 are more preferable.
The oxyalkylene units in the poly (oxyalkylene) group may be the same as in poly (oxypropylene), or two or more different oxyalkylenes may be randomly distributed. It may be a linear or branched oxypropylene or oxyethylene unit, or a linear or branched oxypropylene unit block and an oxyethylene unit block.
The poly (oxyalkylene) chain may include those linked by one or more chain bonds (for example, -CONH-Ph-NHCO-, -S-, etc .: Ph represents a phenylene group). If the chain bond has a valence of 3 or more, this provides a means for obtaining branched oxyalkylene units. When this copolymer is used in the present invention, the molecular weight of the poly (oxyalkylene) group is suitably from 250 to 3,000.
Poly (oxyalkylene) acrylates and methacrylates are commercially available hydroxypoly (oxyalkylene) materials such as trade name "Pluronic" (Asahi Denka Kogyo Co., Ltd.), Adeka Polyether (Asahi Denka Kogyo Co., Ltd.). ) "Carbowax (Carbowax (Glico Products))", "Triton" (Toriton (Rohm and Haas (Rohm and Haas))) and PEG (Daiichi Kogyo Seiyaku Co., Ltd.) Can be produced by reacting them with acrylic acid, methacrylic acid, acryl chloride, methacryl chloride or acrylic anhydride, etc. Separately, poly (oxyalkylene) diacrylate produced by a known method is used. You can also

  The amount of the fluoroaliphatic group-containing monomer represented by the general formula A used in the production of the fluoropolymer used in the present invention is 10% by mass or more based on the total monomer amount of the fluoropolymer, Preferably it is 50 mass% or more, More preferably, it is 70-100 mass%, More preferably, it is the range of 80-100 mass%.

The preferred mass average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 6,000 to 80,000, and still more preferably 8,000 to 60,000.
Here, the mass average molecular weight and the molecular weight are converted to polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation), and solvent THF and differential refractometer detection. Is the molecular weight. The molecular weight was calculated from the peak area of 300 or more components.

  Furthermore, the preferable addition amount of the fluorine-based polymer used in the present invention is 0.001 to 5 mass with respect to the mass of the coating solution from the viewpoint of expression of the effect due to the addition, drying, and suppression of occurrence of surface failure. %, Preferably 0.005 to 3% by mass, and more preferably 0.01 to 1% by mass.

  Hereinafter, examples of specific structures of the fluorine-based polymer according to the present invention are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

Further, the present inventors have found that the antireflection film of the present invention has an effect of improving the viewing angle of an image display device such as a liquid crystal display device, and more specifically, the scattered light of the antireflection film measured by a goniophotometer. It was confirmed that the intensity distribution correlated with the effect. That is, the more the light emitted from the backlight is diffused by the antireflection film of the present invention installed on the polarizing plate surface on the viewing side, the better the viewing angle characteristics. 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 within a certain range. Therefore, as a result of intensive studies, in order to achieve the desired visual characteristics, the scattered light intensity at 30 °, which correlates particularly with the visual angle improvement effect, is 0.01 with respect to the light intensity at the output angle 0 ° of the scattered light profile. % To 0.2% is preferable, 0.02% to 0.15% is more preferable, and 0.03% to 0.1% is particularly preferable.
The scattered light profile can be measured using the automatic variable angle photometer GP-5 manufactured by Murakami Color Research Laboratory Co., Ltd. for the created light scattering film.

In the present invention, it is preferable to provide an antistatic layer (that is, a conductive layer) from the viewpoint of preventing static electricity on the film surface. In the present invention, the lower layer of the hard coat layer can be an antistatic layer.
The antistatic layer can be formed by, for example, applying a conductive coating solution containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or metal oxide that forms a transparent film. Conventionally known methods such as a method of forming a conductive thin film can be listed. The antistatic layer can be formed directly on the base film or via a primer layer that strengthens adhesion to the base film. Further, the antistatic layer can be used as a part of the antireflection film. In this case, when used in a layer close to the outermost layer, the coating method capable of obtaining sufficient antistatic properties even when the film is thin is not particularly limited. According to the work amount, for example, an optimal method may be selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, and the like.

The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. By providing the antistatic layer, the surface resistance (SR (Ω / sq)) of the antireflection film under the conditions of 25 ° C. and 60% RH is preferably such that the Log SR is 11 or less, and is 4 to 9. Is more preferable, and 5 to 8 is most preferable. The surface resistance can be measured by a four-probe method, a circular electrode method, or the like.
The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. . The transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.
The antistatic layer of the present invention has excellent strength, and the specific antistatic layer has a pencil hardness of 1 kg (as defined in JIS-K-5400), preferably H or higher, preferably 2H or higher. Is more preferably 3H or more, and most preferably 4H or more.

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

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

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

You may surface-treat a conductive inorganic filler. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica, and silica treatment is particularly 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. Two or more kinds of surface treatments may be performed in combination.
The shape of the conductive inorganic filler is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape.
Two or more kinds of conductive inorganic fillers may be used in combination in the antistatic layer.

  The proportion of the conductive inorganic filler in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 80% by mass, and more preferably 30 to 70% by mass.

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

(Antistatic layer binder)
As the binder for the antistatic layer, those described as the binder for the hard coat layer can be used.
In the antistatic layer, a crosslinked polymer can also be used as a binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked. The anionic group has a function of maintaining the dispersion state of the conductive inorganic filler. The crosslinked structure has a function of imparting a film forming ability to the polymer and strengthening the antistatic layer.

