JP2007102206A - Optical film, antireflection film, and polarizing plate and image display device using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a coating composition and a coated film which contain fluorine-based leveling agent, and satisfy both of improvement of drying irregularity/wind irregularity, and suppression of deterioration in film properties; an antireflection film having high surface uniformity and sufficient antireflection performance; and a polarizing plate and image display device using such a antireflection film. <P>SOLUTION: The coating composition includes a fluoroaliphatic group-containing copolymer which contains a repeated unit corresponding to a monomer (A) containing at least one of fluoroaliphatic-group and a repeated unit corresponding to a monomer (B) containing at least no fluoroaliphatic group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  In recent years, development of materials using various coating methods has progressed, and in particular, thin layer coating technology of several μm to several tens of nm level is necessary for optical films, printing, photolithography, etc., and the required coating accuracy is also high It has become higher as the film thickness is reduced, the substrate size is increased, and the coating speed is increased. Particularly in the production of optical films, the control of the film thickness is a very important point that affects the optical performance, and there is an increasing demand for a technique capable of realizing a high coating speed while maintaining high accuracy.

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

In recent years, with the widespread use of these display devices, in particular, display devices that are thinner in depth than conventional CRTs and have a large display area, display devices with higher definition and higher quality have been required. Accordingly, not only the optical performance of the antireflection film but also film physical properties such as scratch resistance and antifouling performance of the film surface are regarded as important performance requirements of the antireflection film. Further, the surface uniformity of the antireflection film is also strongly required. The term “planar uniformity” as used herein means that there is practically no variation in optical performance represented by antireflection performance in the entire display section.
As an antireflection film production method, there is an inorganic vapor deposition method in which an antiglare antireflection film excellent in gas barrier property, antiglare property, and antireflection property using a silicon oxide film by CVD is described in Patent Document 1. From the viewpoint of mass productivity, a method for producing an antireflection film by all wet coating on a long web is advantageous.

However, all-wet coating using a solvent is very advantageous from the viewpoint of productivity, but it is very difficult to keep the solvent drying conditions immediately after coating, and surface unevenness is likely to occur.
Typical examples of the surface unevenness mentioned here include drying unevenness caused by a difference in solvent drying speed and wind unevenness caused by drying air. In order to improve productivity in all wet coating, it is an essential technique to increase the coating speed. However, if the coating speed is simply increased, the wind speed of the drying wind is also relatively increased, and the wind unevenness is aggravated by the influence of the accompanying wind accompanying the high-speed movement of the support. Thus, conventionally, in order to obtain an antireflection film with suppressed variations in optical performance and film physical properties, the coating speed could not be increased too much.

On the other hand, it is known that improving leveling is effective in reducing unevenness during drying. As one means for improving the leveling property, a method of adding a leveling agent to the coating composition has been proposed. When a leveling agent is added to the coating, the surface tension change during the coating film formation process is reduced or reduced to prevent thermal convection and improve the film uniformity (Non-Patent Document 1). The optimum leveling agent type varies depending on the compatibility with the solvent, resin, and various additives in the target coating composition, but it is effective to use a fluorine-based leveling agent when coating with a solvent. . In general, the fluorine-based leveling agent has the same fluoroaliphatic group as the philic group that contributes to affinity for various compositions such as coatings and molding materials when the activator is used as an additive. Such a compound is generally obtained by copolymerizing a monomer having a fluoroaliphatic group and a monomer having a philic group.
Typical examples of the monomer having an amphiphilic group copolymerized with a monomer having a fluoroaliphatic group include poly (oxyalkylene) acrylate and poly (oxyalkylene) methacrylate.

  However, when conventional fluorine-based leveling agents are used, drying unevenness and wind unevenness are improved, but there may be a problem that film physical properties deteriorate. In particular, when another layer is applied over a layer coated with a coating solution containing a fluorine-based leveling agent, the adhesion between the layer added with the leveling agent and the layer applied over this layer decreases. In some cases, the problem of a decrease in scratch resistance may occur remarkably.

JP 7-333404 A The latest technology of coating additives, supervised by Haruo Kiryu, CMC, 2001

  Accordingly, an object of the present invention is to provide (1) an optical film containing a fluorine leveling agent that achieves both improvement in drying unevenness and wind unevenness and suppression of deterioration in film physical properties, and (2) planar uniformity. It is to provide an antireflection film that is high and achieves sufficient antireflection performance, and (3) to provide a polarizing plate and an image display device using such an antireflection film.

As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved, and the present invention has been completed.
That is, the present invention achieves the object by the following configuration.

(1) A fluoroaliphatic group containing a repeating unit corresponding to at least one fluoroaliphatic group-containing monomer (A) and a repeating unit corresponding to a monomer (B) not containing at least one fluoroaliphatic group After forming a coating film using a coating composition containing a copolymer, when forming a coating film adjacent to the coating film, adjacent to the coating film containing the fluoroaliphatic group-containing copolymer The difference between the solubility parameter of the organic solvent contained in the coating composition for forming the layer and the solubility parameter of the monomer (B) as a whole is 1.0 [(J / cm ³ ) ^{1 / 2} ] An optical film characterized by the following.
(2) The optical film according to (1), wherein a mass fraction of the monomer (A) in the fluoroaliphatic group-containing copolymer is 40 wt% or more and 95 wt% or less.
(3) The optical film as described in (1) or (2), wherein the monomer (B) contains a monomer represented by the following general formula [I].

(In General Formula [I], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, and Y represents a straight chain having 1 to 20 carbon atoms which may have a substituent. A chain, branched or cyclic alkyl group, or an aromatic group which may have a substituent.
(4) The optical film according to any one of (1) to (3), wherein the monomer (B) contains tertiary butyl acrylate or tertiary butyl methacrylate.
(5) The organic solvent contained in the coating composition for forming the adjacent layer contains at least one ketone solvent, (1) to (4), Optical film.
(6) The optical film according to any one of (1) to (5), wherein the organic solvent contained in the coating composition for forming the adjacent layers contains methyl ethyl ketone.
(7) The optical film according to any one of (1) to (6), wherein the film has antireflection performance.
(8) The antireflection film is formed by applying two layers of a hard coat layer and a low refractive index layer having a lower refractive index than the hard coat layer on the hard coat layer, and the hard coat layer. The antireflective film according to (7), wherein the fluoroaliphatic group-containing copolymer is contained.
(9) The antireflection film according to claim 8, wherein the hard coat layer has an antiglare property.
(10) A polarizing plate, wherein the antireflection film according to any one of (7) to (9) is used on at least one side of the polarizing film.
(11) The antireflection film described in any one of (7) to (9) is used as one protective film of the polarizing film, and optical compensation having optical anisotropy is used as the other protective film of the polarizing film. A polarizing plate using a film.
(12) An image display device comprising the antireflection film according to any one of (7) to (9) or the polarizing plate according to (10) or (11).

  According to the present invention, it is possible to provide an antireflection film having high surface uniformity and achieving sufficient antireflection performance, and an image display device having excellent visibility by using the antireflection film.

  Hereinafter, the present invention will be described in more detail. In the present specification, when a numerical value represents a physical property value, a characteristic value, etc., the description “(numerical value 1) to (numerical value 2)” means “(numerical value 1) or more and (numerical value 2) or less”. . In the present specification, the description “(meth) acrylate” means “at least one of acrylate and methacrylate”. The same applies to “(meth) acrylic acid” and the like.

A coating composition for forming a layer that does not contain a fluoroaliphatic group and has a solubility parameter of a repeating unit corresponding to the monomer B and a layer adjacent to the layer containing the fluoroaliphatic group-containing copolymer containing the monomer B The solubility parameter of the organic solvent to be contained can be determined as follows.
The solubility parameter is defined for the first time in the theoretical development of regular solutions in Non-Patent Document 2, and since then, when evaluating the solubility of liquid-liquid, gas-liquid, solid-liquid, and the solubility of substances. Used frequently. Solubility parameters are used to predict and select solubility characteristics of solvents used for the purpose of solubility, permeability, chemical protection, etc. when developing materials in industrial fields such as chemical products, pigments, fibers, and adhesives. (Non-Patent Documents 3 and 4). In general, it has been experimentally confirmed that liquids having similar solubility parameter values are easily dissolved, and polymers such as polymers are soluble in solvents having similar solubility parameters. The solubility parameter used in the present invention was estimated using the numerical values described in Non-Patent Document 6 according to Small's estimation method (Non-Patent Document 5) for monomer B not containing a fluoroaliphatic group. For the solubility parameter of the organic solvent, general numerical values described in Non-Patent Document 7 and the like were used.
When the monomer B contains two or more types of monomers, the solubility parameter was a numerical value obtained by arithmetically averaging the solubility parameters of each monomer by the weight fraction. The solubility parameter is similarly calculated when the organic solvent contained in the coating composition for forming a layer adjacent to the layer containing the fluoroaliphatic group-containing copolymer contains two or more organic solvents. did.

