JP2011180523A - Antistatic optical film, polarizing plate, and image display apparatus - Google Patents

Abstract

An object of the present invention is to provide an antistatic optical film having excellent antistatic properties, excellent scratch resistance, and less antistatic humidity dependency.
A layer formed on a transparent substrate film from a composition comprising a binder, a conductive polymer compound having a hydrophilic group, and a fluoropolymer containing a fluoroaliphatic group and a hydrophilic group. (A), the conductive polymer compound is present on the surface opposite to the transparent substrate film more than the transparent substrate film side in the thickness direction in the layer (A). An antistatic optical film having a resistivity of 1 × 10 ¹² Ω / □ or less.
[Selection figure] None

Description

  The present invention relates to an antistatic optical film, a polarizing plate using the antistatic optical film, and an image display device using the antistatic optical film or the polarizing plate on the outermost surface of a display.

  Anti-reflection films are generally used in display devices such as cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), and liquid crystal display (LCD) to reduce contrast and reflect images. In order to prevent engraving, it is placed on the outermost surface of the display to reduce reflectivity using the principle of optical interference.

  Such an antireflection film is produced by forming a low refractive index layer having an appropriate thickness on the outermost surface, and optionally a high refractive index layer, a middle refractive index layer, a hard coat layer, etc. between the support and the support. it can. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer. In addition, since the antireflection film is used on the outermost surface, a function as a protective film of the display device is expected. It is required that dirt and dust are difficult to adhere and that scratch resistance is strong. In order to realize high scratch resistance in a thin film having a thickness of around 100 nm, the strength of the coating itself and the adhesion to the lower layer are required.

  In order to lower the refractive index of the material, a method of introducing a fluorine atom is known, and in particular, means using a fluorine-containing crosslinkable material has been proposed (see Patent Document 1). However, when the proportion of fluorine atoms in the compound is increased in order to reduce the refractive index, there is a problem that the film surface tends to be negatively charged and dust tends to adhere. From the viewpoint of reducing dust adhesion, a method is known in which charges on the surface of the antireflection film are leaked by providing a conductive layer (antistatic layer) on the antireflection film. For example, in patent documents 2 to 4, conductive particles made of a metal oxide are contained in the layer. This method has a problem that it is necessary to provide a new layer in addition to the low refractive index layer, and the load of equipment and time during production is large, resulting in poor productivity. In addition, conductive particles made of metal oxides for antistatic use generally used in the past generally have a refractive index of about 1.6 to 2.2. The refractive index will increase. If the refractive index of the antistatic layer increases, problems such as unintentional interference unevenness due to the difference in refractive index between adjacent layers and an increase in the color of the reflected color occur in the optical film.

Hard coat films and antireflection films to which an organic compound is added as an antistatic agent have also been proposed. For example, Patent Documents 5 and 6 disclose a technique in which an organic antistatic agent is used in the low refractive index layer. In the low refractive index layer, an antistatic agent is used with an amount of 5 to 10% by mass of the organic antistatic agent used. Sex has been obtained. However, even when the antistatic agent is used in such an amount, the strength of the film is weakened. Further, when a low molecular weight antistatic agent is used, the antistatic ability is not sufficiently maintained. In addition, the concentration of the antistatic agent may be changed in the thickness direction in the low refractive index layer, and the antistatic component becomes high concentration on the surface of the low refractive index layer to form a conductive path. However, there is no description about a concrete means for realization. Therefore, it has been difficult to maintain the hardness and scratch resistance of the film while exhibiting sufficient antistatic performance. Furthermore, since the refractive index changes depending on the amount of the antistatic compound added, it is difficult to simultaneously control both the antistatic property and the refractive index.
Patent Document 7 discloses a hard coat film in which antistatic properties are expressed with a relatively small amount of an antistatic agent to maintain scratch resistance. However, since the refractive index cannot be arbitrarily controlled, the film is reflected. There are limitations to applying the prevention film to the optical interference layer. Further, Patent Document 8 discloses a technique of using fine particles having a conductive metal oxide coating layer as a low refractive index particle. However, the production process of the particle is complicated, and a simpler technique is required. It was done.
Patent Documents 9 to 11 disclose optical films containing a fluorine-containing polymer and a conductive compound in the same layer, but further improvements are made in terms of antistatic properties, their humidity dependence, and scratch resistance. Desired.
As described above, it has been difficult to produce an antireflection film with high productivity while simultaneously satisfying antistatic properties, scratch resistance, and optical functions.

JP 2006-28409 A JP 2003-294904 A JP-A-11-92750 JP 2005-196122 A JP 2005-316425 A JP 2007-185824 A JP 2007-216525 A JP 2007-293325 A JP 2005-115359 A JP 2007-277318 A JP 2001-81131 A

  An object of the present invention is to provide an antistatic optical film having excellent antistatic properties, excellent scratch resistance, and low antistatic humidity dependency.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the following configuration can solve the problems and achieve the object, and the present invention has been completed.

1.
A layer formed from a composition comprising at least a binder, a conductive polymer compound having a hydrophilic group, and a fluoropolymer containing a fluoroaliphatic group and a hydrophilic group on a transparent substrate film (A The conductive polymer compound is present more on the opposite side of the transparent substrate film than on the transparent substrate film side in the thickness direction in the layer (A), and has a surface resistivity. Is an antistatic optical film having a value of 1 × 10 ¹² Ω / □ or less.
2.
The hydrophilic group of the conductive polymer compound and the hydrophilic group of the fluorine-containing polymer are ionic groups, and the conductive polymer compound and the fluorine-containing polymer are ions that can be oppositely charged. 2. The antistatic optical film as described in 1 above, which has a functional group.
3.
In the layer (A), the amount of the conductive polymer compound present on the transparent substrate film side surface is a, and the amount of the conductive polymer compound present on the surface opposite to the transparent substrate film is b. The antistatic optical film as described in 1 or 2 above, wherein a / b is 0 to 0.4.
4).
Any one of the above 1-3, wherein the composition forming the layer (A) contains 0.01 to 5% by mass of the conductive polymer compound with respect to the total solid content contained in the composition. An antistatic optical film as described in the item.
5.
The fluoropolymer containing a fluoroaliphatic group and a hydrophilic group comprises a monomer (1) containing a polymerizable functional group and a hydrophilic group, a functional group copolymerizable with the monomer, and a fluoroaliphatic group. 5. The antistatic optical film as described in any one of 1 to 4 above, which is a copolymer with the monomer (2) contained.
6).
6. The antistatic optical film as described in 5 above, wherein the monomer (2) containing the fluoroaliphatic group is represented by the following general formula [1].

(In the formula, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or —N (R ² ) —, Z represents a hydrogen atom or a fluorine atom, and m represents an integer of 1 to 6. And n represents an integer of 2 to 4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
7).
The fluoropolymer containing a fluoroaliphatic group and a hydrophilic group is a group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ] and salts thereof. The antistatic optical film according to any one of 1 to 6, which has at least one hydrophilic group selected from the above, and the conductive polymer compound has a cationic group.
8).
8. The antistatic optical film as described in 7 above, wherein the cationic group of the conductive polymer compound is a quaternary ammonium salt.
9.
The fluorine-containing polymer containing a fluoroaliphatic group and a hydrophilic group has a quaternary ammonium salt as a hydrophilic group, and the conductive polymer compound has an anionic group, 2. An antistatic optical film according to item 1.
10.
The anionic group of the conductive polymer compound is at least one selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ], and salts thereof. 10. The antistatic optical film as described in 9 above, which is a seed.
11.
11. The antistatic optical film according to any one of 1 to 10, wherein the conductive polymer compound further has a functional group that can be covalently bonded to a functional group of the binder.
12
The antistatic optical film according to any one of 1 to 11, wherein the layer (A) is a hard coat layer.
13.
13. The antistatic optical film as described in 12 above, which is an antireflection film having at least one layer having a refractive index smaller than that of the hard coat layer on the hard coat layer.
14
The antistatic property according to any one of 1 to 11 above, which is an antireflection film having at least one optical interference layer, wherein at least one of the optical interference layers is the layer (A). Optical film.
15.
15. A polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, wherein at least one of the protective films is the antistatic optical film according to any one of 1 to 14 above A polarizing plate.
16.
15. An image display device having the antistatic optical film according to any one of 1 to 14 or the polarizing plate according to 15 above on the outermost surface of a display.

  According to the present invention, it is possible to provide an antistatic optical film having excellent antistatic properties, excellent scratch resistance, and low antistatic humidity dependency. Further, by laminating an antireflection layer such as a low refractive index layer, an optical film having an excellent antireflection function can be provided.

  The present invention will be described below. However, the present invention is not limited by the following description. 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.

The antistatic optical film of the present invention includes a binder, a conductive polymer compound having a hydrophilic group, and a fluoropolymer containing a fluoroaliphatic group and a hydrophilic group on a transparent substrate film. It has a layer (A) formed from the composition, and the conductive polymer compound is more opposite to the transparent substrate film than the transparent substrate film side in the thickness direction in the layer (A). The surface resistivity is 1 × 10 ¹² Ω / □ or less.

The surface resistivity of the antistatic optical film of the present invention is 1 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less, and preferably 1 × 10 ¹⁰ Ω / □ or less. More preferably it is.