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

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

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

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

  The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.

The low refractive index layer of the present invention will be described below.
The refractive index of the low refractive index layer of the antireflection film of the present invention is 1.30 to 1.49, preferably 1.35 to 1.44.
Further, the low refractive index layer preferably satisfies the following formula (I) from the viewpoint of reducing the reflectance.
Formula (I)
(M / 4) × 0.7 <n ₁ d ₁ <(m / 4) × 1.3
In the formula, m is a positive odd number, n ₁ is the refractive index of the low refractive index layer, and d ₁ is the film thickness (nm) of the low refractive index layer. Further, λ is a wavelength, which is a value in the range of 500 to 550 nm.
In addition, satisfy | filling said numerical formula (I) means that m (positive odd number, usually 1) which satisfy | fills numerical formula (I) exists in the said wavelength range.

The material for forming the low refractive index layer of the present invention will be described below.
The low refractive index layer of the present invention contains a fluorine-containing polymer as a low refractive index binder. As the fluoropolymer, the coefficient of dynamic friction on the surface of the low refractive index layer is 0.03 to 0.15, preferably 0.03 to 0.10, more preferably 0.03 to 0.08, and the contact angle with respect to water is 90 to 90. A fluorine-containing polymer that is crosslinked by heating or irradiation with ionizing radiation, such as 120 °, preferably 90 to 110 °, more preferably 95 to 105 °, is preferable. By using the fluoropolymer, dust resistance and antifouling properties can be remarkably improved. Moreover, film | membrane intensity | strength can be improved by using an inorganic filler for the low refractive index layer of this invention.

  Examples of the fluorine-containing polymer used in the low refractive index layer include hydrolysis and dehydration condensate of perfluoroalkyl group-containing silane compounds (for example, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane). And a fluorine-containing copolymer having a fluorine-containing monomer unit and a structural unit for imparting crosslinking reactivity as structural components.

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

  As structural units for imparting crosslinking reactivity, structural units obtained by polymerization of monomers having a self-crosslinkable functional group in advance in the molecule such as glycidyl (meth) acrylate and glycidyl vinyl ether, carboxyl groups, hydroxy groups, amino groups , Obtained by polymerization of a monomer having a sulfo group or the like (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc.) And a structural unit obtained by introducing a crosslinking reactive group such as a (meth) acryloyl group into these structural units by a polymer reaction (for example, it can be introduced by a technique such as allowing acrylic acid chloride to act on a hydroxy group) And the like.

  In addition to the above-mentioned fluorine-containing monomer units and structural units for imparting crosslinking reactivity, monomers not containing fluorine atoms can be copolymerized as appropriate from the viewpoints of solubility in solvents and film transparency. The 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), methacrylates (methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, etc.), styrene derivatives (styrene, divinylbenzene, vinyl toluene, α-methylstyrene, etc.), vinyl ethers ( Methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, etc.), vinyl esters (vinyl acetate, vinyl propionate, vinyl cinnamate etc.), acrylamides (N-tert-butylacrylamide, N Cyclohexyl acrylamide), methacrylamides, and acrylonitrile derivatives.

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

  The fluorine-containing polymer particularly useful in the low refractive index layer of the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These cross-linking reactive group-containing polymer units preferably occupy 5 to 70 mol%, particularly preferably 30 to 60 mol% of the total polymer units of the polymer.

A preferred form of the copolymer used in the low refractive index layer of the present invention is that of general formula 1.

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 a connecting site on the polymer main chain side, and ** represents a link on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

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

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

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

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

  As a particularly preferred form of the copolymer used for the low refractive index layer of the present invention, general formula 2 can be mentioned.

In the general formula 2, X, x, and y have the same meaning as in the general formula 1, and preferred ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a unit of a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
Z1 and Z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  The copolymer represented by the general formula 1 or 2 can be obtained by, for example, introducing a (meth) acryloyl group into a copolymer comprising a hexafluoropropylene component and a hydroxyalkyl vinyl ether component by any of the above-described methods. Can be synthesized.

  Preferred examples of the copolymer useful in the low refractive index layer of the present invention are shown below, but the present invention is not limited thereto.

  The copolymer used in the present invention is synthesized by synthesizing a precursor such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. It can carry out by introduce | transducing a (meth) acryloyl group by the said polymerization reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

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

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

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, 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.

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

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

Next, the inorganic filler contained in the low refractive index layer of the present invention will be described below.
The coating amount of the inorganic filler is preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of 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 filler is contained in the low refractive index layer, the inorganic filler desirably has a low refractive index, and 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 content of the inorganic filler is preferably 15 to 40% of the total mass of the low refractive index layer, more preferably 20 to 40%, and further preferably 25 to 35%.
The average particle diameter of the silica fine particles is preferably 30% or more and 150% or less of the thickness of the low refractive index layer, more preferably 35% or more and 80% or less, and further preferably 40% or more and 60% or less. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Here, the average particle diameter of the inorganic filler is measured by a Coulter counter.

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 have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1. .35, more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, 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 (II) is (formula II)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10-60%, More preferably, it is 20-60%, Most preferably, it is 30-60%.
If the 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 was 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 size can be present in the gaps between the fine silica particles having a large size, the fine particles can contribute as a retaining agent for the fine silica particles having a large size.
When the low refractive index layer is 100 nm, the average particle size of the silica fine particles having a small particle size is preferably 1 nm to 25 nm, more preferably 5 nm to 20 nm, and particularly preferably 10 nm to 20 nm. Use of such silica fine particles is preferable in terms of raw material costs and a retaining agent effect.