[Non-Patent Document 2] JH Hildebrand; JM Praunitz and RL Scott, Regular and Related Solutions, van Nostrand Reinhold (1969)
[Non-Patent Document 3] K. Hibino; Y. Kimura, J. Appl. Pol. Sci. 77, 1794 (2000)
[Non-Patent Document 4] Nao Kinoshita, Junichi Kanno Paint Research, No.143, 28, Apr.2005
[Non-Patent Document 5] PA Small, J. Appl. Chem. 3, 71 (1953)
[Non-patent document 6] SP value Basics / applications and calculation methods, Hideki Yamamoto, P55, Information Organization, 2005 [Non-patent document 7] Plastic Processing Technology Handbook, edited by Polymer Society, Nikkan Kogyo Shimbun, 1995

The solubility parameter of the repeating unit corresponding to the monomer B, which does not contain a fluoroaliphatic group, and the organic solvent contained in the coating liquid of the layer adjacent to the layer containing the fluoroaliphatic group-containing copolymer containing the monomer B In the present invention, the difference from the solubility parameter is 1.0 [(J / cm ³ ) ^1/2 ] or less, more preferably 0.85 [(J / cm ³ ) ^1/2 ] or less. 7 [(J / cm ³ ) ^1/2 ] or less is particularly preferable. The solubility parameter difference is preferably 1.0 [(J / cm ³ ) ^1/2 ] or less in that it is easy to obtain an optical film having excellent planar uniformity.

1. First, the various compounds that can be used in the optical film of the present invention will be described.

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

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

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

1- (2) Leveling Agent Hereinafter, the copolymer containing a fluoroaliphatic group in the present invention (hereinafter, the copolymer may be simply referred to as “fluorine leveling agent”) will be described in detail.
In addition, you may use leveling agents other than the fluorine-type leveling agent of this invention together.

The fluorine-based leveling agent of the present invention comprises a repeating unit corresponding to at least one fluoroaliphatic group-containing monomer (A) and a repeating unit corresponding to a monomer (B) not containing at least one fluoroaliphatic group. A fluoroaliphatic group-containing copolymer.
The fluorine-based leveling agent of the present invention is a repeating agent corresponding to the fluoroaliphatic group-containing monomer (A) represented by the following general formula [1], general formula [2], general formula [3] or general formula [4]. A fluoroaliphatic group-containing copolymer comprising at least one unit and at least one repeating unit corresponding to the monomer (B) represented by the following general formula [I] that does not contain a fluoroaliphatic group It is preferable.

(In the general formula [1], R ⁰ represents a hydrogen atom, a halogen atom or a methyl group, L represents a divalent linking group, and n represents an integer of 1 to 18)

(In the general formula [2], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ² ) —, m is an integer of 1-6, n Represents an integer of 1 to 18. Here, R ² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.

(In the general formula [3], R ³ represents a hydrogen atom, a halogen atom or a methyl group, L ² represents a divalent linking group, and n represents an integer of 1 to 6.)

(In the general formula [4], R ⁴ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ² ) —, m is an integer of 1 to 6, and n is 1 to 6. Represents the following integer: represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.

(In General Formula [I], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, and Y represents a straight chain having 1 to 20 carbon atoms which may have a substituent. A chain, branched, or cyclic alkyl group or an aromatic group that may have a substituent.

The fluoroaliphatic group-containing monomer represented by the general formula [1] will be described.
In the general formula [1], R ⁰ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. L represents a divalent linking group containing any of an oxygen atom, a nitrogen atom, and a sulfur atom, and represents —COO—, —COO (R ⁵ ) —, —COS—, —COS (R ⁵ ) —, — CON (R ⁶ ) —, —CON (R ⁵ ) (R ⁶ ) — and the like are preferable. Here, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, R ⁶ represents a hydrogen atom, and an alkyl group having 1 to 8 carbon atoms. n represents an integer of 1 to 18, more preferably 4 to 12, still more preferably 6 to 8, and most preferably 6.
In addition, two or more kinds of polymerization units of the fluoroaliphatic group-containing monomer represented by the general formula [1] may be included in the fluorine-based leveling agent as structural units.

In the general formula [2], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ² ) —, more preferably an oxygen atom or —N (R ² ) —, and still more preferably an oxygen atom. R ² 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 still more preferably a hydrogen atom or a methyl group. m represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1. n represents an integer of 1 to 18, more preferably 4 to 12, still more preferably 6 to 8, and most preferably 6.
In addition, two or more kinds of polymerization units of the fluoroaliphatic group-containing monomer represented by the general formula [2] may be included in the fluorine-based leveling agent as structural units.

  Specific examples of the fluoroaliphatic group-containing monomer represented by the general formulas [1] and [2] are given below, but the present invention is not limited to these.

In the general formula [3], R ³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. L ² represents a divalent linking group containing any of an oxygen atom, a nitrogen atom, and a sulfur atom, and represents —COO—, —COO (R ⁵ ) —, —COS—, —COS (R ⁵ ) —, —CON (R ⁶ ) —, —CON (R ⁵ ) (R ⁶ ) — and the like are preferable. Here, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, R ⁶ represents a hydrogen atom, and an alkyl group having 1 to 8 carbon atoms. n represents an integer of 1 or more and 6 or less, more preferably 4 to 6, and still more preferably 6.
Two or more kinds of polymer units of the fluoroaliphatic group-containing monomer represented by the general formula [3] may be contained as a structural unit in the fluoroaliphatic group-containing copolymer.

In the general formula [4], R ⁴ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X represents an oxygen atom, a sulfur atom or —N (R ² ) —, more preferably an oxygen atom or —N (R ² ) —, and still more preferably an oxygen atom. R ² 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 still more preferably a hydrogen atom or a methyl group. m represents an integer of 1 to 6, more preferably 1 to 3, and still more preferably 1. n represents an integer of 1 or more and 6 or less, more preferably 4 to 6, and still more preferably 6. Two or more kinds of polymer units of the fluoroaliphatic group-containing monomer represented by the general formula [4] may be contained as a structural unit in the fluoroaliphatic group-containing copolymer.

  Although the example of the more specific monomer of the fluoro aliphatic group containing monomer represented by General formula [3] or [4] is given below, this invention is not limited to these.

  In addition, some of the fluorinated chemical products produced by the electrolytic fluorination method that has been favorably used in the past are substances that have low biodegradability and high bioaccumulation. There is concern about toxicity and developmental toxicity. Also in the present invention, a fluorine leveling agent having a hydrogen atom at the end of the fluoroaliphatic group and a fluorine atom at the end and a short fluoroalkyl chain length of C6 or less is a more environmentally safe substance. It can be said that it is an advantage.

The repeating unit corresponding to the monomer B represented by the general formula [I] that does not contain a fluoroaliphatic group will be described.
As a repeating unit corresponding to the monomer B represented by the general formula [I], 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.

Specifically, the following monomers can be mentioned.
Acrylic esters:
Methyl acrylate, ethyl acrylate, propyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, tertiary butyl acrylate, etc.
Methacrylic acid esters:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, tertiary butyl methacrylate, etc.

Acrylamides:
Acrylamide, N-alkyl acrylamide (alkyl group having 1 to 3 carbon atoms, for example, methyl group, ethyl group, propyl group), N, N-dialkyl acrylamide (alkyl group having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.
Methacrylamide:
Methacrylamide, N-alkylmethacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl group), N, N-dialkylmethacrylamide (alkyl group having 1 to 6 carbon atoms) ), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.
Allyl compounds:
Allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol and the like.

Vinyl ethers:
Alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, Diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether and the like.
Vinyl esters:
Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl-β-phenyl Butyrate, vinyl cyclohexyl carboxylate, etc.

Dialkyl itaconates:
Dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.
Dialkyl or monoalkyl esters of fumaric acid:
Dibutyl fumarate etc.
In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, styrene, etc.