In order for the conductive compound to exhibit sufficient antistatic performance, it is preferable that the conductive compound is closely packed in the layer, and it is preferable that the conductive compound is localized on the outermost surface side of the layer. If a large amount of the conductive compound is added to densely fill the layer, the strength of the layer becomes weak and the refractive index changes. Therefore, it is preferable to pack a small amount of the conductive compound densely. Usually, the cohesiveness and localization of a conductive compound depend on the properties of the compound itself, and are determined by the combination with the binder contained in the same layer, the combination with the lower layer, etc. It is difficult to control arbitrarily, and the choices of materials and their combinations are limited.
According to the present invention, in the composition for forming the layer (A), a binder, a conductive polymer compound having a hydrophilic group, a fluoropolymer containing a fluoroaliphatic group and a hydrophilic group, By containing, the surface localization of the fluorine-containing polymer is used, and further by utilizing the affinity between the fluorine-containing polymer and the conductive polymer compound, a small amount of the conductive polymer compound is transparent in the layer (A). It can be densely localized on the surface side opposite to the base film. The fluoroaliphatic group-containing polymer is a compound that is localized on the surface side opposite to the transparent base film because it has a fluoroaliphatic group having low polarity. In the fluoropolymer localized on the surface side, The aliphatic group tends to face the surface side (upper side) opposite to the transparent base film, and the hydrophilic group tends to face the transparent base film side (lower side). In a layer using a general organic compound as a binder or in a layer in which fine particles are dispersed, a hydrophilic group in the fluoropolymer and a conductive polymer compound having a hydrophilic group are: Since the affinity is high, the conductive polymer compound can be accumulated on the surface side. By designing the hydrophilic group of the fluorine-containing polymer and the conductive polymer compound having a hydrophilic group, higher affinity can be obtained, and a smaller amount of the conductive polymer compound can be integrated at a higher density. Can be made. The hydrophilic group of the fluoropolymer has an ionic group that can be charged negatively or positively, and it is preferable to combine a conductive polymer compound having an ionic group that is paired with the ionic group.

  In the present invention, when the thickness of the layer (A) is 0.5 μm or less, the transparent substrate film side of the layer (A) is the outermost surface on the side close to the transparent substrate film of the layer (A) Represents an arbitrary region included within 20% of the total thickness of the layer (A), and the side opposite to the transparent substrate film of the layer (A) is the side far from the transparent substrate film of the layer (A) It represents an arbitrary region included within 20% of the entire thickness of the layer (A) from the outermost surface. Moreover, when the thickness of a layer (A) is larger than 0.5 micrometer, the transparent base film side of a layer (A) is a depth from the outermost surface of the side close | similar to the transparent base film of a layer (A). Represents an arbitrary region included within 100 nm, and the side opposite to the transparent substrate film of layer (A) is an arbitrary region included within a depth of 100 nm from the outermost surface on the side far from the transparent substrate film of layer (A) Represents the region. At this time, the transparent base film side surface and the opposite side are analyzed by the same means, and substantially the same depth region is analyzed to determine the amount (a, b) of the following conductive polymer compound. Shall.

  In the layer (A), the amount of the conductive polymer compound present on the transparent substrate film side surface is a, and the amount of the conductive polymer compound present on the surface opposite to the transparent substrate film is b. The a / b is preferably 0 to 0.4, and more preferably 0 to 0.2. The amount (a, b) of the conductive polymer compound can be determined by conducting elemental analysis on the front and back of the film using ESCA or the like.

[Conductive polymer compound having a hydrophilic group]
A conductive polymer compound is a polymer compound that can be added to a medium to lower the electrical resistance value compared to a medium to which the compound is not added. Since the conductive compound used for the layer (A) in the optical film of the present invention is a polymer, it is excellent in stability and sustainability in an environment where the optical film is used.

The conductive polymer compound in the present invention has a hydrophilic group. As the hydrophilic group, a functional group or a linking group having a polarity higher than that of the binder as a main component can be selected, but an ionic group that can be negatively or positively charged is preferable. The cationic group is preferably a quaternary ammonium salt, and the anionic group includes a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ] and the like. It is preferably at least one selected from the group consisting of these salts.

When the conductive polymer compound further has a functional group that can be covalently bonded to the functional group of the binder, the conductive polymer compound can be immobilized in the binder, so that the scratch resistance of the film is not impaired, Due to the fact that the temperature and humidity dependence of the antistatic performance can be reduced, and further, the falling off of the antistatic agent due to bleeding out, washing with water, cloth wiping, etc. can be reduced. Preferably it is. Although it does not specifically limit as a polymeric functional group, The group which has ethylenically unsaturated bonds, such as an acryl group, a vinyl group, and an allyl group, an epoxy group, etc. are mentioned, It can select according to the binder to be used.
Examples of the conductive polymer compound include ionic conductive polymers and π-conjugated conductive polymers. The conductive polymer compound is preferably an ionic polymer compound in order to localize in a pair with the hydrophilic group of the fluoropolymer.
In particular, the hydrophilic group of the conductive polymer compound and the hydrophilic group of the fluorine-containing polymer are ionic groups, and the conductive polymer compound and the fluorine-containing polymer can be charged in opposite directions. It is preferable to have In order not to impair the affinity between the conductive polymer compound and the fluorine-containing polymer, the binder preferably has no ionic group.

  Examples of the ionic polymer compound include anionic polymer compounds as described in JP-B Nos. 49-23828, 49-23827, 47-28937, JP-A-10-251621, and JP-A-2005-148861. See JP-B-55-734, JP-A-50-54672, JP-B-59-14735, JP-A-57-18175, JP-A-57-18176, JP-A-57-56059, JP-A-2005-148681, etc. An ionene type polymer having a dissociation group in the main chain; Japanese Patent Publication Nos. 53-13223, 57-15376, 58-56858, Japanese Patent Laid-Open Nos. 55-145783, 55-65950, A cutlet having a cationic group in the side chain as seen in 55-67746, 62-9346, and JP-A-2005-148861 Down pendant type polymers; and the like.

As the conductive polymer compound having a cationic group, polymer compounds obtained by increasing the molecular weight of alkylamines, quaternary ammonium salts, and the like are preferably used.
Examples of conductive polymer compounds having an anionic group include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene Polymer compounds obtained by increasing the molecular weight of alkyl sulfates, polyoxyethylene alkylallyl sulfates, naphthalenesulfonic acid formalin condensates, special carboxylic acid type polymer surfactants, and the like are preferably used.

Examples of the quaternary ammonium-based conductive polymer compound include a quaternary ammonium base-containing polymer, a quaternary ammonium base-containing silane coupling agent, or a hydrolysis condensate thereof. Specific examples of such a quaternary ammonium base-containing polymer are shown below.
(A) quaternary ammonium salt of N, N-dialkylaminoalkyl (meth) acrylic acid ester / other (meth) acrylic acid ester copolymer,
(B) quaternary ammonium salt of N, N-dialkylaminoalkyl (meth) acrylamide / copolymer with other (meth) acrylic acid ester,
(C) N, N-dialkylaminoalkyl (meth) acrylic acid ester / other (meth) acrylic acid ester (/ styrenes) / hydroxyalkyl (meth) acrylic acid ester copolymer, and (meth) acryloyl group Quaternary ammonium salts of adducts with isocyanate compounds,
(D) N, N-dialkylaminoalkyl (meth) acrylic acid ester / other (meth) acrylic acid ester (/ styrenes) / hydroxyalkyl (meth) acrylic acid ester / (meth) acryloyl-terminated polydimethylsiloxane A quaternary ammonium salt of an adduct of a polymer and a (meth) acryloyl group-containing isocyanate compound,
(E) N, N-dialkylaminoalkyl (meth) acrylic acid ester / other (meth) acrylic acid ester / (/ styrenes) / hydroxyalkyl (meth) acrylic acid ester / (meth) acryloyl-terminated polydimethylsiloxane A polymer obtained by further adding an amino group-containing polydimethylsiloxane to a quaternary ammonium salt of a copolymer and an adduct of a (meth) acryloyl group-containing isocyanate compound,
(F) a copolymer of N, N-dialkylaminoalkyl (meth) acrylic acid ester / (meth) acrylic acid ester (/ styrenes) / hydroxyalkyl (meth) acrylic acid ester / mercapto-terminated polydimethylsiloxane; Quaternary ammonium salts of adducts with (meth) acryloyl group-containing isocyanate compounds,
(G) a copolymer of N, N-dialkylaminoalkyl (meth) acrylamide / (meth) acrylic acid ester (/ styrenes) / hydroxyalkyl (meth) acrylic acid ester / mercapto-terminated polydimethylsiloxane, and (meth) Examples include adducts with acryloyl group-containing isocyanate compounds, quaternary ammonium salts, and the like.