Silica fine particles are treated by 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 properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent or the like may be performed, and the use of a coupling agent is particularly preferable. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Among these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is further added as an additive during preparation of the layer coating solution. It is also preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
What has been described above for silica fine particles also applies to other inorganic fillers.

  The composition for forming a low refractive index layer of the present invention is usually in the form of a liquid, and the copolymer is an essential constituent, and various additives and a radical polymerization initiator are dissolved in an appropriate solvent as necessary. Produced. At this time, the concentration of the solid content is appropriately selected according to the use, but is generally about 0.01 to 60% by mass, preferably 0.5 to 50% by mass, particularly preferably 1% to 20% by mass. %.

  As described above, it is not always advantageous to add an additive such as a curing agent from the viewpoint of the optical characteristics of the low refractive index layer, but from the viewpoint of interfacial adhesion to the high refractive index layer, etc. ) 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 an inorganic filler 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 membrane | film | coat, It is more preferable that it is the range of 0-20 mass%, 0-10 mass % Range is particularly preferred.

  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 of the total solid content of the low refractive index layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferred is 0.1 to 5% by mass.

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

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, a branched structure (eg, CH (CF ₃ ) ₂ , CH ₂ CF (CF ₃ ) ₂ , CH (CH ₃ ) CF ₂ CF ₃ , CH (CH ₃ ) (CF ₂ ) ₅ CF ₂ H, etc.), but alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH ₂ OCH ₂ CF ₂ CF ₃ , CH ₂ CH ₂ OCH ₂ C ₄ F ₈ H, CH ₂ CH ₂ OCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ CH ₂ OCF ₂ CF ₂ OCF ₂ CF ₂ H Do). 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.

  At least one of the hard coat layer and the low refractive index layer constituting the antireflection film of the present invention has an organosilane compound and / or a hydrolyzate thereof and / or a partial condensation thereof in a coating solution forming the layer. From the viewpoint of scratch resistance, it is preferable to contain a so-called sol component (hereinafter referred to as such). In particular, the low refractive index layer preferably contains an organosilane compound, a hydrolyzate thereof and / or a partial condensate thereof in order to achieve both antireflection performance and scratch resistance, and the hard coat layer contains an organosilane compound, its It is preferable to contain either a hydrolyzate and / or a partial condensate thereof, or a mixture thereof. 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 represented by the following general formula 3.
Formula _{^{3: (R 10) m -Si}} (X) 4-m
In the general formula 3, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ), And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, such as CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

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

When there are a plurality of R ¹⁰ , 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 4 is preferable.
General formula 4:

In the general formula 4, R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferred, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferred, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹ ) —, and ** represents a position bonded to L.

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

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as in formula 3, preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as in formula 3, 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 of the compounds represented by formulas 3 and 4 may be used in combination. Specific examples of the compounds represented by formulas 3 and 4 are shown below, but are not limited thereto.

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

The hydrolyzate and / or partial condensate of the organosilane compound used in the present invention will be described in detail.
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 having an acid dissociation constant of 2.5 or less in hydrochloric acid, sulfuric acid or water, more preferred is an organic acid having an acid dissociation constant of 2.5 or less in water, and methanesulfonic acid. Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable. A metal chelate compound having a metal such as Zr, Ti or Al as a central metal is also particularly preferable as a catalyst.

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 the alcohols include monohydric alcohols and dihydric alcohols. Among these, monohydric alcohols are preferably saturated aliphatic alcohols having 1 to 8 carbon atoms. Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol. 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.
In the present invention, (wherein, R ³ represents an alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol of the general formula R ⁴ COCH ₂ COR ⁵ (formula represented by, R ⁴ is carbon From Zr, Ti, and Al having a ligand represented by a compound represented by an alkyl group having 1 to 10 carbon atoms, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms) It is preferable to perform hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a selected metal as a central metal.

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

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

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. 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, the coating liquid for the hard coat layer or low refractive index layer used in the present invention includes a β-diketone compound and / or Alternatively, a β-keto ester compound is preferably added. This will be further described below.

The β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used in the present invention and acts as a stability improver for the composition used in the present invention. Is. 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.

In the case of a surface layer such as a low refractive index layer, the content of the hydrolyzate and / or partial condensate of the organosilane compound is 0.1 to 50% by mass of the total solid content of the containing layer (added layer). Preferably, 0.5-20 mass% is more preferable, and 1-10 mass% is the most preferable. 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 obtained by adding a β-diketone compound and / or a β-ketoester compound 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.

  The inorganic filler added to each layer in the antireflection film of the present invention may be the same or different, and depending on the required performance such as refractive index, film strength, film thickness, coatability of each layer, the type, amount added, It is preferable to adjust appropriately.

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. Thereafter, a method of further hydrolysis and condensation can be employed, but the latter is more preferable.

  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.