Among these, in the general formula [I], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, and a hydrogen atom and a methyl group are more preferable. L ¹ represents a divalent linking group, Y is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, and an aromatic group which may have a substituent. Represents. L ¹ represents a divalent linking group containing any ^one of an oxygen atom, a nitrogen atom, and a sulfur atom, and represents —COO—, —COO (R ⁵ ) —, —COS—, —COS (R ⁵ ) —, —CON (R ⁶ ) —, —CON (R ⁵ ) (R ⁶ ) — and the like are preferable. Here, R ⁵ represents an alkyl group having 1 to 8 carbon atoms, R ⁶ represents a hydrogen atom, and an alkyl group having 1 to 8 carbon atoms. Y is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

  Although the example of the more specific monomer of the monomer represented by general formula [I] of this invention is given below, it is not this limitation.

1000-50000 are preferable, as for the mass average molecular weight of the fluorine-type leveling agent used by this invention, 5000-50000 are more preferable, 8000-30000 are further more preferable, and 10000-20000 are especially preferable. A mass average molecular weight of 1000 or more is preferable in terms of sufficient wind unevenness preventing ability. In addition, the mass average molecular weight is preferably 50000 or less in view of sufficient solubility and elution in an organic solvent. Depending on the prescription to be added, the main object is to suppress planar failures such as repelling, and the mass average molecular weight may be preferably 1000 to 20000.
Here, the mass average molecular weight and the molecular weight are converted into 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 fluorine-type leveling agent of this invention can be manufactured by a well-known method. For example, the above-mentioned monomers such as (meth) acrylate having a fluoroaliphatic group and (meth) acrylate having a linear, branched or cyclic alkyl group are added to a general-purpose radical polymerization initiator in an organic solvent. Can be produced by polymerization. Alternatively, other addition-polymerizable unsaturated compounds can be added in some cases and produced in the same manner as described above. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition.

  Hereinafter, examples of specific structures of the fluorine-based leveling agent that can be used in the present invention are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the mass ratio of each monomer component. Mw represents a mass average molecular weight.

  The amount of the polymer units of these fluoroaliphatic group-containing monomers A constituting the fluoroaliphatic group-containing copolymer (fluorine leveling agent) used in the present invention is based on the total polymer units constituting the fluorine leveling agent. Based on this, it is preferably more than 10% by mass, more preferably 40 to 95% by mass, and still more preferably 80 to 95% by mass.

The amount of the fluorine leveling agent added to the coating composition is preferably 0.001% by mass to 1.0% by mass, and more preferably 0.01% by mass to 0.2% by mass.
The coating composition preferably has a water content of 30% by mass or less, more preferably 10% by mass or less, from the viewpoint of improving the surface shape.

  The composition of the present invention can contain necessary components such as a binder, an inorganic filler, and a dispersion stabilizer depending on applications. One or more functional layers are formed by coating one or more coating compositions of the present invention on a support or a support provided with one or more other layers, and if necessary, other layers are further formed. For example, an antireflection film or a polarizing plate can be formed.

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

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

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

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

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

Two or more polyfunctional monomers may be used in combination.
Polymerization of 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.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

1- (4) Polymer Binder In the present invention, a polymer or a crosslinked polymer can 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.

Examples of the polymer main chain include polyolefin (saturated hydrocarbon), polyether, polyurea, polyurethane, polyester, polyamine, polyamide and melamine resin. A polyolefin main chain, a polyether main chain and a polyurea main chain are preferable, a polyolefin main chain and a polyether main chain are more preferable, and a polyolefin main chain is most preferable.
The polyolefin main chain consists of saturated hydrocarbons. The polyolefin main chain is obtained, for example, by an addition polymerization reaction of an unsaturated polymerizable group. The polyether main chain has repeating units bonded by an ether bond (—O—). The polyether main chain is obtained, for example, by a ring-opening polymerization reaction of an epoxy group. In the polyurea main chain, repeating units are bonded by a urea bond (—NH—CO—NH—). The polyurea main chain is obtained, for example, by a condensation polymerization reaction between an isocyanate group and an amino group. In the polyurethane main chain, repeating units are bonded by a urethane bond (—NH—CO—O—). The polyurethane main chain is obtained, for example, by a polycondensation reaction between an isocyanate group and a hydroxyl group (including an N-methylol group). The polyester main chain has repeating units bonded by an ester bond (—CO—O—). The polyester main chain is obtained, for example, by a polycondensation reaction between a carboxyl group (including an acid halide group) and a hydroxyl group (including an N-methylol group). The polyamine main chain has repeating units bonded by imino bonds (—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 is a structure in which two or more main chains are chemically bonded (preferably covalent bonds), but it is preferable to covalently bond three or more main chains. The cross-linked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

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

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

  In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. It is more preferable that it is 0.1 to 28% by mass.

1- (5) Fluorine-containing polymer binder Among the polymer binders in the present invention, a fluorine-containing copolymer compound can be preferably used, particularly for the low refractive index layer.
Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (trade name) , Osaka Organic Chemical Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Co., Ltd.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, and transparency. From the viewpoint of availability, hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, the fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50%. This is a case of mass%.

  Examples of the structural unit for imparting crosslinking reactivity include units represented by the following (A), (B), and (C). (A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether, (B): a carboxyl group, a hydroxy group, an amino group, or a sulfo group A structural unit obtained by polymerization of monomers having, for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, maleic acid, crotonic acid, etc. , (C): a group that reacts with the functional groups of (A) and (B) in the molecule and a compound having a crosslinkable functional group separately from the structural unit of (A) and (B). Structural units obtained (eg acrylic acid for hydroxyl groups) Configuration Unit) and the like which can be synthesized by a method such as the action of Rorido.

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

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

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

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

  The fluorine-containing polymer particularly useful in 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 crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

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

  The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.

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

1- (6) Organosilane Compound The film of the present invention contains a hydrolyzate of organosilane compound and / or a partial condensate thereof (hereinafter, the obtained reaction solution is also referred to as “sol component”). However, it is preferable in terms of scratch resistance.
This sol component functions as a binder by applying the curable composition and then condensing in a drying and heating process to form a cured product. Moreover, when it has a polyfunctional acrylate polymer, 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 [A].
Formula [A]
_{^{(R 10) t -Si (X}} 1) 4-t
In the general formula [A], R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X ¹ 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 And a group represented by R ¹¹ COO (R ¹¹ 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 Is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
t represents an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

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

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

In the general formula [B], R ¹² 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 preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.
Y ¹ represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, a single bond And * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ¹² ) —, and ** represents a position bonded to L ³ .

L ³ 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, and an alkylene group having a linking group therein are preferred. An unsubstituted alkylene group and an unsubstituted arylene group Further, an alkylene group having an ether or ester linking group inside is more preferred, an unsubstituted alkylene group, and an alkylene group having an ether or ester linking group inside is particularly preferred. 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.

u represents 0 or 1; When X ¹ there are a plurality, it may be different even multiple of X ¹ is the same, respectively. u is preferably 0.
R ¹⁰ has the same meaning as in formula [A], 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 ¹ has the same meaning as the general formula [A], preferably a halogen atom, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine atom, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number. 1-3 alkoxy groups are more preferable, and a methoxy group is particularly preferable.

  Two or more compounds of the general formula [A] and general formula [B] may be used in combination. When using together, it is preferable to use together the organosilane compound which has a vinyl polymerizable substituent represented by general formula [B], and the below-mentioned silicon alkoxide compound.

  Although the specific example of a compound represented by general formula [A] and general formula [B] is shown below, it is not limited.

  Of these, (M-1), (M-2), and (M-5) are particularly preferable. These compounds can be used in combination with a silicon alkoxide described later. The silicon alkoxide used in combination is preferably a compound having three alkoxy groups such as methyltrimethoxysilane.

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

Examples of the metal chelate compound include an alcohol represented by the general formula R ³³ OH (wherein R ³³ represents an alkyl group having 1 to 10 carbon atoms) and 3 ³⁴ COCH ₂ COR ³⁵ (wherein R ³⁴ represents the number of carbon atoms). 1 to 10 alkyl groups, R ³⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti and Al. Any metal having a central metal as the metal can be used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³³ ) _p1 (R ³⁴ COCHCOR ³⁵ ) _p2 , Ti (OR ³³ ) _q1 (R ³⁴ COCHCOR ³⁵ ) _q2 , and Al (OR ³³ ) _r1 (R ³⁴ Those selected from the group of compounds represented by COCHCOR ³⁵ ) _r2 are preferred and serve to promote the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound.
R ³³ and R ³⁴ 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 ³⁵ 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.