  Quaternizing agents for modifying amino groups to quaternary ammonium salts include alkyl halides (such as methyl chloride), alkenyl halides (such as allyl chloride), aralkyl halides (such as benzyl chloride), dimethyl sulfate, diethyl Alkyl sulfates such as sulfuric acid, sulfonate esters such as methyl p-toluenesulfonate, α-haloaliphatic carboxylic acid derivatives such as methyl chloroacetate, α-haloketones such as chloroacetone, α-haloalkyl such as chloroacetonitrile A nitrile etc. can be illustrated. Among these, in order to obtain excellent antistatic properties, it is preferable to use an alkyl halide having 4 or less carbon atoms, an alkenyl halide, an α-haloaliphatic carboxylic acid derivative, or the like as a quaternizing agent. In addition, N, N-dialkylaminoalkyl (meth) acrylic acid ester as in the above (f), other (meth) acrylic acid ester and / or styrenes, hydroxyalkyl (meth) acrylic acid ester, mercapto A quaternary ammonium base-containing polymer obtained by modifying an adduct of a terminal polydimethylsiloxane copolymer and a (meth) acryloyl group-containing isocyanate compound with a quaternizing agent such as methyl chloride, allyl chloride, or methyl chloroacetate preferable.

  Although some quaternary ammonium base-containing silane coupling agents are commercially available, their functions as antistatic agents are generally low. This is because the molecular weight is low, so that it is easily adsorbed on the surface of the inorganic oxide particles, and the concentration of the quaternary ammonium group is lowered. As shown below, N, N-dialkylaminoalcohol and a silane coupling agent having an NCO group are connected by a urethane bond and then quaternized with an appropriate quaternizing agent, and a silane having a molecular weight of 400 or more. Molecular weight obtained by quaternization of an adduct of a coupling agent and / or a hydrolysis condensate thereof, or an N, N-dialkylaminoalkyl (meth) acrylic acid ester and a silane coupling agent having an SH group with a thioether bond Is preferably a silane coupling agent having a molecular weight of 400 or more, a hydrolysis condensate of such a silane coupling agent alone, a hydrolysis cocondensation product with another silane coupling agent, or the like.

  Specific examples of such quaternary ammonium base-containing silane coupling agents include N, N-dialkylamino aliphatic alcohols (N, N-dimethylaminoethanol, N, N-dimethylaminopropanol, etc.) and NCO groups. Quaternary ammonium salts, N, N-dialkylaminoalkyl (meth) acrylic acid esters (N, N-dimethylaminomethacrylate, etc.) and mercapto groups of reaction products of trialkoxysilane (γ-trimethoxysilylpropyl isocyanate etc.) contained A quaternary ammonium salt of a reaction product with a trialkoxysilane (γ-mercaptopropyltrimethoxysilane or the like) having a silane, a single hydrolysis condensate of these, a cohydrolysis condensate of these with another silane coupling agent, etc. Can be mentioned. As other silane coupling agents, silane coupling agents having an alkylene oxide chain exemplified above and silane coupling agents capable of radical polymerization are particularly preferred.

  Specific examples of the ionic polymer compound are listed below, but the present invention is not limited to these. In addition, the subscripts (m, p, q (including q1, q2, q3), r, x, y, z) in the following specific examples IP-7 to 21 are molar ratios of each repeating unit in the polymer. Represents.

  Examples of the other conductive polymer compound include a polyhydric alcohol having an ethylene oxide chain or a derivative thereof. Some typical examples of such compounds are: polyalkylene glycol mono (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polyhydric alcohols (glycerin, trimethylolpropane, pentaerythritol, dipenta An alkylene oxide adduct of erythritol and the like, and (meth) acrylic acid esters thereof. Examples of other conductive polymer compounds include phosphates such as sodium polyphosphate.

  Examples of other conductive polymer compounds include π-conjugated conductive polymers. The π-conjugated conductive polymer is not particularly limited as long as it is an organic polymer having a main chain composed of a π-conjugated system. The π-conjugated conductive polymer is preferably a π-conjugated heterocyclic compound or a derivative of a π-conjugated heterocyclic compound because of compound stability and high conductivity. Examples of the π-conjugated conductive polymer include aliphatic conjugated polyacetylene, polyacene, polyazulene, aromatic conjugated polyphenylene, heterocyclic conjugated polypyrrole, polythiophene, polyisothianaphthene, and heteroatom-containing polyaniline. , Polythienylene vinylene, mixed conjugated poly (phenylene vinylene), double chain conjugated system having a plurality of conjugated chains in the molecule, derivatives of these conductive polymers, and conjugated high There may be mentioned at least one selected from the group consisting of conductive composites which are polymers in which molecular chains are grafted or block-copolymerized onto saturated polymers. From the viewpoint of stability in air, polypyrrole, polythiophene and polyaniline or derivatives thereof are preferable, and polythiophene, polyaniline, or derivatives thereof (that is, polythiophene, polyaniline, polythiophene derivatives, and polyaniline derivatives) are more preferable.

  The conductive polymer compound in the present invention preferably has a mass average molecular weight of 1,000 to 1,000,000, more preferably 2,000 to 500,000, still more preferably 3,000 to 300,000. 000. The mass average molecular weight can be measured by gel permeation chromatography or the like.

  It is preferable that 0.01-5 mass% of conductive polymer compounds are contained with respect to the total solid content contained in the composition forming the layer (A). In order to develop a sufficient antistatic function without impairing the strength and optical performance inherent in the binder, the content of the conductive polymer compound can be adjusted according to the thickness of the layer (A). preferable.

When the layer (A) is a hard coat layer to be described later, the thickness of the layer is preferably selected from the range of 0.5 to 50 μm, and the conductive polymer compound with respect to the total solid content of the layer Is preferably 0.01 to 3% by mass, and more preferably 0.01 to 1% by mass.
When the layer (A) is an optical interference layer (low refractive index layer, medium refractive index layer, high refractive index layer, etc.) described later, the thickness of the layer is selected from the range of 0.05 to 0.2 μm. The conductive polymer compound is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total solid content of the layer.

[Fluoropolymer containing fluoroaliphatic group and hydrophilic group]
Fluoropolymers containing fluoroaliphatic groups and hydrophilic groups contained in the composition for forming the layer (A) in the optical film of the present invention ("fluorine-containing polymer", "fluoroaliphatic group-containing polymer") (Also called).

As the hydrophilic group possessed by the fluoropolymer, a functional group or a linking group having a polarity higher than that of the binder as the main component can be selected, and examples thereof include an ionic group, a hydroxyl group, and a (poly) ether group. The hydrophilic group preferably has an affinity for the conductive polymer compound, and more preferably an ionic group. Examples of the ionic group include an anionic group comprising a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ] and a salt thereof, and a cation comprising a quaternary ammonium salt. It is preferably selected from sex groups.

  Examples of the fluoroaliphatic group possessed by the fluoropolymer include linear, branched, and cyclic aliphatic groups in which a part of hydrogen atoms are replaced by fluorine atoms. The atomic ratio is preferably 0 to 0.5, and more preferably 0 to 0.3.

  The fluoroaliphatic group-containing polymer in the present invention includes a monomer (1) containing a polymerizable functional group and a hydrophilic group, and a monomer containing a functional group and a fluoroaliphatic group copolymerizable with the monomer (1). A copolymer with (2) is preferable because it is easy to design a molecule in which the molecular weight of the polymer and the composition ratio of the monomer are adjusted.

  The monomer (1) containing a polymerizable functional group and a hydrophilic group has at least one polymerizable group such as an ethylenically unsaturated bond group such as an acrylic group, a vinyl group, and an allyl group in the molecule, Further, a monomer having one or more hydrophilic groups can be mentioned, and a monofunctional monomer having one polymerizable group is preferable.

  As the monomer (2) containing a functional group copolymerizable with the monomer (1) and a fluoroaliphatic group, a fluoroaliphatic group-containing monomer represented by the following general formula [1] is preferably used.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or —N (R ² ) —, Z represents a hydrogen atom or a fluorine atom, and m represents an integer of 1 to 6. And n represents an integer of 2 to 4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  Specific examples of the polymer containing a fluorine-containing polymer anionic group and a fluoroaliphatic group that can be used in the present invention and methods for producing them are described in JP-A-2005-179636, JP-A-2005-181977, and JP-A-2006. -251642 and the like have detailed descriptions. Similarly, a polymer containing a cationic group and a fluoroaliphatic group can also be produced by using a polymerizable monomer having a cationic group.

The fluoroaliphatic group-containing polymer is preferably 0.1 to 10% by mass based on the total solid content contained in the composition forming the layer (A). If the amount is not less than the lower limit of the range, the amount of the fluoroaliphatic group-containing polymer is sufficient to cover the surface. Since it does not exist, crying out from the film is less likely to occur, and the conductive polymer compound can be accumulated on the surface side, which is preferable.
The mass average molecular weight of the fluoroaliphatic group-containing polymer is preferably 3,000 to 100,000, and more preferably 6,000 to 80,000.

  Fluoroaliphatic group-containing polymer can also function as a leveling agent, and by making it within the above addition amount and molecular weight range, it has the effect of reducing unevenness and repellency during coating and drying, making it more uniform and defective It is possible to obtain a coating film free from any problem.

  Specific examples of the fluoroaliphatic group-containing polymer that can be preferably used in the present invention are shown below, but the present invention is not limited to these specific examples. Here, the numerical value in a formula is a mass percentage which shows the composition ratio of each monomer, respectively, and Mw is the mass mean molecular weight of standard polystyrene conversion measured by GPC. Numerical values such as a, b, c, and d represent mass ratios. Other specific examples of the following compounds include P-1 to 30 described in [0062] to [0064] of JP-A-2005-181977, and P-- described in [0068] to [0071] of JP-A-2006-251642. 1-30, etc. are mentioned.