As the transparent support of the antireflection film of the present invention, a plastic film is preferably used. Examples of the polymer forming the plastic film include cellulose acylate (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, Polyethylene naphthalate), polystyrene, polyolefin, norbornene-based resin (Arton: trade name, manufactured by JSR Corporation), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON Corporation), and the like. Among these, cellulose acylate such as triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.
Triacetyl cellulose consists of a single layer or a plurality of layers. Single-layer triacetyl cellulose is prepared by drum casting or band casting disclosed in JP-A-7-11055, and the latter triacetyl cellulose is a special feature of the published patent publication. It is prepared by the so-called co-casting method disclosed in Japanese Utility Model Publication Nos. 61-94725 and 62-43846. That is, the raw material flakes are solvents such as halogenated hydrocarbons (dichloromethane, alcohols (methanol, ethanol, butanol, etc.), esters (methyl formate, methyl acetate, etc.), ethers (dioxane, dioxolane, diethyl ether, etc.), etc. A solution (called a dope) containing various additives such as a plasticizer, an ultraviolet absorber, an anti-degradation agent, a slipping agent and a peeling accelerator as required is dissolved in a horizontal endless. When casting by a dope supply means (called a die) on a support consisting of a metal belt or a rotating drum, a single dope is cast as a single layer, and a high concentration is used as a plurality of layers. A low-concentration dope is co-cast on both sides of the cellulose ester dope, and the film is dried to some extent on the support to release the rigid film, and then peeled off from the support. A process comprising passed through a drying section by species of the conveying means to remove the solvent.

A typical solvent for dissolving cellulose acylate as described above is dichloromethane. However, from the viewpoint of the global environment and working environment, the solvent preferably does not substantially contain a halogenated hydrocarbon such as dichloromethane. “Substantially free” means that the proportion of halogenated hydrocarbon in the organic solvent is less than 5% by mass (preferably less than 2% by mass).
When preparing a cellulose acylate dope using a solvent substantially free of dichloromethane or the like, a special dissolution method as described below is essential.

  The first dissolution method is called a cooling dissolution method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this manner, the mixture of triacetyl cellulose and solvent solidifies. Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), a solution in which triacetyl cellulose flows in the solvent is obtained. The temperature can be raised by simply leaving it at room temperature or in a warm bath.

  The second method is called a high temperature melting method and will be described below. First, triacetyl cellulose is gradually added to a solvent at a temperature around room temperature (-10 to 40 ° C.) while stirring. The triacetyl cellulose solution of the present invention is preferably swollen beforehand by adding triacetyl cellulose to a mixed solvent containing various solvents. In this method, the dissolution concentration of triacetyl cellulose is preferably 30% by mass or less, but is preferably as high as possible from the viewpoint of drying efficiency during film formation. Next, the organic solvent mixed solution is heated to 70 to 240 ° C. under a pressure of 0.2 MPa to 30 MPa (preferably 80 to 220 ° C., more preferably 100 to 200 ° C., most preferably 100 to 190 ° C.). Next, since these heated solutions cannot be applied as they are, it is necessary to cool them below the lowest boiling point of the solvent used. In that case, it is common to cool to -10-50 degreeC and to return to a normal pressure. For cooling, the high-pressure and high-temperature vessel or line containing the triacetylcellulose solution may be left at room temperature, and more preferably, the apparatus may be cooled using a coolant such as cooling water. A cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and a method for producing the same are disclosed in JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001, hereinafter published Technical Report 2001- No. 1745).

  When the antireflection film of the present invention is used in an image display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing film of the polarizing plate. Therefore, it is preferable in terms of cost to use the antireflection film of the present invention as it is for the protective film.

When the antireflection film of the present invention is disposed on the outermost surface of a display by providing an adhesive layer on one side or used as it is as a protective film for a polarizing plate, It is preferable to perform a saponification treatment after forming an outermost layer mainly composed of a fluorine-containing 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 alkali solution, it is preferable to sufficiently wash with water or neutralize the alkali component by immersing in a dilute acid so that the alkali component does not remain in the film.
By the 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 deflection 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 it is difficult for dust to enter between the deflection film and the antireflection film when bonded to the deflection film, thus preventing point defects due to 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 surface of the antireflection film is saponified, 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 the antireflection layer is formed 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 antireflection layer on the transparent support, an alkaline solution is applied to the surface of the antireflection film opposite to the surface on which the antireflection film is formed, and is heated, washed and / or washed. By summing, only the back surface of the film is saponified.

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. Next, a coating solution for forming a hard coat layer is prepared by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (US Pat. No. 2,681,294). (Refer to the description), and the coating is applied on a transparent support and heated and dried. A micro gravure coating method is particularly preferred. Thereafter, the monomer for forming the antiglare hard coat layer is polymerized and cured by light irradiation or heating. Thereby, a hard coat layer is formed.
Here, if necessary, the hard coat layer may be formed into a plurality of layers, and smooth hard coat layer application and curing can be performed by the same method before application of the antiglare hard coat layer.
Next, a coating solution for forming a low refractive index layer is applied onto the hard coat layer in the same manner, and light irradiation or heating is performed to form the low refractive index layer. In this way, the antireflection film of the present invention is obtained.

  The micro gravure coating method used in the present invention is a gravure roll having a diameter of about 10 to 100 mm, preferably about 20 to 50 mm and engraved with a gravure pattern on the entire circumference, below the support and in the transport direction of the support. The gravure roll is rotated in reverse with respect to the gravure roll, the excess coating liquid is scraped off from the surface of the gravure roll by a doctor blade, and a fixed amount of the coating liquid is removed from the support in a position where the upper surface of the support is in a free state. The coating method is characterized in that the coating liquid is transferred onto the lower surface for coating. A roll-shaped transparent support is continuously unwound, and at least one layer of at least one of a hard coat layer or a low refractive index layer containing a fluorine-containing polymer is provided on one side of the unwound support. Can be applied by.