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

The β-diketone compound and / or β-ketoester compound represented by the general formula R ³⁴ COCH ₂ COR ³⁵ is preferably used in the present invention, and is an agent for improving the stability of the curable composition used in the present invention. It acts as. Here, R ³⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ³⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. That is, by coordinating with a metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the condensation reaction of the hydrolyzate and / or partial condensate of the organosilane compound by these metal chelate compounds is performed. It is considered that the promoting action is suppressed and the storage stability of the resulting composition is improved. R ³⁴ and R ³⁵ constitute a β- diketone compound and / or β- ketoester compound are the same as R ³⁴ and R ³⁵ 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. 2 mol or more is preferable at the point that the storage stability of the composition obtained is sufficient.

In the case of the low refractive index layer, the compounding amount of the organosilane compound is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and most preferably 1 to 10% by mass.
The organosilane compound may be directly added to a curable composition (for example, a coating solution for an antiglare layer, a low refractive index layer, etc.), but the organosilane compound is treated in the presence of a catalyst in advance. It is preferable to prepare a hydrolyzate and / or partial condensate of an organosilane compound and prepare the curable composition using the resulting reaction solution (sol solution). In the present invention, first, the organosilane compound is prepared. A composition containing a hydrolyzate and / or a partial condensate of the above and a metal chelate compound, and a liquid obtained by adding a β-diketone compound and / or a β-ketoester compound to the antiglare layer or low refractive index layer It is preferable that the coating liquid is contained in at least one coating solution.

a, silicon alkoxide A compound represented by RvSi (OR ′) w, wherein R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and v and w are integers such that v + w = 4, respectively. For example, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, Tetrapenta-iso-propoxysilane, tetrapenta-n-proxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutane Toxisilane, methyldimethoxysilane, methyldiethoxysilane, hexyltrimethoxysilane and the like can be mentioned.

b. Silane coupling agents For example, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ Aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane , Methyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (to Trimethoxysilyl) propyl] ammonium chloride, methyl trichlorosilane, dimethyl dichlorosilane, and the like.

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

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

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

1- (7) Initiator Polymerization of monomers having various ethylenically unsaturated groups can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
In preparing the film of the present invention, a photoinitiator or a thermal initiator can be used in combination.

<Photoinitiator>
Examples of photo radical polymerization initiators include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2, 3 -Dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

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

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

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

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

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

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

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

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

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

1- (8) Crosslinkable compound When the monomer or polymer binder according to the present invention alone does not have sufficient curability, necessary curability can be imparted by blending the crosslinkable compound. .
For example, when the polymer body contains a hydroxyl group, various amino compounds are preferably used as the curing agent. The amino compound used as the crosslinkable compound is, for example, a compound containing a total of two or more of any one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specifically, for example, a melamine compound, Examples include urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

  Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine, alkoxylated methylmelamine, or a derivative thereof obtained by reacting melamine and formaldehyde under basic conditions is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained. There are no particular restrictions on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun). Various resinous materials can be used.

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

1- (9) Curing Catalyst In the present invention, a compound that generates a radical or an acid upon irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

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

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

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

1- (10) Translucent Particles Various translucent particles are used for imparting antiglare properties (surface scattering properties) and internal scattering properties to the film of the present invention, particularly the antiglare layer and the hard coat layer. I can do it.

The translucent particles may be organic particles or inorganic particles. As the particle size is not varied, the scattering characteristics are less varied, and the design of the haze value is facilitated. As the translucent particles, plastic beads are preferable, and those having particularly high transparency and a difference in refractive index from the binder as described below are preferable.
As organic particles, polymethyl methacrylate particles (refractive index 1.49), crosslinked poly (acryl-styrene) copolymer particles (refractive index 1.54), melamine resin particles (refractive index 1.57), polycarbonate particles ( Refractive index 1.57), polystyrene particles (refractive index 1.60), crosslinked polystyrene particles (refractive index 1.61), polyvinyl chloride particles (refractive index 1.60), benzoguanamine-melamine formaldehyde particles (refractive index 1. 68) etc. are used.
Examples of the inorganic particles include silica particles (refractive index: 1.44), alumina particles (refractive index: 1.63), zirconia particles, titania particles, and inorganic particles having hollows and pores.

Of these, cross-linked polystyrene particles, cross-linked poly ((meth) acrylate) particles, and cross-linked poly (acryl-styrene) particles are preferably used, and a binder is selected according to the refractive index of each light-transmitting particle selected from these particles. By adjusting the refractive index, the internal haze, surface haze, and centerline average roughness of the present invention can be achieved.
Further, a binder (having a refractive index after curing of 1.50 to 1.53) composed mainly of a trifunctional or higher functional (meth) acrylate monomer and a crosslinked poly (meth) acrylate weight having an acrylic content of 50 to 100 mass percent. It is preferable to use a combination of translucent particles composed of a combination, and in particular, a combination of a binder and translucent particles composed of a crosslinked poly (styrene-acrylic) copolymer (with a refractive index of 1.48 to 1.54). preferable.

The refractive index of the binder (translucent resin) and translucent particles in the present invention is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the binder and the translucent particles (the refractive index of the translucent particles−the refractive index of the binder) is preferably 0.001 to 0.030 as an absolute value, More preferably, it is 0.001-0.020, More preferably, it is 0.001-0.015. The difference is preferably 0.030 or less in terms of suppressing problems such as film character blur, a decrease in dark room contrast, and surface turbidity.

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

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

  The average particle size of the translucent particles is preferably 0.5 to 10 μm, more preferably 2.0 to 6.0 μm. If the average particle size is less than 0.5 μm, the light scattering angle distribution spreads to a wide angle, which may cause blurring of characters on the display. On the other hand, if it exceeds 10 μm, it is necessary to increase the thickness of the layer to be added, which causes problems such as curling and cost increase.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs. It is possible to impart an antiglare property with a light-transmitting particle having a larger particle diameter, and to reduce the surface roughness with a light-transmitting particle having a smaller particle diameter.

  The said translucent particle | grain is mix | blended so that 3-30 mass% may be contained in the addition layer total solid. More preferably, it is 5-20 mass%. If it is less than 3% by mass, the effect of addition is insufficient, and if it exceeds 30% by mass, problems such as image blur, surface turbidity and glare occur.

Moreover, the density of the translucent particles is preferably 10 to 1000 mg / m ² , more preferably 100 to 700 mg / m ² .

<Translucent particle preparation, classification method>

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

The particle size distribution of the translucent particles is preferably monodisperse particles in terms of haze value and control of diffusibility, and uniformity of the coated surface. 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 the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. Particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .
It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification.

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

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

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

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

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

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

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

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

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

  The addition amount of the monomer and inorganic particles in the layer is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the binder. Two or more kinds of inorganic particles may be used in the layer.

<Low refractive index particles>
The inorganic particles contained in the low refractive index layer desirably have 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 average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

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

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

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

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

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x expressed by the following formula (VIII) is (formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
Preferably it is 10-60%, 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 1.15. Rate particles are not preferred.

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

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

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

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

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

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

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

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

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

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

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

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

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
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 added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in WO 2004/017105.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

1- (16) Thickener The thickener according to the present invention increases the viscosity of the coating composition when the coating composition is coated on a support, and prevents phenomena such as repelling and sedimentation of translucent particles. By suppressing it, it has a function of forming a uniform and stable film surface.
The term “thickener” as used in the present invention means that the viscosity of the liquid increases when it is added, and is preferably 0.05 to 10 cP, more preferably as the magnitude of increase in viscosity when added. Is 0.07 to 7.5 cP, more preferably 0.10 to 5 cP.

  Examples of such thickeners include, but are not limited to: Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate) poly (1,4-butylene adipate) poly (1,4-butylene glutarate) poly (1,4-butylene succinate) Poly (1,4-butylene terephthalate) poly (ethylene terephthalate) poly (2-methyl-1,3-propylene adipate) poly (2-methyl-1,3-propylene glutarate) poly (neopentylglycol adipate) poly (neo Pentyl glycol sebacate) poly (1,3-propylene adipate) poly (1,3-propylene glutarate) polyvinyl butyral polyvinyl formal polyvinyl acetal polyvinyl propanal polyvinyl Kisa knurls polyvinylpyrrolidone polyacrylic acid ester polymethacrylic acid ester cellulose acetate butyrate

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

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

1- (18) Support The support of the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.