[binder]
The composition for forming the layer (A) contains a binder. The binder is preferably selected from one or both of a thermosetting resin and an ionizing radiation curable compound. That is, it is preferable to form a layer (A) by applying a composition coating containing a polymerizable compound (monomer or oligomer) or a polymer as a binder forming material on a support and causing a crosslinking reaction or a polymerization reaction. The polymerizable compound is preferably ionizing radiation curable, and the functional group is preferably a light (ultraviolet ray), electron beam, or radiation-polymerizable one, 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. It is preferably a polyfunctional compound containing two or more polymerizable groups in one molecule.

  As the low refractive index binder, a polymerizable compound having a fluorine atom and a polymerizable unsaturated group in the molecule can be used, and the compounds described in paragraphs [0023] to [0027] of JP-A-2006-28409, Compounds described in paragraphs [0054] to [0079] of JP-A-2008-134585, compounds described in paragraphs [0008] to [0017] of JP-A-3890022, paragraphs of JP-A-11-80312 And the compounds described in the numbers [0011] to [0013].

Specific examples of the compound having a polymerizable unsaturated bond that does not contain a fluorine atom include alkylene glycol (meta) such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate, and the like. ) Acrylic acid diesters;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy · diethoxy) phenyl} propane and 2-bis {4- (acryloxy · polypropoxy) phenyl} propane ;
Etc.

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

  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. For example, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, EO Modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohexane tetramethacrylate, polyurethane polyacrylate Over DOO, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.

  Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group are described in paragraph [0119] of JP-A-2009-98658, and the same applies to the present invention.

  Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins. And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols.

  As the monomer binder, 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 be used.

  Two or more polyfunctional monomers may be used in combination. Polymerization of the monomer 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.

(Polymer binder)
As the binder, not only a polyfunctional monomer or polyfunctional oligomer but also a crosslinked polymer obtained by reacting a reactive curable resin can be used as the binder. The polymer binder is described in paragraph numbers [0194] to [0200] of JP-A-2008-262187, and the same applies to the present invention.

[Antistatic optical film]
(Method for producing antistatic optical film)
The antistatic optical film of the present invention can be formed by the following method, but is not limited to this method. First, a coating composition for forming the layer (A) is prepared. Next, the composition is applied onto a transparent substrate film by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, die coating, etc., and heated and dried. . A micro gravure coating method, a wire bar coating method, and a die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferable, and a die coating method is particularly preferable.

  After coating, the layer formed from the coating composition is cured by light irradiation or heating. If necessary, other layers (layers constituting the film described below, for example, a hard coat layer, an antiglare layer, a medium refractive index layer, a high refractive index layer, etc.) are coated on the transparent base film in advance. In addition, a layer can be formed thereon. In this way, the optical film of the present invention is obtained.

(Layer structure of optical film)
The optical film of the present invention can be produced by providing a layer (A) and a functional layer required according to the purpose singly or in layers on a transparent substrate film. As a preferred embodiment, an embodiment in which the layer (A) is a hard coat layer, an embodiment of an antireflection film having a layer having a refractive index smaller than that of the hard coat layer on the hard coat layer, and at least on a transparent substrate film An antireflection film having one optical interference layer, in which at least one of the optical interference layers is the layer (A). The antireflection film having at least one optical interference layer on the transparent base film was laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, etc. so as to reduce the reflectance by optical interference. It can be set as an antireflection film.
In the simplest configuration, the antireflection film has a configuration in which only a low refractive index layer is coated on a transparent support. In order to further reduce the reflectance, the antireflection layer is preferably composed of a high refractive index layer having a higher refractive index than the transparent support and a low refractive index layer having a lower refractive index than the transparent support. . Examples of the configuration include two layers of a high refractive index layer / low refractive index layer from the transparent support side, and three layers having different refractive indices, a medium refractive index layer (having a refractive index higher than that of the transparent support and having a high refractive index. In which the refractive index layer is lower than that of the refractive index layer) / high refractive index layer / low refractive index layer, and the like, and more antireflection layers are also proposed. Among them, in view of durability, optical characteristics, cost, productivity, etc., it is preferable to have a medium refractive index layer / high refractive index layer / low refractive index layer in this order on a transparent support having a hard coat layer. Examples include the configurations described in Kaihei 8-122504, JP-A-8-110401, JP-A-10-300902, JP-A 2002-243906, JP-A 2000-117066, and the like. Other functions may be imparted to each layer, for example, an antifouling low refractive index layer or an antistatic high refractive index layer (eg, JP-A-10-206603, JP-A-2002). -243906 publication etc.) etc. are mentioned.

The example of the more concrete layer structure of the optical film of this invention is shown below. In the following layer configuration, the support represents a transparent substrate film, and at least one layer other than the support is the layer (A) in the present invention.
・ Support / hard coat layer,
-Support / low refractive index layer,
Support / Anti-Glare layer / Low refractive index layerSupport / Hard coat layer / Low refractive index layer
Support / hard coat layer / antiglare layer / low refractive index layerSupport / hard coat layer / high refractive index layer / low refractive index layerSupport / hard coat layer / medium refractive index layer / high refractive index layer / Low refractive index layer / support / hard coat layer / antiglare layer / high refractive index layer / low refractive index layer / support / hard coat layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index Index layer / support / antiglare layer / high refractive index layer / low refractive index layer / support / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer

  One of the preferred embodiments of the antireflection film of the present invention is that a medium refractive index layer, a high refractive index layer, and a low refractive index layer are laminated in this order from the transparent support side on the transparent support. The refractive index of the refractive index layer at a wavelength of 550 nm is 1.60 to 1.65, the thickness of the medium refractive index layer is 50.0 nm to 70.0 nm, and the refractive index of the high refractive index layer is 550 nm. 1.70 to 1.74, the thickness of the high refractive index layer is 90.0 nm to 115.0 nm, and the refractive index of the low refractive index layer at a wavelength of 550 nm is 1.33 to 1.38. The thickness of the low refractive index layer is 85.0 nm to 95.0 nm.

Among the above-described configurations, the antireflection film of the present invention is particularly preferably the following configuration (1) or configuration (2).
Configuration (1): The refractive index at a wavelength of 550 nm of the medium refractive index layer is 1.60 to 1.64, the thickness of the medium refractive index layer is 55.0 nm to 65.0 nm, and the wavelength of the high refractive index layer The refractive index at 550 nm is 1.70 to 1.74, the thickness of the high refractive index layer is 105.0 nm to 115.0 nm, and the refractive index at a wavelength of 550 nm of the low refractive index layer is 1.33 to 1.75. An antireflection film, which is 38 and is a low refractive index layer having a low refractive index layer having a thickness of 85.0 nm to 95.0 nm.
Configuration (2): The refractive index at a wavelength of 550 nm of the middle refractive index layer is 1.60 to 1.65, the thickness of the middle refractive index layer is 55.0 nm to 65.0 nm, and the wavelength of the high refractive index layer The refractive index at 550 nm is 1.70 to 1.74, the thickness of the high refractive index layer is 90.0 nm to 100.0 nm, and the refractive index at a wavelength of 550 nm of the low refractive index layer is 1.33 to 1.74. 38, and the thickness of the low refractive index layer is 85.0 nm to 95.0 nm.

  By making the refractive index and thickness of each layer within the above ranges, the variation in reflected color can be further reduced. The configuration (1) is a configuration that can particularly reduce the reflectance while suppressing the fluctuation of the reflected color, and is particularly preferable. In addition, the configuration (2) is particularly preferable because the variation in reflectance is further suppressed to be smaller than that in the configuration (1), and the robustness against the variation in film thickness is excellent.

  In the present invention, for the design wavelength λ (= 550 nm: representative of the wavelength region having the highest visibility), the medium refractive index layer is represented by the following formula (I), and the high refractive index layer is represented by the following formula ( II), the low refractive index layer preferably satisfies the following formula (III).

Formula (I) λ / 4 × 0.68 <n ₁ d ₁ <λ / 4 × 0.74
Formula (II) λ / 2 × 0.66 <n ₂ d ₂ <λ / 2 × 0.72
Formula (III) λ / 4 × 0.84 <n ₃ d ₃ <λ / 4 × 0.92

(Where n ₁ is the refractive index of the medium refractive index layer, d ₁ is the layer thickness (nm) of the medium refractive index layer, n ₂ is the refractive index of the high refractive index layer, and d ₂ Is the layer thickness (nm) of the high refractive index layer, n ₃ is the refractive index of the low refractive index layer, d ₃ is the layer thickness (nm) of the low refractive index layer, and n ₃ <n ₁ <n ₂ )

  When the above formula (I), formula (II), and formula (III) are satisfied, it is preferable because the reflectance becomes low and the change in reflected color can be suppressed. In addition, this is preferable because the change in color is small when an oil or fat component such as fingerprints or sebum adheres, so that dirt is hardly visible.