As coating conditions by the micro gravure coating method, the number of gravure patterns engraved on the gravure roll is preferably 50 to 800 lines / inch, more preferably 100 to 300 lines / inch, and the depth of the gravure pattern is 1 to 600 μm. Is preferable, 5 to 200 μm is more preferable, the rotation speed of the gravure roll is preferably 3 to 800 rpm, more preferably 5 to 200 rpm, and the conveyance speed of the support is 0.5 to 100 m / min. 1 to 50 m / min is more preferable.
The antireflection film of the present invention thus formed has a haze value of 3 to 70%, preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is preferably 3.0% or less, preferably Is 2.5% or less.
When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good light diffusibility and / or antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

  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. Of the two protective films sandwiching the polarizing film, the antireflection film of the present invention is used as the outermost layer, so that reflection of external light is prevented and the polarizing plate has excellent scratch resistance, antifouling properties, etc. It can be.

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 between the moving direction of the film at the exit of the process of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. 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 ° 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.

  The antireflection film of the present invention can be applied to an image display device such as a liquid crystal display device (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), or a cathode ray tube display device (CRT). Since the antireflection film of the present invention has a transparent support, the transparent support side is adhered to the image display surface of the image display device.

  The antireflection film of the present invention, when used as one side of the surface protective film of the polarizing film, is twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optical It can be preferably used for a transmissive, reflective, or transflective liquid crystal display device of a mode such as a curry compensate bend cell (OCB).

  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-). 176625) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) in order to enlarge the viewing angle. ), (3) A 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 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between the upper part and the lower part of the liquid crystal cell. It is disclosed in the specifications of Japanese Patent Nos. 45882525 and 5410422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. Therefore, this liquid crystal mode is also referred to as an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In an ECB mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and is most frequently used as a color TFT liquid crystal display device, and is described in many documents. For example, it is described in “EL, PDP, LCD display” published by Toray Research Center (2001).

  Particularly for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening the viewing angle is used as a protective film on the back and front surfaces of the polarizing film. By using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle expansion effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

(Synthesis of perfluoroolefin copolymer (1))

Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 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 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 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 from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. 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 perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(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.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After that, 30 parts of ion-exchanged water was added and 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.
(Preparation of sol liquid b)
After the reaction, after cooling to room temperature, a sol solution b was obtained in the same manner as in the sol composition a except that 6 parts of acetylacetone was added.

(Preparation of coating liquid A for hard coat layer)
50 g of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA (KAYARAD PET-30: trade name) manufactured by Nippon Kayaku Co., Ltd.) was diluted with 38.5 g of toluene. Furthermore, 2 g of a polymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was added and mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.51.
Further, a 30% toluene dispersion of a crosslinked polystyrene particle having an average particle size of 3.5 μm (refractive index 1.61, SX-350, manufactured by Soken Chemical Co., Ltd.) dispersed in this solution for 20 minutes at 10,000 rpm with a polytron disperser. Add 13.3 g of a 30% toluene dispersion of 1.7 g and crosslinked acrylic-styrene particles having an average particle size of 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd.), and finally, fluorine-based surface modification 0.75 g of an agent (FP-132 (exemplary compound)) and 10 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) were added to obtain a finished solution.
The mixture solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution A for an antiglare hard coat layer.

(Preparation of coating liquid B for hard coat layer)
A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate of coating liquid A for hard coat layer (PETA (KAYARAD PET-30: trade name) manufactured by Nippon Kayaku Co., Ltd.) is a commercially available zirconia-containing UV curable hard coat liquid (Desolite) Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, solid content of ZrO ₂ (refractive index 2.10) content of about 70%, polymerizable monomer (refractive index 1.53), containing polymerization initiator) 321 g It was prepared in the same manner except that the toluene was replaced with 37 g of methyl ethyl ketone.

(Preparation of coating liquid C for hard coat layer)
It was prepared in the same manner except that the crosslinked polystyrene particles and the crosslinked acrylic-styrene particles were removed from the coating liquid B for hard coat layer.

(Preparation of coating liquid D for hard coat layer)
50% of the mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA (KAYARAD PET-30: trade name) manufactured by Nippon Kayaku Co., Ltd.) of the coating liquid A for hard coat layer is made of silica sol (silica, MEK-ST). It was prepared in the same manner except that toluene added to PETA as a solvent was replaced with 83 g of a particle size difference, an average particle size of 45 nm, a solid content concentration of 30%, manufactured by Nissan Chemical Co., Ltd.).

(Preparation of coating liquid E for hard coat layer)
15% of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate of the coating liquid A for hard coat layer (PETA (KAYARAD PET-30: trade name) manufactured by Nippon Kayaku Co., Ltd.) is made of silica sol (silica, MEK-ST This was prepared in the same manner except that toluene added to PETA as a solvent was replaced with 25 g of a particle size difference, refractive index of 1.45, average particle size of 45 nm, solid content concentration of 30%, manufactured by Nissan Chemical Co., Ltd.