<Cellulose acylate film>
Among them, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for a polarizing plate is preferable, and a cellulose triacetate film is particularly preferable. The thickness of the transparent support is usually about 25 μm to 1000 μm.

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

In general, the 2, 3, and 6 hydroxyl groups of cellulose acylate are not evenly distributed by 1/3 of the total substitution degree, and the substitution degree of the 6-position hydroxyl group tends to be small. In the present invention, it is preferable that the substitution degree of the 6-position hydroxyl group of cellulose acylate is larger than that of the 2- and 3-positions.
The hydroxyl group at the 6-position with respect to the total degree of substitution is preferably substituted with an acyl group of 32% or more, more preferably 33% or more, and particularly preferably 34% or more. Furthermore, the substitution degree of the 6-position acyl group of cellulose acylate is preferably 0.88 or more. The 6-position hydroxyl group may be substituted with a propionyl group, butyroyl group, valeroyl group, benzoyl group, acryloyl group or the like, which is an acyl group having 3 or more carbon atoms, in addition to the acetyl group. The degree of substitution at each position can be determined by NMR.
In the present invention, as cellulose acylate, paragraphs “0043” to “0044” [Example] [Synthesis Example 1], paragraphs “0048” to “0049” [Synthesis Example 2], paragraph “ Cellulose acetate obtained by the method described in “0051” to “0052” [Synthesis Example 3] can be used.

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

2. Layers constituting the film The film of the present invention is usually obtained by mixing and coating the above-mentioned various compounds. Next, the layers constituting the film of the present invention will be described.

2- (1) Hard Coat Layer The film of the present invention is preferably provided with a hard coat layer on one surface of the transparent support in order to impart the physical strength of the film.
Preferably, a low refractive index layer is provided thereon, and more preferably, an intermediate refractive index layer and a high refractive index layer are provided between the hard coat layer and the low refractive index layer to constitute an antireflection film.
The hard coat layer may be composed of two or more layers.

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

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

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

  For the purpose of imparting internal scattering properties, the hard coat layer preferably has matte particles having an average particle diameter of preferably 1.0 to 10.0 μm, more preferably 1.5 to 7.0 μm, such as inorganic compound particles or resin particles. It may contain.

  For the purpose of controlling the refractive index of the hard coat layer, a high refractive index monomer, inorganic particles, or both can be added to the binder of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the description of the layers constituting the film, the binder containing the polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after forming the hard coat layer, and the inorganic particles dispersed therein. Called.

The haze of the hard coat layer varies depending on the function imparted to the antireflection film.
In the case where the sharpness of the image is maintained, the reflectance of the surface is suppressed, and the light scattering function is not imparted inside and on the surface of the hard coat layer, the haze value is preferably as low as possible, specifically 10% or less is preferable. More preferably, it is 5% or less, and most preferably 2% or less.

On the other hand, in addition to the function of suppressing the reflectance of the surface, in the case of imparting an antiglare function by surface scattering of the hard coat layer, the surface haze is preferably 5% to 15%, preferably 5% to 10%. It is more preferable that
Also, when it is difficult to see the pattern, color unevenness, brightness unevenness, glare, etc. of the liquid crystal panel due to internal scattering of the hard coat layer, or to add the function of expanding the viewing angle by scattering, the internal haze value (from the total haze value) The value obtained by subtracting the surface haze value) is preferably 10% to 90%, more preferably 15% to 80%, and most preferably 20% to 70%.
The film of the present invention can freely set surface haze and internal haze according to the purpose.

  In addition, for the surface irregularity shape of the hard coat layer, in order to obtain a clear surface for the purpose of maintaining the sharpness of the image, among the characteristics indicating the surface roughness, for example, the centerline average roughness (Ra) is set. The thickness is preferably 0.10 μm or less. Ra is more preferably 0.09 μm or less, and still more preferably 0.08 μm or less. In the film of the present invention, the surface unevenness of the hard coat layer is dominant to the surface unevenness of the film, and the center line average roughness of the antireflection film is adjusted by adjusting the center line average roughness of the hard coat layer. It can be set as the said range.

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

  In addition, it is also a preferable aspect to use the coating film formed using the composition of this invention as a hard-coat layer.

2- (2) Antiglare Layer The antiglare layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering and preferably hard coat properties for improving the scratch resistance of the film.

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

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

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

The mat particles are contained in the antiglare layer so that the amount of mat particles in the formed antiglare 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 film thickness of the antiglare layer is preferably 1 to 10 μm, and more preferably 1.2 to 8 μm. If it is too thin, the hard property is insufficient, and if it is too thick, curling and brittleness may be deteriorated and workability may be lowered.

  On the other hand, the center line average roughness (Ra) of the antiglare layer is preferably in the range of 0.10 to 0.40 μm. 0.40 μm or less is preferable in that it can suppress problems such as glare and whitening of the surface when external light is reflected. Further, it is preferable that the value of the transmitted image definition is 5 to 60%.

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

  In addition, it is also a preferable aspect to use the coating film formed using the composition of this invention as an anti-glare layer.

2- (3) High Refractive Index Layer, Medium Refractive Index Layer The film of the present invention can be provided with a high refractive index layer and a medium refractive index layer to enhance antireflection properties.
In the following specification, the high refractive index layer and the medium refractive index layer may be collectively referred to as a high refractive index layer. In the present invention, “high”, “medium”, and “low” in the high refractive index layer, the medium refractive index layer, and the low refractive index layer represent the relative refractive index relationship between the layers. In terms of the relationship with the transparent support, the refractive index preferably satisfies the relationship of transparent support> low refractive index layer, high refractive index layer> transparent support.
In the present specification, the high refractive index layer, the middle refractive index layer, and the low refractive index layer may be collectively referred to as an antireflection layer.

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

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

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the middle refractive index layer are preferably used for forming the high refractive index layer and the middle refractive index layer in a dispersion state.
In the dispersion of the inorganic particles, it is preferable to disperse in the dispersion medium in the presence of a dispersant.

  The high refractive index layer and the medium refractive index layer used in the present invention are preferably used in a dispersion liquid in which inorganic particles are dispersed in a dispersion medium, preferably a binder precursor necessary for matrix formation (for example, an ionizing radiation curable composition described later). Polyfunctional monomer, polyfunctional oligomer, etc.), photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a medium refractive index layer, and a high refractive index layer and a medium refractive index layer are formed on a transparent support. It is preferable that the coating composition is applied and cured by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound (for example, a polyfunctional monomer or a polyfunctional oligomer).

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

  The binder of the high refractive index layer is preferably added in an amount of 5 to 80% by mass based on the solid content of the coating composition of the layer.

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

  The film thickness of the high refractive index layer can be appropriately designed depending on the application. When using a high refractive index layer as an optical interference layer described later, the thickness is preferably 30 to 200 nm, more preferably 50 to 170 nm, and particularly preferably 60 to 150 nm.

The haze of the high refractive index layer is preferably as low as possible when it does not contain particles that impart an antiglare function. It is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.
The high refractive index layer is preferably constructed directly on the transparent support or via another layer.

2- (4) Low Refractive Index Layer The low refractive index layer is usually used for reducing the reflectance of the film.

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

  The curable composition preferably contains (A) the fluoropolymer, (B) inorganic particles, and (C) an organosilane compound.

  In the low refractive index layer, a binder is preferably used for dispersing and fixing the fine particles according to the present invention. As the binder, the binder described in the hard coat layer can be used, but it is preferable to use a fluorine-containing polymer having a low refractive index or a fluorine-containing sol-gel material. The fluorine-containing polymer or fluorine-containing sol-gel is a material that has a dynamic friction coefficient of 0.03 to 0.30 on the surface of the low refractive index layer formed by crosslinking by heat or ionizing radiation and a contact angle of 85 to 120 ° with water. Is preferred.

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

  The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm. The surface resistance of the antistatic layer is preferably 105 to 1012 Ω / sq, more preferably 105 to 109 Ω / sq, and most preferably 105 to 108 Ω / sq. The surface resistance of the antistatic layer can be measured by a four probe method.

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

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

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

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

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

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

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

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

2- (9) Anti-curl layer The film of the present technology may be subjected to anti-curl processing. The anti-curl processing is to give the function of trying to curl with the surface to which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent resin film and both sides are processed. When surface treatments of different degrees and types are applied, it functions to prevent curling with the surface facing inward.
The anti-curl layer may be provided on the side opposite to the side having the anti-glare layer or anti-reflection layer of the base material, or for example, an easy-adhesion layer may be coated on one side of the transparent resin film, and the anti-curl processing is performed on the opposite side The mode which coats is mentioned.