  The CIE standard light source D65 in the wavelength range of 380 nm to 780 nm has a color of specularly reflected light with respect to 5 ° incident light, and the a * and b * values of the CIE 1976 L * a * b * color space are 0 ≦ a * ≦ 8, respectively In the range of −10 ≦ b * ≦ 0, and further within the above-mentioned color fluctuation range, the color difference ΔE when the layer thickness of any layer among the layers fluctuates by 2.5% is expressed by the following formula ( The range 5) is preferable because the neutrality of the reflected color is good, there is no difference in the reflected color for each product, and dirt is not noticeable when oil or fat components such as fingerprints and sebum adhere to the surface. . By using the fluorine-containing antifouling agent having a polymerizable unsaturated group in the present invention and a low refractive index layer containing a fluorine-containing polyfunctional acrylate in combination with the above layer structure, even in a multilayer interference film structure, Oils and fats such as fingerprints and sebum are difficult to adhere, and even if they adhere, they can be easily wiped off and made inconspicuous.

Formula (5):
ΔE = {(L * −L * ′) ² + (a * −a * ′) ² + (b * −b * ′) ² } ^1/2 ≦ 3 (L * ′, a * ′, b * ′ Is the color of the reflected light at the design film thickness)

  Further, when it is installed on the surface of the image display device, it is preferable that the average value of the specular reflectance is 0.5% or less, so that the reflection can be remarkably reduced.

  The specular reflectance and color are measured by attaching an adapter “ARV-474” to a spectrophotometer “V-550” (manufactured by JASCO Corporation), and in the wavelength region of 380 to 780 nm, the incident angle θ ( Antireflection properties can be evaluated by measuring the specular reflectivity at an output angle −θ at θ = 5 to 45 ° and 5 ° intervals, and calculating an average reflectivity of 450 to 650 nm. Further, from the measured reflection spectrum, CIE 1976 L * a * b * color L * value, a * value, and b * value representing the color of the regular reflection light with respect to the incident light at each incident angle of the CIE standard light source D65 are obtained. It is possible to calculate and evaluate the color of the reflected light.

  The refractive index of each layer can be measured with a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) by applying the coating solution of each layer to a glass plate so as to have a thickness of 3 to 5 μm. . In this specification, a refractive index measured using a filter of “DR-M2, M4 interference filter 546 (e) nm, part number: RE-3523” was adopted as a refractive index at a wavelength of 550 nm. The film thickness of each layer can be measured by cross-sectional observation using a reflection spectral film thickness meter “FE-3000” (manufactured by Otsuka Electronics Co., Ltd.) utilizing light interference or a TEM (transmission electron microscope). Although the reflection spectral film thickness meter can also measure the refractive index simultaneously with the film thickness, it is desirable to use the refractive index of each layer measured by another means in order to increase the measurement accuracy of the film thickness. When the refractive index of each layer cannot be measured, the film thickness measurement by TEM is desirable. In that case, it is desirable to measure 10 or more locations and use an average value.

  It is preferable that the optical film of the present invention has a form in which the film is wound into a roll shape. In that case, in order to obtain the neutrality of the color of the reflected color, the average value d (average value), minimum value d (minimum value), and maximum value d (maximum value) of the layer thickness in an arbitrary 1000 m long range The value of the layer thickness distribution calculated by the following formula (6) using the value) as a parameter is preferably 5% or less, more preferably 4% or less, and even more preferably 3% or less for each layer of the thin film layer. More preferably, it is particularly preferably 2.5% or less and 2% or less.

  Formula (6): (maximum value d−minimum value d) × 100 / average value d

Next, the transparent base film and each layer in the optical film of the present invention will be described in detail.
[Transparent substrate film]
The transparent substrate film (also referred to as a transparent support) in the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, and a transparent resin sheet. 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. Film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film polyolefin, alicyclic structure Polymer (Norbornene resin (Arton: trade name, manufactured by JSR Corporation, amorphous polyolefin (ZEONEX: Name, Nippon Zeon Co., Ltd.)), and the like. Among these, triacetyl cellulose, polyethylene terephthalate, is preferably a polymer having an alicyclic structure, particularly triacetyl cellulose.
Although the thickness of a transparent support body can use the thing of about 25 micrometers-1000 micrometers normally, Preferably it is 25 micrometers-250 micrometers, and it is more preferable that it is 30 micrometers-90 micrometers.

Although the arbitrary width | variety of a transparent support body can be used, the thing of 100-5000 mm is normally used from the point of handling, a yield, and productivity, and it is preferable that it is 800-3000 mm, 1000-2000 mm More preferably it is. The transparent support can be handled in the form of a roll, and is usually 100 m to 5000 m, preferably 500 m to 3000 m.
The surface of the transparent support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. More preferably.
The transparent support is described in paragraphs [0163] to [0169] of JP-A-2009-98658, and the same applies to the present invention.

(Hard coat layer)
The optical film of the present invention can be provided with a hard coat layer in order to impart the physical strength of the film. In the present invention, it is not necessary to provide a hard coat layer, but it is preferable to provide a hard coat layer because the scratch resistance surface such as a pencil scratch test becomes strong.
Preferably, a low refractive index layer is provided on the hard coat layer, 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 1.48 to 1, from the optical design for obtaining an antireflection film. .60. 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.

The film thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 1 μm to 20 μm, more preferably 5 μm to 20 μm, from the viewpoint of imparting sufficient durability and impact resistance to the film.
The strength of the hard coat layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in the 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 applying a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can. The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Specifically, the compounds mentioned above (polyfunctional monomers having a polymerizable unsaturated group) can be preferably used.

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

  Various refractive index monomers, inorganic particles, or both can be added to the binder of the hard coat layer for the purpose of controlling the refractive index of the hard coat layer. In addition to the effect of controlling the refractive index, the inorganic particles also have the effect of suppressing cure shrinkage due to the crosslinking reaction. In the present invention, a polymer formed by polymerizing the polyfunctional monomer and / or the high refractive index monomer after the formation of the hard coat layer, and the inorganic particles dispersed therein are referred to as a binder. As the inorganic fine particles for controlling the refractive index, it is preferable to use silica fine particles from the viewpoint of suppressing color unevenness due to interference between the support and the hard coat layer.

(Anti-glare layer)
The antiglare layer is formed for the purpose of contributing to the film an antiglare property due to surface scattering and preferably a hard coat property for improving the hardness and scratch resistance of the film.
The antiglare layer is described in paragraphs [0178] to [0189] of JP-A-2009-98658, and the same applies to the present invention.

[High refractive index layer and medium refractive index layer]
As described above, the refractive index of the high refractive index layer is preferably 1.70 to 1.74, more preferably 1.71 to 1.73. 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 medium refractive index layer is preferably 1.60 to 1.64, and more preferably 1.61 to 1.63.
The high refractive index layer and the medium refractive index layer are formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD), particularly by vacuum vapor deposition or sputtering, which is a kind of physical vapor deposition, to form a transparent thin film of inorganic oxide. Although it can be used, an all wet coating method is preferred.

Since the medium refractive index layer can be similarly adjusted using the same material except that the refractive index is different from that of the high refractive index layer, the high refractive index layer will be particularly described below.
The high refractive index layer is coated with a coating composition containing inorganic fine particles, a curable compound having a tri- or higher functional polymerizable group (hereinafter sometimes referred to as “binder”), a solvent and a polymerization initiator, It is preferable that the solvent is dried and then cured by heating, irradiation with ionizing radiation, or a combination of both means. When a curable compound or initiator is used, a medium refractive index layer or a high refractive index layer excellent in scratch resistance and adhesion is formed by curing the curable compound by a polymerization reaction by heat and / or ionizing radiation after coating. it can.

(Inorganic fine particles)
As the inorganic fine particles, inorganic fine particles containing metal oxides are preferable, and inorganic fine particles containing at least one metal oxide selected from Ti, Zr, In, Zn, Sn, Al and Sb are more preferable. preferable. Moreover, in order to assist the antistatic property expressed by the conductive polymer compound introduced into the layer (A), at least one of the medium refractive index layer and the high refractive index layer contains conductive inorganic fine particles. May be.
The inorganic fine particles are preferably zirconium oxide fine particles from the viewpoint of refractive index. Further, from the viewpoint of conductivity, it is preferable to use inorganic fine particles mainly composed of an oxide of at least one kind of metal among Sb, In, and Sn. Examples of the conductive inorganic fine particles include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), phosphorus-doped tin oxide (PTO), zinc antimonate (AZO), and indium-doped zinc oxide. More preferred is a metal oxide selected from the group consisting of (IZO), zinc oxide, ruthenium oxide, rhenium oxide, silver oxide, nickel oxide and copper oxide.
The refractive index can be adjusted to a predetermined refractive index by changing the amount of the inorganic fine particles. The average particle size of the inorganic fine particles in the layer is preferably 1 to 120 nm, more preferably 1 to 60 nm, and further preferably 2 to 40 nm when zirconium oxide is used as a main component. Within this range, haze is suppressed, dispersion stability, and adhesion with the upper layer due to moderate irregularities on the surface become favorable, which is preferable.

  The inorganic fine particles mainly composed of zirconium oxide preferably have a refractive index of 1.90 to 2.80, more preferably 2.00 to 2.40, and 2.00 to 2.20. Most preferred.

  The addition amount of the inorganic fine particles varies depending on the layer to be added. In the medium refractive index layer, the solid refractive index layer is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and more preferably 30 to 50% by mass with respect to the solid content of the entire medium refractive index layer. % Is more preferable. In a high refractive index layer, 40 to 90 mass% is preferable with respect to solid content of the whole high refractive index layer, 50 to 85 mass% is more preferable, and 60 to 80 mass% is still more preferable.

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.

  Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed. The use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, treatment with a silane coupling agent having an acryloyl group or a methacryloyl group is particularly effective. Chemical surface treatment agents for inorganic fine particles, solvents, catalysts, and dispersion stabilizers are described in JP-A-2006-17870, [0058] to [0083].

The inorganic fine particles can be dispersed using a disperser. Examples of the disperser include a sand grinder mill (eg, a bead mill with pins), a high-speed impeller mill, a pebble mill, a roller mill, an attritor, and a colloid mill. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.
The inorganic fine particles are preferably made as fine as possible in the dispersion medium, and the mass average diameter is 10 to 120 nm. Preferably it is 20-100 nm, More preferably, it is 30-90 nm, Most preferably, it is 30-80 nm. By refining the inorganic fine particles to 200 nm or less, a high refractive index layer and a medium refractive index layer that do not impair transparency can be formed.

(Curable compound)
As the curable compound, a polymerizable compound is preferable, and as the polymerizable compound, an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably used. The functional group in these compounds 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 specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group, the compounds described in (Polyfunctional monomer having a polymerizable unsaturated group) can be preferably used.

  In the high refractive index layer, in addition to the above components (inorganic fine particles, curable compounds, polymerization initiators, photosensitizers, etc.), surfactants, antistatic agents, coupling agents, thickeners, anti-coloring agents , Colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, infrared absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, conductive metal particles, Etc. can also be added.

  The high refractive index layer and medium refractive index layer used in the present invention are a curable compound (for example, a binder precursor necessary for matrix formation) in a dispersion in which inorganic fine particles are dispersed in a dispersion medium as described above. The above-mentioned ionizing radiation-curable polyfunctional monomer and polyfunctional oligomer), a photopolymerization initiator, etc. are added to form a coating composition for forming a high refractive index layer and a middle refractive index layer, and a high refractive index on a transparent support. It is preferable to form by applying a coating composition for forming a layer and a medium refractive index layer and curing it by a crosslinking reaction or a polymerization reaction of a curable compound.

  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 fine particles, and the crosslinked or polymerized structure imparts a film forming ability to the binder and contains the inorganic fine particles. To improve the physical strength, chemical resistance and weather resistance of the high refractive index layer and medium refractive index layer.

  In the formation of the high refractive index layer, the crosslinking reaction or polymerization reaction of the curable compound is preferably carried out in an atmosphere having an oxygen concentration of 10% by volume or less. By forming the high refractive index layer in an atmosphere having an oxygen concentration of 10% by volume or less, the physical strength, chemical resistance, and weather resistance of the high refractive index layer, and further, the high refractive index layer and the high refractive index layer are adjacent to each other. Adhesion with the layer can be improved. Preferably, it is formed by a crosslinking reaction or a polymerization reaction of a curable resin in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2% by volume. Hereinafter, it is most preferably 1% by volume or less.

As described above, the medium refractive index layer can be obtained in the same manner by using the same material as that of the high refractive index layer.
Specifically, the type of fine particles and the type of resin are selected so that the medium refractive index layer and the high refractive index layer satisfy the film thickness and refractive index of the above formulas (I) and (II) and the blending ratio thereof. An example is to determine the main composition.

  For the coating composition for forming all the above layers, the same solvent as the composition for the low refractive index layer can be used.

[Low refractive index layer]
The low refractive index layer in the present invention preferably has a refractive index of 1.30 to 1.47. In the case of a multilayer thin film interference type antireflection film (medium refractive index layer / high refractive index layer / low refractive index layer), the refractive index of the low refractive index layer is preferably 1.33 to 1.38, and more preferably. Is preferably 1.35 to 1.37. Within the above range, the reflectance can be suppressed and the film strength can be maintained, which is preferable. The low refractive index layer can be formed by a chemical vapor deposition (CVD) method or a physical vapor deposition (PVD) method, particularly a vacuum vapor deposition method or a sputtering method, which is a kind of physical vapor deposition method. It is preferable to use an all wet coating method using the composition for a low refractive index layer.

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 strength of the antireflection film formed up to the low refractive index layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test under a 500 g load.
In order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of the surface with water is 95 ° or more. More preferably, it is 102 ° or more. In particular, a contact angle of 105 ° or more is particularly preferable because the antifouling performance against fingerprints is remarkably improved. Further, the contact angle of water is 102 ° or more, and the surface free energy is more preferably 25 dyne / cm or less, particularly preferably 23 dyne / cm or less, and further preferably 20 dyne / cm or less. . Most preferably, the contact angle of water is 105 ° or more and the surface free energy is 20 dyne / cm or less.

(Formation of a low refractive index layer)
The low refractive index layer is a coating in which a fluorine-containing antifouling agent having a polymerizable unsaturated group, a fluorine-containing copolymer having a polymerizable unsaturated group, inorganic fine particles, and other optional components contained therein are dissolved or dispersed. Forming the composition by curing with ionizing radiation irradiation (for example, light irradiation, electron beam irradiation, etc.) or heating, or a polymerization reaction at the same time as coating or after coating and drying. Is preferred.
In particular, when the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 1% by volume or less, an outermost layer excellent in physical strength and chemical resistance can be obtained.
The oxygen concentration is preferably 0.5% by volume or less, more preferably the oxygen concentration is 0.1% by volume or less, particularly preferably the oxygen concentration is 0.05% by volume or less, and most preferably 0.02% by volume or less. is there.

  As a method for reducing the oxygen concentration to 1% 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.

  In the present invention, when the layer (A) is a layer different from the layers described so far, the layer (A) is located between the layers or closest to the transparent support. It can be provided as a layer located between the layers or as an upper layer of a layer close to the film surface.

  In the present invention, at least one of the layers described so far in the antireflection film can be used as the layer (A). In particular, it is very preferable to provide a layer (A) by imparting conductivity to at least one of the low refractive index layer, the middle refractive index layer, the high refractive index layer, and the hard coat layer because the process can be simplified. . In this case, the material of the layer (A) is preferably selected so that the thickness and refractive index of the layer satisfy the conditions of the medium refractive index layer and the high refractive index layer described above.

(Organic solvent)
As described above, the organic solvent used in the curable composition for forming a conductive layer is used as a dispersion medium for dispersing conductive inorganic oxide particles. The blending amount of the organic solvent is preferably 20 to 4,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the conductive inorganic oxide particles. When the amount of the solvent is less than 20 parts by mass, a uniform reaction may be difficult due to the high viscosity, and when it exceeds 4,000 parts by mass, the coatability may be deteriorated.

  Examples of such an organic solvent include a solvent having a boiling point of 200 ° C. or less at normal pressure. Specifically, alcohols, ketones, ethers, esters, hydrocarbons, and amides are used, and these can be used alone or in combination of two or more. Of these, alcohols, ketones, ethers and esters are preferred.

  Here, examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, phenethyl alcohol, and the like. . Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether and propylene glycol monoethyl ether acetate. Examples of the esters include ethyl acetate, butyl acetate, and ethyl lactate. Examples of hydrocarbons include toluene and xylene. Examples of amides include formamide, dimethylacetamide, N-methylpyrrolidone and the like. Of these, isopropyl alcohol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monoethyl ether acetate, butyl acetate, and ethyl lactate are preferable.

[Protective film for polarizing plate]
When an optical film is used as a surface protective film for a polarizing film (protective film for polarizing plate), the surface of the transparent support opposite to the side having the thin film layer, that is, the surface to be bonded to the polarizing film is made hydrophilic. Thus, it is possible to improve adhesion with a polarizing film containing polyvinyl alcohol as a main component.
Of the two protective films of the polarizer, the film other than the optical film is preferably an optical compensation film having an optical compensation layer comprising an optical 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.

  When the antireflection film is used as a surface protective film for a polarizing film (protective film for polarizing plate), it is particularly preferable to use a triacetyl cellulose film as the transparent support.

  As a method for producing a protective film for polarizing plate in the present invention, (1) a method of coating each layer constituting the optical film on one surface of a transparent support previously saponified, (2) a transparent support A method in which an antireflection layer is coated on one side of the film, and then the saponification treatment is performed on the side or both sides to be bonded to the polarizing film; (3) a part of each layer is coated on one side of the transparent support; There are three methods, the method of applying the remaining layer after the saponification treatment on the side or both sides to be bonded to the membrane, but (1) is hydrophilized to the surface on which each layer is to be applied, and the transparent support and reflection Since it is difficult to ensure adhesion with the prevention layer, the method (2) is particularly preferable.

[Polarizer]
Next, the polarizing plate of the present invention will be described. The polarizing plate of the present invention is a polarizing plate having a polarizing film and two protective films protecting both surfaces of the polarizing film, wherein at least one of the protective films is the optical film of the present invention. To do.

  A configuration in which the transparent support of the optical film is adhered to the polarizing film through an adhesive layer made of polyvinyl alcohol, if necessary, and a protective film is also provided on the other side of the polarizing film. The surface of the other protective film opposite to the polarizing film may have an adhesive layer.

  By using the optical film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function excellent in physical strength and light resistance can be produced, and the cost can be greatly reduced and the display device can be thinned.

  Moreover, the polarizing plate of the present invention can also have an optical compensation function. In that case, only one side of either the front surface or the back surface of the two surface protective films is formed using the antireflection film, and the side of the polarizing plate having the optical film is the surface protection on the other surface side. The film is preferably an optical compensation film.