(Preparation of coating liquid F for hard coat layer)
Commercially available zirconia-containing UV curable hard coat solution (Desolite Z7404, manufactured by JSR Corporation, solid content concentration of about 61%, solid content of ZrO ₂ (refractive index 2.10) content of about 70%, polymerizable monomer (refractive index 1.53), containing a polymerization initiator) 285 g, 85 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd., refractive index 1.53), and methyl Diluted with 60 g of isobutyl ketone and 17 g of methyl ethyl ketone. Furthermore, 28 g of a silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and stirred. The refractive index of the coating film obtained by applying this solution and curing with ultraviolet rays was 1.61.
Further, a 30% methyl isobutyl ketone dispersion of classified strengthened crosslinked PMMA particles (refractive index 1.49, MXS-300, manufactured by Soken Chemical Co., Ltd.) having an average particle size of 3.0 μm was added to this solution at 10,000 rpm with a Polytron disperser. 35 g of a dispersion dispersed for 20 minutes was added, and then a 30% methyl ethyl ketone dispersion of silica particles having an average particle diameter of 1.5 μm (refractive index: 1.46, Seahosta KE-P150, manufactured by Nippon Shokubai Co., Ltd.) was added to the Polytron Disperser. 90 g of a dispersion dispersed at 10,000 rpm for 30 minutes was added, and finally, 0.12 g of the above-described fluorine-based surface modifier (FP-1 (exemplary compound)) was mixed and stirred to obtain a finished solution.
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution F for a hard coat layer.

(Preparation of coating liquid G for hard coat layer)
A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, (refractive index 1.53) manufactured by Nippon Kayaku Co., Ltd.) in the coating solution F for hard coat layer is all silica sol (silica, MEK-ST particles) It was prepared in the same manner except that it was replaced with 283 g of different size, refractive index 1.45, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.

(Preparation of coating solution A for low refractive index layer)
Thermally crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228, solid content concentration 6%, manufactured by JSR Corporation) 13 g, silica sol (silica, MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30 %, Manufactured by Nissan Chemical Co., Ltd.) 1.3 g, sol solution 0.6 g, methyl ethyl ketone 5 g and cyclohexanone 0.6 g were added, and after stirring, filtered through a polypropylene filter having a pore size of 1 μm, for a low refractive index layer A coating solution was prepared.

(Preparation of coating solution B for low refractive index layer)
In the coating liquid A for the low refractive index layer, heat-crosslinkable fluorine-containing polymer having a refractive index of 1.42 (JN7228, solid content concentration 6%, manufactured by JSR Corporation) was used instead of silica sol to make 16.5 g. In the same manner, a coating solution for a low refractive index layer was prepared.

(Preparation of coating solution C for low refractive index layer)
15.2 g of perfluoroolefin copolymer (1) (same as exemplified structure P-1), silica sol (silica, MEK-ST with different particle size, average particle size 45 nm, solid content concentration 30%, Nissan Chemical Co., Ltd. 20.2 g, reactive silicone X-22-164C (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 g, sol solution a 7.3 g, photopolymerization initiator (Irgacure 907 (trade name), manufactured by Ciba-Geigy Corporation) ) 0.76 g, methyl ethyl ketone 301 g, and cyclohexanone 9.0 g were added, and after stirring, the mixture was filtered through a polypropylene filter having a pore size of 5 μm to prepare a coating solution for a low refractive index layer.

(Preparation of coating solution D for low refractive index layer)
In the coating liquid C for the low refractive index layer, the perfluoroolefin copolymer (1) was used instead of silica sol, and the amount was 18.5 g. A layer coating solution was prepared.

(Preparation of coating liquid E for low refractive index layer)
In the coating liquid C for the low refractive index layer, a low refractive index was similarly obtained except that 21.2 g of hollow silica sol (refractive index 1.31, average particle size 60 nm, solid content concentration 20%) was used instead of silica sol. A layer coating solution was prepared.

(Preparation of coating solution F for low refractive index layer)
In the coating liquid C for the low refractive index layer, the reactive silicone X-22-164C (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with UMS-992 (trade name; manufactured by Gelest). A coating solution for the refractive index layer was prepared.
(Preparation of coating solution G for low refractive index layer)
A coating solution for a low refractive index layer was prepared in the same manner as in the coating solution C for a low refractive index layer, except that the perfluoroolefin copolymer (1) was replaced with the exemplified compound P-2.
(Preparation of coating solution H for low refractive index layer)
In the coating liquid C for the low refractive index layer, the reactive silicone X-22-164C (trade name; manufactured by Shin-Etsu Chemical Co., Ltd.) was replaced with RMS-033 (trade name; manufactured by Gelest). A coating solution for the refractive index layer was prepared.

[Example 1]
(1) Coating of hard coat lower layer (antistatic layer) An 80 μm thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form and manufactured by Nippon Pernox Co., Ltd. Pertron C-4456-S7 ((solid content 45%) ATO-dispersed hard coat agent, trade name) was applied, dried at 60 ° C. for 150 seconds, and further air-cooled metal halide lamp (eye-cooled with 160 W / cm under nitrogen purge) (Graphics Co., Ltd.) was used to irradiate ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² to form an antistatic layer having a thickness of 1 μm.
(2) Coating of hard coat layer The above-mentioned antistatic layer is coated on the antistatic layer, and the uncoated layer is 80 μm thick triacetylcellulose film (TAC-TD80U, Fuji Photo Film Co., Ltd.) )) In the form of a roll, and using the microgravure roll with a diameter of 50 mm having a gravure pattern with a line number of 180 lines / inch and a depth of 40 μm, and a gravure roll. It is applied under the conditions of a rotation speed of 30 rpm and a conveyance speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further under a nitrogen purge, using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) 400 mW / cm ^2, and an irradiation dose of 250 mJ / cm ² to cure the coating layer, to form a layer having a thickness of 6 [mu] m, It took come.