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

2- (10) Water Absorbing Layer A water absorbent can be used in the film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.
The layer containing these water absorbents may be prepared by using a vacuum deposition method or the like as in the barrier layer described later, or nanoparticles may be prepared by various methods. The thickness of the layer is preferably 1 to 100 nm, and more preferably 1 to 10 nm. The layer containing the water absorbent is between the support and the laminate (a laminate of the barrier layer and the organic layer), between the uppermost layer of the laminate, between the laminates, or in the organic layer or barrier layer in the laminate. It may be added. When added to the barrier layer, a co-evaporation method is preferably used.

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

3. Layer structure of film About the film of this invention, a well-known layer structure can be used using the above layers. For example, the following are typical examples.
a. Support / hard coat layer b. Support / hard coat layer / low refractive index layer (FIG. 1)
c. Support / hard coat layer / high refractive index layer / low refractive index layer (FIG. 2)
d. Support / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer (FIG. 3)

As shown in b (FIG. 1), when a hard coat layer is applied on a support and a low refractive index layer is laminated, it can be suitably used as an antireflection film. The low refractive index layer can reduce surface reflection by the principle of thin film interference by forming the low refractive index layer 4 on the hard coat layer with a film thickness of about 1/4 of the wavelength of light.
Moreover, even if a high-refractive index layer and a low-refractive index layer are laminated after applying a hard coat layer on a support as shown in FIG. 2 (c), it can be suitably used as an antireflection film. Further, by installing a layer structure in the order of a support, a hard coat layer, a medium refractive index layer, a high refractive index layer, and a low refractive index layer as shown in d (FIG. 3), the reflectance is 1% or less. can do.

  In the constitutions a to d, the hard coat layer (2) can be an antiglare layer having antiglare properties. The antiglare property may be formed by dispersion of matte particles as shown in FIG. 4 or may be formed by surface shaping by a method such as embossing as shown in FIG. The antiglare layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties, and may be composed of a plurality of layers, for example, 2 to 4 layers.

In addition, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the support and the surface layer or the outermost layer. , If there is a problem with dust on the surface, etc.), another hard coat layer (when one hard coat layer or antiglare layer is insufficient in hardness), gas barrier layer, water absorption layer ( Moisture-proof layer), adhesion improving layer, antifouling layer (contamination preventing layer), and the like.
The refractive index of each layer constituting the antiglare antireflection film having the antireflection layer in the invention preferably satisfies the following relationship.
Refractive index of hard coat layer> refractive index of transparent support> refractive index of low refractive index layer

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

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

<Filtration>
The coating solution used for coating is preferably filtered before coating. As a filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within a range in which components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 50 μm is preferably used, and a filter having an absolute filtration accuracy of 0.1 to 30 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filtration member of the wet dispersion of an inorganic compound mentioned above is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

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

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

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

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

  The micro gravure coating method used 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 olefin-based polymer is formed on one side of the unwound support. It can be applied by a gravure coating method.

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

In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, as a die coater that can be preferably used in a region having a small wet coating amount (20 cc / m ² or less) such as a hard coat layer or an antireflection layer, the coating method described in JP-A-2006-122889 is used. preferable.

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

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

4- (5) Curing After drying the solvent, the film of the present invention can be passed through a zone in which each coating film is cured by ionizing radiation and / or heat on the web to cure the coating film.

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

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

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

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

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

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

  As a method of reducing the oxygen concentration to 6% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

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

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

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

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

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

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

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

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

The above steps may be performed every time each layer is formed, or a plurality of coating parts-drying chambers-curing parts may be provided to continuously form each layer.
In order to create the film of the present invention, as described above, the coating step in the coating unit and the drying step performed in the drying chamber are performed in a highly clean air atmosphere simultaneously with the microfiltration operation of the coating solution, and It is preferable that dust and dust on the film are sufficiently removed before application. The air cleanliness of the coating process and the drying process is desirably class 10 (353 particles / 0.5 m or more / (cubic meter) or less) based on the standard of air cleanliness in the US Federal Standard 209E. Preferably it is class 1 (35.5 particles / (cubic meter) or less) having a particle size of 0.5 μm or more. Moreover, it is more preferable that the degree of air cleanliness is high also in the feeding and winding parts other than the coating-drying process.

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

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

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

b. Method of applying alkaline solution As a means of avoiding damage to each film in the above-mentioned immersion method, an alkali solution is applied, heated, washed with water, and dried only on the surface opposite to the surface having the coating layer under appropriate conditions. A liquid coating method is preferably used. The application in this case means that an alkaline solution or the like is brought into contact only with the surface to be saponified, and in addition to the application, it may be carried out by spraying or contacting a belt containing the solution. Including. By adopting these methods, a separate facility and process for applying an alkaline solution are required, which is inferior to the immersion method (1) from the viewpoint of cost. On the other hand, since the alkali solution contacts only the surface to be saponified, the opposite surface can have a layer using a material that is weak against the alkali solution. For example, vapor deposition films and sol-gel films have various effects such as corrosion, dissolution, and peeling due to alkali solution, so it is not desirable to use the immersion method. Is possible.

  In any of the saponification methods (1) and (2), since each layer can be formed by unwinding from a roll-shaped support, it may be performed by a series of operations in addition to the film manufacturing process. . Furthermore, the polarizing plate can be produced more efficiently than the same operation with a single wafer by continuously performing the pasting step with the polarizing plate made of the unwound support.

c. Method of protecting and saponifying with a laminate film As in (2) above, when the coating layer is insufficient in resistance to an alkaline solution, a laminate film is pasted on the surface on which the final layer is formed after forming the final layer. By immersing them in an alkaline solution after combining them, only the triacetyl cellulose surface opposite to the surface on which the final layer is formed can be hydrophilized, and then the laminate film can be peeled off. Even in this method, the hydrophilic treatment necessary for the polarizing plate protective film can be applied only to the surface opposite to the surface on which the final layer of the triacetyl cellulose film is formed without damaging the coating layer. Compared with the method (2), there is an advantage that a laminate film is generated as waste, but a device for applying a special alkaline solution is unnecessary.

d. Method of immersing in alkaline solution after forming up to middle layer Although resistant to alkaline solution up to lower layer, but insufficient resistance to alkaline solution of upper layer, dip into alkaline solution after forming up to lower layer to make both sides hydrophilic The upper layer can also be formed after processing. Although the manufacturing process is complicated, for example, in a film composed of an antiglare layer and a low refractive index layer of a fluorine-containing sol-gel film, when there is a hydrophilic group, the interlayer adhesion between the antiglare layer and the low refractive index layer is improved. There are advantages to doing.

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

4- (8) Production of Polarizing Film The film of the present invention can be used as a polarizing film and a protective film disposed on one side or both sides thereof, and can be used as a polarizing film.
As one protective film, the film of the present invention is used. The other protective film may be a normal cellulose acetate film, but is produced by the above-mentioned solution casting method and at a stretch ratio of 10 to 100%. It is preferable to use a cellulose acetate film stretched in the width direction in the form of a roll film.
Furthermore, in the polarizing plate of the present invention, it is preferable that one side is an antireflection film, whereas the other protective film is an optical compensation film having an optically anisotropic layer made of a liquid crystalline compound.

Examples of the polarizing film include iodine-based polarizing films, dye-based polarizing films using dichroic dyes, and polyene-based polarizing films. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film.
The transparent support of the antireflection film and the slow axis of the cellulose acetate film and the transmission axis of the polarizing film are arranged so as to be substantially parallel.

The moisture permeability of the protective film is important for the productivity of the polarizing plate. The polarizing film and the protective film are bonded together with an aqueous adhesive, and the adhesive solvent is dried by diffusing in the protective film. The higher the moisture permeability of the protective film, the faster the drying and the higher the productivity. However, if the protective film is too high, moisture will enter the polarizing film depending on the usage environment (high humidity) of the liquid crystal display device. Polarization ability decreases.
The moisture permeability of the protective film is determined by the thickness, free volume, hydrophilicity / hydrophobicity, etc. of the transparent support or polymer film (and polymerizable liquid crystal compound).
When using the film of the present invention as a protective film of a polarizing plate, the moisture permeability is preferably from 100~1000g / m ² · 24hrs, and more preferably a 300~700g / m ² · 24hrs.
In the case of film formation, the thickness of the transparent support can be adjusted by lip flow rate and line speed, or stretching and compression. Since the moisture permeability varies depending on the main material to be used, it is possible to make a preferable range by adjusting the thickness.
In the case of film formation, the free volume of the transparent support can be adjusted by the drying temperature and time.
Also in this case, moisture permeability varies depending on the main material to be used, so that a preferable range can be obtained by adjusting the free volume.
The hydrophilicity / hydrophobicity of the transparent support can be adjusted by an additive. The moisture permeability can be increased by adding a hydrophilic additive to the free volume, and conversely, the moisture permeability can be lowered by adding a hydrophobic additive.
By independently controlling the moisture permeability, a polarizing plate having an optical compensation ability can be manufactured at low cost with high productivity.