  By producing a polarizing plate using the optical film of the present invention as one of the protective films for polarizing plates and the optical compensation film having optical anisotropy as the other protective film of the polarizing film, It can improve the contrast in the bright room and the viewing angle of up, down, left and right.

  Among the configurations of the optical film of the present invention, particularly when the following antireflection film configuration (3) or (4) is used, the reflection color is uniform with a low reflectance and neutral, and fingerprints and sebum are attached. It is preferable because it can be easily wiped off, exhibits excellent antifouling properties that are not easily noticeable, and has excellent scratch resistance.

Structure (3) Transparent support: Tricellulose acetate film (refractive index: 1.49, film thickness 80 μm) Hard coat layer: polyfunctional monomer having a polymerizable unsaturated group, silica sol, photopolymerization initiator (refractive index 1. 49, film thickness 10 μm) middle refractive index layer: polyfunctional monomer having polymerizable unsaturated group, zirconium oxide fine particles, photopolymerization initiator (refractive index: 1.62, film thickness 60 nm) high refractive index layer: polymerizable non-polymerizable Polyfunctional monomer having a saturated group, zirconium oxide fine particles, photopolymerization initiator (refractive index: 1.72, film thickness 110 nm) low refractive index layer: fluorine-containing copolymer having a polymerizable unsaturated group, hollow silica fine particles, Polyfunctional monomer having a polymerizable unsaturated group (a compound containing fluorine and a compound not containing fluorine), a fluorine-containing antifouling agent having a polymerizable unsaturated group, a photopolymerization initiator (refractive index: 1.3) 6, film thickness 90nm)
Structure (4) Transparent support: Tricellulose acetate film (refractive index: 1.49, film thickness 80 μm) Hard coat layer: polyfunctional monomer having a polymerizable unsaturated group, silica sol, photopolymerization initiator (refractive index 1. 49, film thickness 10 μm) middle refractive index layer: polyfunctional monomer having polymerizable unsaturated group, phosphorus-containing tin oxide fine particles or antimony-doped tin oxide fine particles, photopolymerization initiator (refractive index: 1.635, film thickness 60 nm, ) High refractive index layer: polyfunctional monomer having a polymerizable unsaturated group, zirconium oxide fine particles, photopolymerization initiator (refractive index: 1.72, film thickness 95 nm) Low refractive index layer: containing a polymerizable unsaturated group Fluorine copolymer, hollow silica fine particles, polyfunctional monomer having polymerizable unsaturated group (fluorine-containing compound and fluorine-free compound), fluorine-containing antifouling having polymerizable unsaturated group Agent, photopolymerization initiator (refractive index: 1.36, film thickness 90 nm)

  The image display device of the present invention is characterized by having the antireflection film or polarizing plate of the present invention on the outermost surface of the display.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention should not be construed as being limited thereto.

[Preparation of coating solution for hard coat layer]
(Preparation of coating solution HC-1)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-1). The content of the conductive polymer (CP-1) was 0.1% by mass with respect to the total solid content contained in HC-1. The weight average molecular weight (Mw) of the conductive polymer and the fluoroaliphatic group-containing polymer was determined by polystyrene conversion by GPC analysis.

<Composition of hard coat layer coating solution (HC-1)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 759 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30% by mass)
600 parts by mass photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals) 50 parts by mass conductive polymer (CP-1, Mw = 23,000) 1 part by mass fluoroaliphatic group-containing polymer (FP- 1, Mw = 15,000) 10 parts by mass Methyl ethyl ketone 480 parts by mass Cyclohexanone 100 parts by mass

(Preparation of coating solution HC-2)
In the hard coat layer coating solution (HC-1), except that the content of the cationic conductive polymer (CP-1) in the solid content is 0.5% by mass, the same as the preparation of HC-1, A hard coat layer coating solution (HC-2) was prepared.
(Preparation of coating solution HC-3)
In the hard coat layer coating solution (HC-1), except that the content of the cationic conductive polymer (CP-1) in the solid content is 3.0% by mass, as in the preparation of HC-1, A hard coat layer coating solution (HC-3) was prepared.

(Preparation of coating solution HC-4)
Hydrochloric acid was added to a poly (sodium 4-styrenesulfonate) solution to make the sodium salt a free acid, and excess hydrochloric acid and sodium chloride were removed by dialysis. Thereafter, polystyrenesulfonic acid was obtained by drying under reduced pressure. This was designated as a conductive polymer (CP-2).

The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-4). The content of (CP-2) was 0.8% by mass with respect to the total solid content contained in HC-4.
<Composition of hard coat layer coating solution (HC-4)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 752 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba 50 parts by mass conductive polymer (CP-2, Mw = 39,000) 8 parts by mass fluoroaliphatic group-containing polymer (FP-2, Mw = 25,000) 10 parts by mass methyl ethyl ketone 480 100 parts by mass of cyclohexanone

(Preparation of coating solution HC-5)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-5). The content of the conductive polymer (CP-3) was 0.6% by mass with respect to the total solid content contained in HC-5.
<Composition of hard coat layer coating solution (HC-5)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 754 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba 50 parts by mass conductive polymer (CP-3, Mw = 41,000) 6 parts by mass fluoroaliphatic group-containing polymer (FP-3, Mw = 19,000) 10 parts by mass methyl ethyl ketone 480 100 parts by mass of cyclohexanone

(Preparation of coating solution HC-6)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-6). The content of the conductive polymer (CP-4) was 0.6% by mass with respect to the total solid content contained in HC-6.
<Composition of hard coat layer coating solution (HC-6)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 754 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba 50 parts by mass conductive polymer (CP-4, Mw = 31,000) 6 parts by mass fluoroaliphatic group-containing polymer (FP-4, Mw = 13,000) 10 parts by mass methyl ethyl ketone 480 100 parts by mass of cyclohexanone

(Preparation of coating solution HC-7)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-7). The content of the conductive polymer (CP-1) was 0.5% by mass with respect to the total solid content contained in HC-7.
<Composition of hard coat layer coating solution (HC-7)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 754 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba 50 parts by weight conductive polymer (CP-1) 5 parts by weight fluoroaliphatic group-containing polymer (FP-5, Mw = 29,000) 10 parts by weight methyl ethyl ketone 480 parts by weight cyclohexanone 100 parts by weight

(Preparation of coating solution HC-8)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-8).
<Composition of hard coat layer coating solution (HC-8)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 760 parts by mass of silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass of photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) 50 parts by mass Methyl ethyl ketone 480 parts by mass Cyclohexanone 100 parts by mass

(Preparation of coating solution HC-9)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-9).
<Composition of hard coat layer coating solution (HC-9)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 755 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) 50 parts by weight conductive polymer (CP-1) 5 parts by weight methyl ethyl ketone 480 parts by weight cyclohexanone 100 parts by weight

(Preparation of coating solution HC-10)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-10).
<Composition of hard coat layer coating solution (HC-10)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 752 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) 50 parts by weight conductive polymer (CP-2) 8 parts by weight methyl ethyl ketone 480 parts by weight cyclohexanone 100 parts by weight

(Preparation of coating solution HC-11)
The following composition was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer coating solution (HC-11).
<Composition of hard coat layer coating solution (HC-11)>
Partially caprolactone-modified polyfunctional acrylate (DPCA-20, manufactured by Nippon Kayaku Co., Ltd.) 610 parts by mass silica sol (MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.) 600 parts by mass Photopolymerization initiator (Irgacure 184, Ciba Specialty Chemicals Co., Ltd.) 50 parts by weight conductive polymer (CP-1) 150 parts by weight methyl ethyl ketone 480 parts by weight cyclohexanone 100 parts by weight

(Preparation of coating solution HC-12)
In the hard coat layer coating solution (HC-5), instead of the fluoroaliphatic group-containing polymer (FP-3), the following fluoroaliphatic group-containing polymer (FP-6, Mw = The hard coat layer coating solution (HC-12) was prepared in the same manner as in the preparation of HC-5 except that 20,000) was used.

[Preparation of coating solution for medium refractive index layer]
(Preparation of coating liquid Mn-1)
Hard coating agent containing ZrO ₂ fine particles (Desolite Z7404 [refractive index 1.72, solid content concentration: 60% by mass, zirconium oxide fine particle content: 70% by mass (based on solid content), average particle size of zirconium oxide fine particles: about 20 nm, Solvent composition: methyl isobutyl ketone / methyl ethyl ketone = 9/1, manufactured by JSR Corporation]) 5.1 parts by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA) 1.5 parts by mass, light A polymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.05 parts by mass, methyl ethyl ketone 66.6 parts by mass, methyl isobutyl ketone 7.7 parts by mass and cyclohexanone 19.1 parts by mass were added and stirred. did. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a medium refractive index layer coating solution (Mn-1).

(Preparation of coating solution Mn-2)
A hard coating agent containing ZrO ₂ particles (desolite Z7404) 5.1 parts by mass, 1.28 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), a photopolymerization initiator (Irgacure 907, Ciba -Specialty Chemicals Co., Ltd.) 0.05 parts by mass, 0.12 parts by mass of the conductive polymer (CP-1), 0.1 parts by mass of the fluoroaliphatic group-containing polymer (FP-1), methyl ethyl ketone 66 .6 parts by mass, 7.7 parts by mass of methyl isobutyl ketone and 19.1 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a medium refractive index layer coating solution (Mn-2).