(3) Coating of low refractive index layer The triacetyl cellulose film coated with the antistatic layer and the hard coat layer or the hard coat layer is unwound again, and the coating liquid for the low refractive index layer is added at a line number of 180 / Using a gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern with an inch and a depth of 40 μm, it was applied under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 15 m / min, dried at 120 ° C. for 150 seconds, and further 140 Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 240 W / cm under a nitrogen purge, irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 900 mJ / cm ² , A low refractive index layer having a thickness of 100 nm was formed and wound up.

(Preparation of antireflection film sample)
As shown in Table 1, samples 018 were prepared from the antireflection film samples 001 to 001 by the above method. In the table, the inorganic content is mass% with respect to the total solid content of the inorganic filler added to each layer. N represents the refractive index in each layer. The mat / binder (mass%) was expressed in terms of mass% with respect to the binder amount of the added amount of mat particles in the hard coat layer.

(Saponification treatment of antireflection film)
After film formation, the sample was subjected to the following treatment.
A 1.5 mol / l sodium hydroxide aqueous solution was prepared and kept at 55 ° C. A 0.01 mol / l dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The prepared antireflection film was immersed in the aqueous sodium hydroxide solution for 2 minutes, and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C.

(Evaluation of antireflection film)
The following items were evaluated for film samples 001 to 018 obtained after the saponification treatment.
(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 average reflectance of 450-650 nm was used for the result.
(2) Pencil hardness evaluation Pencil hardness evaluation described in JIS K 5400 was performed as an index of scratch resistance. The antireflection film was conditioned at 25 ° C. and 60% RH for 2 hours, and then subjected to a load of 1 kg using a 3H test pencil specified in JIS S 6006, and evaluated as follows.
○: No scratches are observed in the evaluation of n = 5 Δ: One or two scratches in the evaluation of n = 5 ×: Three or more scratches in the evaluation of n = 5

(3) Contact angle and fingerprint adhesion evaluation As an index of surface contamination resistance, the optical material was conditioned at a temperature of 25 ° C. and 60% RH for 2 hours, and then the contact angle against water was measured. Further, after the fingerprint was attached to the surface of the sample, the state when the sample was wiped off with a cleaning cloth was observed, and the fingerprint adhesion was evaluated as follows.
○: Fingerprints can be completely wiped △: Fingerprints can be seen a little ×: Fingerprints can hardly be wiped off

(4) Glitter evaluation Fluorescent lamp diffused light with a louver was projected on the prepared antireflection film, and surface glare was evaluated according to the following criteria.
○: Almost no glare △: Slight glare ×: There is a size that can be discerned by eyes

(5) Evaluation of steel wool scratch resistance Using a rubbing tester, a rubbing test was conducted under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Gelade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ × ˜ ×: There is a scratch that can be seen at first glance.

(6) Evaluation of curl It measured using the template for curl measurement of the method A in "Measurement method of curl of photographic film" of JISK7619-1988. The test conditions are 25 ° C. and 60% RH. In the present invention, “curl plus” means a curl in which the hard coat layer coating side of the film is inside the curve, and “minus” means a curl in which the coating side is outside the curve. The higher the value, the more curl.

(7) Evaluation of dustiness The transparent support side of the antireflection film is attached to the CRT surface, and dust and tissue paper waste of 0.5 μm or more are 1 to ² million per 1 ft ³ (cubic foot, about 0.0283 m ³ ). Used for 24 hours in the room. When the number of adhering dust and tissue paper waste is measured per 100 cm ^{2 of the} antireflection film, the average value of each result is less than 20, A is 20 to 49, B is 50 to 199 Was evaluated as C, and 200 or more cases were evaluated as D.

(8) Adhesion evaluation The surface of the antireflective film having the low refractive index layer is cut with a cutter knife into a grid pattern of 11 vertical and 11 horizontal cuts to make a total of 100 square grids. Nitto A polyester adhesive tape (NO.31B) manufactured by Denko Co., Ltd. was pressure-bonded and the adhesion test was repeated three times at the same place. The presence or absence of peeling was visually observed, and the following four-stage evaluation was performed.
◎: No peeling was observed in 100 squares ○: No peeling was found in 100 squares within 2 squares △: peeling was observed in 100 squares 3 to 10 mm x: Thickness exceeding 100 mm was observed in 100 cells

(9) Surface roughness evaluation Ra and Rz were determined by the method defined in JIS-B0601.

(10) Measurement of surface resistance value After placing the samples for 2 hours under the conditions of 25 ° C. and 60% RH for all the samples, the surface resistance value (SR) was measured by the circular electrode method under the same conditions.

(11) Dynamic friction coefficient measurement The dynamic friction coefficient was evaluated as an index of surface slipperiness. As the dynamic friction coefficient, the sample was conditioned at 25 ° C. and 60% RH for 2 hours, and then a value measured with a HEIDON-14 dynamic friction measuring machine at a 5 mmφ stainless steel ball, a load of 100 g, and a speed of 60 cm / min was used.

From the results shown in Tables 1 and 2, the following is clear.
The antireflection film of the present invention is excellent in durability scratch resistance and curl by adding an inorganic filler, can improve glare by adding matte particles, can improve dusting by introducing a conductive layer, and further has a surface segregation type silicone. It is clear that the combined use can improve slipperiness and improve antifouling properties represented by fingerprint adhesion. That is, according to the present invention, it has excellent scratch resistance, antifouling properties, dustproof properties, optical properties such as adhesion and glare, etc., satisfying a good balance including performance that often becomes a trade-off, and as an antireflection film Total performance can be improved.
Further, when the sol solution b was used in place of the organosilane sol solution a used in the low refractive index layer coating solution, the stability of the coating solution with time was improved and the suitability for continuous coating was enhanced.
Further, instead of the thermally crosslinkable fluoropolymer used in the low refractive index layer coating solutions A and B, a thermally crosslinkable fluoropolymer having a refractive index of 1.44 (JTA-113, solid content concentration 6%, JSR ( Scratch resistance was remarkably improved.