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, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film 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.
Of the two protective films of the polarizer, the film other than the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

6). Form of use of the present invention The film of the present invention is used in image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD) and cathode ray tube display devices (CRT). The optical filter according to the present invention can be used on a known display such as a plasma display panel (PDP) or a cathode ray tube display (CRT).

6- (1) Liquid Crystal Display Device The film and polarizing plate of the present invention can be advantageously used for an image display device such as a liquid crystal display device, and are preferably used for the outermost layer of the display.
The liquid crystal display device has a liquid crystal cell and two polarizing plates arranged on both sides thereof, and the liquid crystal cell carries a liquid crystal between two electrode substrates. Furthermore, one optically anisotropic layer may be disposed between the liquid crystal cell and one polarizing plate, or two optically anisotropic layers may be disposed between the liquid crystal cell and both polarizing plates.

  The liquid crystal cell is preferably in TN mode, VA mode, OCB mode, IPS mode or ECB mode.

<TN mode>
In the TN mode liquid crystal cell, rod-like liquid crystal molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °.
The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

<VA mode>
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 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 (for 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).

<OCB mode>
The OCB mode liquid crystal cell is a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in substantially opposite directions (symmetrically) at the upper and lower portions of the liquid crystal cell. US Pat. No. 4,583,825, No. 5,410,422. 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 called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.

<IPS mode>
The IPS mode liquid crystal cell is a type in which a nematic liquid crystal is switched by applying a lateral electric field. IDRC (Asia Display '95), p. 577-580 and p. 707-710.

<ECB mode>
In the ECB mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied. The ECB mode is one of the liquid crystal display modes having the simplest structure, and is described in detail in, for example, Japanese Patent Application Laid-Open No. 5-203946.

5- (2) Display other than liquid crystal display device <PDP>
A plasma display panel (PDP) is generally composed of a gas, a glass substrate, an electrode, an electrode lead material, a thick film printing material, and a phosphor. Two glass substrates are a front glass substrate and a rear glass substrate. An electrode and an insulating layer are formed on the two glass substrates. A phosphor layer is further formed on the rear glass substrate. Two glass substrates are assembled and gas is sealed between them.
Plasma display panels (PDP) are already commercially available. The plasma display panel is described in JP-A-5-205643 and JP-A-9-306366.

The front plate may be disposed on the front surface of the plasma display panel. The front plate preferably has sufficient strength to protect the plasma display panel. The front plate can be used with a gap from the plasma display panel, or can be used by directly pasting the front plate to the plasma display body.
In an image display device such as a plasma display panel, an optical filter can be directly attached to the display surface. When a front plate is provided in front of the display, an optical filter can be attached to the front side (outside) or the back side (display side) of the front plate.

<Touch panel>
The film of the present invention can be applied to touch panels described in JP-A-5-127822 and JP-A-2002-48913.

<Organic EL device>
The film of the present invention can be used as a substrate (base film) such as an organic EL element or a protective film.
When the film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653, JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776, etc. The contents described in each publication can be applied. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

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

(Preparation of coating solution for antiglare hard coat layer (HCL-1))

  279.4 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), 13 photopolymerization initiators (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) .7 parts by mass, crosslinked acrylic styrene particles (average particle size 3.5 μm, refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% by mass MiBK dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser) 239.9 parts by mass, 1.14 parts by mass of a fluorine-based leveling agent (P-90 described in the specification, 40% by mass MEK solution), silane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) 60.5 parts by mass, MiBK 210.0 parts by mass, MEK 112.5 parts by mass, propylene glycol 28.1 parts by mass Part, CAB-531-1 (cellulose acetate butyrate, molecular weight 40,000, manufactured by Eastman Chemical Co., Ltd., 20% by mass MiBK solution) was added and 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 for antiglare hard coat layer (HCL-1).

(Preparation of anti-glare hard coat layer coating solution (HCL-2))
Instead of the fluorine leveling agent (P-90), the fluorine leveling agent (P-96 described in the specification, 40% by mass MEK solution) 1 in the above-mentioned coating liquid for antiglare hard coat layer (HCL-1) An anti-glare hard coat layer coating solution (HCL-2) was prepared in exactly the same manner as the coating solution (HCL-1), except for the addition of .14 parts by mass.

(Preparation of coating solution for antiglare hard coat layer (HCL-3))
Fluorine leveling agent (P-109, 40 mass% MEK solution described in the specification) in place of the fluorine leveling agent (P-90) in the antiglare hard coat layer coating solution (HCL-1) An antiglare hard coat layer coating solution (HCL-3) was prepared in exactly the same manner as the coating solution (HCL-1), including the amount added, except that 14 parts by mass was added.

(Preparation of anti-glare hard coat layer coating solution (HCL-4))
Fluorine leveling agent (P-110 described in the specification, 40 mass% MEK solution) in place of the fluorine leveling agent (P-90) in the antiglare hard coat layer coating solution (HCL-1) An antiglare hard coat layer coating solution (HCL-4) was prepared in exactly the same manner as the coating solution (HCL-1), including the amount added, except that 14 parts by mass was added.

(Preparation of anti-glare hard coat layer coating solution (HCL-5))
In the antiglare hard coat layer coating solution (HCL-1), the addition of a fluorine-based leveling agent (P-90 described in the specification) was not performed, but instead, 1.14 parts by mass of MEK was added. In addition, an antiglare hard coat layer coating solution (HCL-5) was prepared in exactly the same manner as the coating solution (HCL-1), including the amount added.

(Preparation of sol solution a)
In a reactor equipped with a stirrer and a reflux condenser, 119 parts of methyl ethyl ketone, 101 parts of acryloyloxypropyltrimethoxysilane (KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.) and 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 of the sol liquid a 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 coating solution for low refractive index layer (LL-1))
JTA113 (trade name, refractive index 1.44, solid content concentration 6%, MEK solution, manufactured by JSR Corporation) 13.1 parts by mass, colloidal silica dispersion MEK-ST-L (trade name, average particle size 45 nm, MEK solution, solid concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.31 parts by mass, 0.59 parts by mass of the sol a, and 5.7 parts by mass of methyl ethyl ketone were added, and after stirring, made of polypropylene with a pore size of 1 μm The solution was filtered through a filter to prepare a coating solution for low refractive index layer (LL-1).

(Preparation of coating solution for low refractive index layer (LL-2))
13.1 parts by mass of a solvent-substituted product (solid content concentration 6%, toluene solution) of JTA113 (trade name, refractive index 1.44, solid content concentration 6%, MEK solution, manufactured by JSR Corporation), colloidal silica dispersion MEK-ST-L (trade name, average particle size 45 nm, MEK solution, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) solvent replacement product (solid content concentration 30%, toluene solution) 1.31 parts by mass, 0.59 parts by mass of the solvent-substituted product (toluene solution) and 5.7 parts by mass of toluene were added to the sol solution a, and after stirring, the mixture was filtered with a polypropylene filter having a pore size of 1 μm to obtain a coating solution for a low refractive index layer. (LL-2) was prepared.

(Preparation of coating solution for low refractive index layer (LL-3))
13.1 parts by mass of a solvent-substituted product (solid content concentration 6%, cyclohexanone solution) of JTA113 (trade name, refractive index 1.44, solid content concentration 6%, MEK solution, manufactured by JSR Corporation), colloidal silica dispersion MEK-ST-L (trade name, average particle size 45 nm, MEK solution, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.) 1.31 parts by mass of solvent replacement product (solid content concentration 30%, cyclohexanone solution) 0.59 parts by mass of the solvent-substituted product (cyclohexanone solution) and 5.7 parts by mass of cyclohexanone were added to the sol solution a, and after stirring, the mixture was filtered with a polypropylene filter having a pore size of 1 μm to obtain a coating solution for a low refractive index layer. (LL-3) was prepared.

(Die coater configuration)
As the die coater, the die coater described in Example 1 of JP-A-2006-122889 was used. The upstream lip land length IUP was 0.5 mm, the downstream lip land length ILO was 50 μm, the length of the opening of the slot 16 in the web running direction was 150 μm, and the length of the slot 16 was 50 mm.

  The gap between the upstream lip land 18a and the web W is 50 μm longer than the gap between the downstream lip land 18b and the web W (hereinafter referred to as an overbite length of 50 μm), and the gap between the downstream lip land 18b and the web W GL was set to 50 μm.

  Further, the gap GS between the side plate 40b and the web W of the decompression chamber 40 and the gap GB between the back plate 40a and the web W were both 200 μm.

<Example 1>
(Preparation of antiglare hard coat layer 1)
With an ultrasonic dust remover, the surface of the application side of a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm is subjected to charge removal treatment, and then the hard coat layer coating liquid (HCL-1) is applied. A 21.0 cc / m ² coating solution was applied at a coating speed of 30 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.4 kPa. In the application of (HCL-1), the gap GL between the downstream lip land 18b and the web W was set to 100 μm. The coated web was then dried at 80 ° C., and then a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. Then, the coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 60 mJ / cm ² , and the antiglare hard coat layer 1 having a thickness of 7 μm was formed.

<Examples 2 to 5>
(Preparation of antiglare hard coat layers 2 to 5)
Antiglare hard coat layer 2 in the same manner as in Example 1 except that the hard coat layer coating liquids (HCL-2) to (HCL-5) are used instead of the hard coat layer coating liquid (HCL-1). ~ 5 were created.

[Evaluation of antiglare hard coat layer]
About the anti-glare hard-coat layers 1-5 obtained in Examples 1-5, the following items were evaluated.

(Surface evaluation)
The back surfaces of the antiglare hard coat layers 1 to 5 obtained in Examples 1 to 5 were painted black, and the state of the antireflection film surface was visually observed under a tungsten lamp. The results are shown in Table 1. When the in-plane anti-glare property was uniform, it was evaluated as ◯, and when in-plane anti-glare property variation was observed, it was evaluated as x. The antiglare hard coat layers prepared in Examples 1 to 4 coated with a coating liquid containing a fluorine leveling agent had a uniform antiglare property over the entire surface and a good surface shape. On the other hand, since the antiglare hard coat layer prepared in Example 5 did not contain a fluorine leveling agent, variation in antiglare properties occurred in the surface, and the surface shape was not uniform.

<Examples 6 to 10>
(Preparation of antireflection film)
On the anti-glare hard coat layers 1 to 5 obtained in Examples 1 to 5, the low refractive index layer coating solution (LL-1) was applied at 30 m / min using the die coater. The degree of vacuum in the vacuum chamber was 0.8 kPa. The coated web was then dried at 90 ° C. for 30 seconds, and then purged with nitrogen so that the atmosphere had an oxygen concentration of 0.05% by volume or less, and a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). ) Was irradiated with ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² to form a low refractive index layer (refractive index 1.45, film thickness 95 nm). In this way, antireflection films 1 to 5 were produced.

  In the above steps, the coating and drying steps are carried out in an air atmosphere with an air cleanliness of 30 particles / (cubic meter) or less as particles of 0.5 μm or more, and the cleanliness described in JP-A-10-309553 just before the coating. The air was sprayed at a high speed to peel off the deposits from the film surface, and the coating was performed while removing dust by a method of sucking with a suction port close to the film. The charged voltage of the base before dust removal was 200 V or less. Said application | coating was performed in each process of sending-out-dust removal-application-dry- (UV or heat) hardening-winding up for every layer.

<Examples 11 to 15>
Antireflection films 6 to 10 were prepared in the same manner as in Examples 6 to 10 except that the coating liquid for low refractive index layer (LL-2) was used instead of the coating liquid for low refractive index layer (LL-1). .

<Examples 16 to 20>
Antireflection films 11 to 15 were prepared in the same manner as in Examples 6 to 10 except that the coating solution for low refractive index layer (LL-3) was used instead of the coating solution for low refractive index layer (LL-1). .

[Evaluation of antireflection film]
The antireflection films obtained in Examples 6 to 20 were evaluated for the following items.

(Abrasion resistance evaluation)
The antireflective films obtained in Examples 6 to 20 were subjected to a rubbing test on the sample surface under the following conditions using a rubbing tester.

Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool “Gelade No. 0000” (manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester 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.
◎ and ○ levels are preferred because they are clearly less likely to be scratched even under actual use conditions, but levels below ○ △ are not preferred because they are easily scratched under actual use conditions.

As apparent from Table 2, the difference between the solubility parameter of the monomer B that does not contain the fluoroaliphatic group of the fluorine-based leveling agent and the solubility parameter of the organic solvent contained in the low refractive index layer is 1.0 [(( J / cm ³ ) ^1/2 ] or less, it can be seen that the scratch resistance is good.

  The antireflective films 1 to 15 obtained in Examples 6 to 20 were immersed in a 2.0 normal 55 ° C. NaOH aqueous solution for 2 minutes to saponify the triacetyl cellulose surface on the back side of the film, and had a thickness of 80 μm. Adheres and protects both sides of a polarizer made by adsorbing iodine to polyvinyl alcohol and stretching it with a saponified triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) under the same conditions. Thus, a polarizing plate was created. A polarizing plate on the viewing side of a liquid crystal display device (TH-15TA2, manufactured by Matsushita Electric Industrial Co., Ltd.) using a TN-type liquid crystal cell so that the antireflection film side becomes the outermost surface is the polarizing plate thus prepared. As a result, it was possible to obtain a display device with extremely high display quality in which the background reflection was extremely small and the uniformity within the display surface was ensured.

It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention.

Explanation of symbols

(1) Support (2) Hard coat layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer

Claims (12)

Fluoroaliphatic group-containing copolymer comprising a repeating unit corresponding to at least one fluoroaliphatic group-containing monomer (A) and a repeating unit corresponding to a monomer (B) not containing at least one fluoroaliphatic group After forming a coating film using a coating composition containing, a layer adjacent to the coating film containing the fluoroaliphatic group-containing copolymer is formed when a coating film is further formed adjacent to the coating film. The difference between the solubility parameter as the total of the organic solvent contained in the coating composition for the coating and the solubility parameter as the total of the monomer (B) is 1.0 [(J / cm ³ ) ^1/2 ] or less An optical film characterized in that   2. The optical film according to claim 1, wherein a mass fraction of the monomer (A) in the fluoroaliphatic group-containing copolymer is 40 wt% or more and 95 wt% or less. The said monomer (B) contains the monomer represented by the following general formula [I], The optical film as described in any one of Claim 1 or 2 characterized by the above-mentioned.

(In General Formula [I], R ¹ represents a hydrogen atom, a halogen atom or a methyl group, L ¹ represents a divalent linking group, and Y represents a straight chain having 1 to 20 carbon atoms which may have a substituent. A chain, branched or cyclic alkyl group, or an aromatic group which may have a substituent.   The said monomer (B) contains tertiary butyl acrylate or tertiary butyl methacrylate, The optical film as described in any one of Claims 1-3 characterized by the above-mentioned.   The optical film according to any one of claims 1 to 4, wherein the organic solvent contained in the coating composition for forming the adjacent layer contains at least one ketone-based solvent.   The optical film according to claim 1, wherein the organic solvent contained in the coating composition for forming the adjacent layer contains methyl ethyl ketone.   It is an optical film as described in any one of Claims 1-6, Comprising: It has antireflection performance, The antireflection film characterized by the above-mentioned.   The antireflection film is formed by applying two layers of a hard coat layer and a low refractive index layer having a refractive index lower than that of the hard coat layer on the hard coat layer, and the fluoro fat is applied to the hard coat layer. The antireflective film according to claim 7, comprising a group group-containing copolymer.   The antireflection film according to claim 8, wherein the hard coat layer has an antiglare property.   A polarizing plate, wherein the antireflection film according to claim 7 is used on at least one side of the polarizing film.   The antireflection film according to any one of claims 7 to 9 is used as one protective film of the polarizing film, and an optical compensation film having optical anisotropy is used as the other protective film of the polarizing film. A polarizing plate characterized by having   An image display apparatus comprising the antireflection film according to any one of claims 7 to 9, or the polarizing plate according to claim 10 or 11.

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