[Example 2]
80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.), which was immersed in a 1.5 mol / l, 55 ° C. NaOH aqueous solution for 2 minutes and then neutralized and washed with water, Example 1 A polarizing plate was prepared by adhering and protecting both sides of a polarizing film prepared by adsorbing iodine to polyvinyl alcohol and then stretching the film on the backside saponified triacetylcellulose film of the present invention sample. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the polarizing plate on the viewing side of D-BEF made of the product between the backlight and the liquid crystal cell was replaced, a display device with very high display quality was obtained with very little background reflection.

[Example 3]
A discotic structural unit as a protective film on the liquid crystal cell side of the polarizing plate on the viewing side of the transmission type TN liquid crystal cell to which the sample of the present invention of Example 1 is attached, and on the liquid crystal cell side of the polarizing plate on the backlight side An optical compensation layer in which the disc surface is inclined with respect to the transparent support surface and the angle formed by the disc surface of the discotic structural unit and the transparent support surface varies in the depth direction of the optical anisotropic layer. When using the wide viewing angle film (wide view film SA-12B, manufactured by Fuji Photo Film Co., Ltd.), the contrast in the bright room is excellent, the viewing angles in the top, bottom, left and right are very wide, and the visibility is extremely high. A liquid crystal display device with high display quality was obtained.

[Example 4]
When the sample of the present invention of Example 1 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.

[Example 5]
Using the sample of the present invention of Example 1, a polarizing plate with a single-sided antireflection film was prepared, and a λ / 4 plate was laminated on the opposite side of the polarizing plate on the side having the antireflection film, with the antireflection film side being the outermost side. When attached to the glass plate on the surface of the organic EL display device so as to be on the surface, the surface reflection and the reflection from the inside of the surface glass were cut, and a display with extremely high visibility was obtained.

It is a cross-sectional schematic diagram which shows the laminated constitution of an antireflection film.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Antireflection film 2 Transparent support 3 Hard coat lower layer 4 Hard coat layer 5 Low refractive index layer 6 Matte particle

Claims (17)

  On the transparent support, mat particles are dispersed in a binder, the difference in refractive index between the mat particles and the binder is 0.02 to 0.20, the particle size of the mat particles is 0.5 to 5.0 μm, A hard coat layer in which the addition amount of the mat particles to the binder is 3 to 30% by mass, and a low refractive index layer having a refractive index of 1.30 to 1.49, and all layers except the transparent support are An antireflection film containing an inorganic filler.   The antireflection film according to claim 1, wherein the hard coat layer has two or more kinds of mat particles having different refractive indexes.   The antireflection film according to claim 2, wherein a difference in refractive index between the two or more kinds of mat particles is 0.02 or more and 0.10 or less.   The average particle diameter of an inorganic filler is 0.001-0.2 micrometer, The antireflection film in any one of Claims 1-3 characterized by the above-mentioned.   The antireflection film according to claim 1, wherein the hard coat layer contains an inorganic filler, and the refractive index of the hard coat layer is 1.50 to 2.00.   The inorganic filler contained in the hard coat layer is an oxide of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, antimony, and silicon, and the content thereof is the total amount of the hard coat layer. It is 10 to 90% of mass, The antireflection film in any one of Claims 1-5 characterized by the above-mentioned.   The antireflection film according to claim 1, wherein a surface resistance value (SR (Ω / □)) measured at 25 ° C. and 60% RH is LogSR ≦ 11.0.   The antireflection film according to any one of claims 1 to 7, comprising a conductive inorganic filler in a lower layer of the hard coat layer.   The conductive inorganic filler contained in the lower layer of the hard coat layer is an oxide or nitride of at least one metal selected from zirconium, titanium, aluminum, indium, zinc, tin, and antimony, and its content Is 30 to 70% of the total mass of the layer, The antireflection film according to claim 1.   The antireflection film according to any one of claims 1 to 9, wherein Ra and JIS defined in JIS-B0601 are 0.12 to 0.30 and 1.0 to 2.9, respectively.   The low refractive index layer is composed of a fluorine-containing compound and an inorganic filler crosslinked by heating or irradiation with ionizing radiation, and has a dynamic friction coefficient of 0.03 to 0.15 on the layer surface and a contact angle with water of 90 to 120 °. It exists, The antireflection film in any one of Claims 1-10 characterized by the above-mentioned.   The inorganic filler contained in the low refractive index layer is silica, hollow silica or magnesium fluoride, and the content thereof is 15 to 40% of the total mass of the low refractive index layer. The antireflection film according to any one of the above.   The antireflection film according to claim 1, wherein the haze is 3.0 to 70.0% and the average reflectance of 450 to 650 nm is 1.8% or less.   The antireflective film according to any one of claims 1 to 13, wherein a material of the transparent support is triacetyl cellulose, polyethylene terephthalate, or polyethylene naphthalate.   A polarizing plate, wherein the antireflection film according to claim 1 is used for at least one of two protective films of a polarizing film in a polarizing plate.   An image display device comprising the antireflection film according to claim 1 as an outermost layer of a display.   An image display device, wherein the polarizing plate according to claim 15 is used so that an antireflection film as a protective layer of the polarizing plate is an outermost layer of the display.