[Preparation of coating solution for high refractive index layer]
(Preparation of coating solution Hn-1)
15.5 parts by mass of the ZrO ₂ fine particle-containing hard coating agent (desolite Z7404) 0.5 parts by mass of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 61.9 parts by mass of methyl ethyl ketone, methyl isobutyl 3.4 parts by mass of ketone and 1.1 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for high refractive index layer (Hn-1).

(Preparation of coating solution Hn-2)
15.5 parts by mass of a ZrO ₂ fine particle-containing hard coating agent (desolite Z7404), 0.1 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), the conductive polymer (CP-1) 0.2 parts by mass, 0.2 part by mass of the above-described fluoroaliphatic group-containing polymer (FP-1), 61.9 parts by mass of methyl ethyl ketone, 3.4 parts by mass of methyl isobutyl ketone, 1.1 parts by mass of cyclohexanone were added. Stir. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for high refractive index layer (Hn-2).

(Preparation of coating solution Hn-3)
ZrO ₂ fine particle-containing hard coating agent (desolite Z7404) 15.5 parts by mass, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA) 0.4 part by mass, conductive polymer (CP-1) 0.2 parts by mass, 61.9 parts by mass of methyl ethyl ketone, 3.4 parts by mass of methyl isobutyl ketone, and 1.1 parts by mass of cyclohexanone were added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for high refractive index layer (Hn-3).

(Preparation of coating solution Hn-4)
To 14.2 parts by mass of the hard coating agent containing ZrO ₂ fine particles (desolite Z7404) 1.3 parts by mass of the conductive polymer (CP-1), 61.9 parts by mass of methyl ethyl ketone, 3.4 parts by mass of methyl isobutyl ketone, 1.1 parts by mass of cyclohexanone was added and stirred. The mixture was filtered through a polypropylene filter having a pore diameter of 0.4 μm to prepare a coating solution for high refractive index layer (Hn-4).

[Preparation of coating solution for low refractive index layer]
(Synthesis of perfluoroolefin copolymer (1))

  In the above structural formula, 50:50 represents a molar ratio.

Into an autoclave with a stirrer made of stainless steel having an internal volume of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Further, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 0.53 MPa (5.4 kg / cm ² ). The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 0.31 MPa (3.2 kg / cm ² ), the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The refractive index of the obtained polymer was 1.422, and the mass average molecular weight determined from GPC analysis was about 50,000.

(Preparation of hollow silica particle dispersion)
Hollow silica particle fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalyst Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20% by mass, silica particle refractive index 1.31) in 500 parts by mass, After adding 30 parts by mass of acryloyloxypropyltrimethoxysilane and 1.51 parts by mass of diisopropoxyaluminum ethyl acetate, 9 parts by mass of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature and added 1.8 mass parts of acetylacetone, and obtained the dispersion liquid. Then, while adding cyclohexanone so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 30 Torr, and finally a dispersion S having a solid content concentration of 18.2% by mass was obtained by adjusting the concentration. . When the amount of IPA remaining in the obtained dispersion was analyzed by gas chromatography, it was 0.5% or less.

(Preparation of coating liquid Ln-1)
Each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a low refractive index layer coating solution (Ln-1) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-1)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 7 parts by mass Defensa MCF-323 (fluorine surfactant, Dainippon Ink & Chemicals, Inc.) 5 parts by mass fluorinated polymerizable compound M-1 20 parts by mass hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass Irgacure 127 (photopolymerization initiator) , Ciba Specialty Chemicals Co., Ltd.) 3 parts by mass

(Preparation of coating liquid Ln-2)
Each component was mixed as follows and dissolved in MEK to prepare a low refractive index layer coating solution (Ln-2) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-2)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 4.3 parts by mass Defensa MCF-323 (fluorine surface activity) Agent, manufactured by Dainippon Ink and Chemicals, Inc.) 5 parts by mass of fluorine-containing polymerizable compound M-1 20 parts by mass of hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass of Irgacure 127 (photopolymerization) Initiator, Ciba Specialty Chemicals Co., Ltd.) 3 parts by mass conductive polymer (CP-1) 1.2 parts by mass fluoroaliphatic group-containing polymer (FP-1) 1.5 parts by mass

(Preparation of coating liquid Ln-3)
Each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a low refractive index layer coating solution (Ln-3) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-3)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 4.5 parts by mass Defensa MCF-323 (fluorine-based surfactant) Agent, manufactured by Dainippon Ink and Chemicals, Inc.) 5 parts by mass of fluorine-containing polymerizable compound M-1 20 parts by mass of hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass of Irgacure 127 (photopolymerization) Initiator, Ciba Specialty Chemicals Co., Ltd.) 3 parts by weight conductive polymer (CP-2) 1.5 parts by weight fluoroaliphatic group-containing polymer (FP-2) 2.0 parts by weight

(Preparation of coating liquid Ln-4)
Each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a low refractive index layer coating solution (Ln-4) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-4)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts by mass of defensa MCF-323 (fluorine-based surfactant) Agent, manufactured by Dainippon Ink and Chemicals, Inc.) 5 parts by mass of fluorine-containing polymerizable compound M-1 20 parts by mass of hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass of Irgacure 127 (photopolymerization) Initiator, Ciba Specialty Chemicals Co., Ltd.) 3 parts by weight conductive polymer (CP-1) 1.2 parts by weight

(Preparation of coating liquid Ln-5)
Each component was mixed as described below, and dissolved in methyl ethyl ketone to prepare a low refractive index layer coating solution (Ln-5) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-5)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 5.5 parts by mass Defensa MCF-323 (fluorine surface activity) Agent, manufactured by Dainippon Ink and Chemicals, Inc.) 5 parts by mass of fluorine-containing polymerizable compound M-1 20 parts by mass of hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass of Irgacure 127 (photopolymerization) Initiator, Ciba Specialty Chemicals Co., Ltd.) 3 parts by weight conductive polymer (CP-2) 1.5 parts by weight

(Preparation of coating liquid Ln-6)
Each component was mixed as described below and dissolved in methyl ethyl ketone to prepare a low refractive index layer coating solution (Ln-6) having a solid content of 5% by mass.
<Composition of low refractive index layer coating liquid (Ln-6)>
Perfluoroolefin copolymer (1) 15 parts by mass DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass defensa MCF-323 (fluorine surfactant, Dainippon Ink & Chemicals, Inc.) 5 parts by mass fluorinated polymerizable compound M-1 20 parts by mass hollow silica particle dispersion S (solid content concentration 18.2% by mass) 50 parts by mass Irgacure 127 (photopolymerization initiator) , Manufactured by Ciba Specialty Chemicals Co., Ltd.) 3 parts by mass of conductive polymer (CP-1) 6 parts by mass

[Preparation of antireflection film]
Each layer was formed as follows using the coating liquid prepared as described above. As shown in Table 1, the layers were laminated to prepare hard coat films and antireflection films of Examples 1 to 15 and Comparative Examples 1 to 11.

(Formation of hard coat layer)
The hard coat layer coating solution was applied onto a triacetyl cellulose film (TD80UF, manufactured by Fuji Film Co., Ltd., refractive index 1.48) as a transparent support having a layer thickness of 80 μm using a gravure coater. After drying at 100 ° C., using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less, the illuminance is 400 mW / The coating layer was cured by irradiating with an ultraviolet ray of cm ² and an irradiation amount of 150 mJ / cm ² to form a hard coat layer having a thickness of 12 μm.

(Formation of medium refractive index layer)
The medium refractive index layer coating solution was applied onto the hard coat layer prepared above using a gravure coater. Using a 180 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while irradiating at 90 ° C. for 30 seconds and purging with nitrogen so that the oxygen concentration is 1.0 vol% or less, the illuminance is 300 mW. / Cm ² , irradiation of 240 mJ / cm ² of ultraviolet rays was applied to cure the coating layer to form a medium refractive index layer having a thickness of 60 nm.

(Formation of high refractive index layer)
The high refractive index layer coating solution was applied onto the intermediate refractive index layer produced using a gravure coater. Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) with an illuminance of 300 mW while drying at 90 ° C. for 30 seconds and purging with nitrogen so that the oxygen concentration is 1.0 vol% or less. The coating layer was cured by irradiating with UV light of / cm ² and an irradiation amount of 240 mJ / cm ² to form a high refractive index layer having a thickness of 110 nm.

(Formation of a low refractive index layer)
The low-refractive-index layer coating solution was applied on the hard coat layer or the high-refractive index layer prepared above using a gravure coater. Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) while irradiating at 90 ° C. for 30 seconds and purging with nitrogen so that the oxygen concentration is 0.1 vol% or less, the illuminance is 600 mW. The coating layer was cured by irradiating with UV light of / cm ² and an irradiation amount of 600 mJ / cm ² to form a low refractive index layer having a thickness of 90 nm.

(Measurement of surface abundance ratio of conductive compounds)
The coating solution containing the conductive compound for each layer was applied on a glass plate so as to have the same film thickness as each of the layers, and each layer was formed by ultraviolet irradiation. Each layer was peeled off from the glass plate, and ESCA measurement on the glass plate side surface and the opposite surface (ESCA-3400, manufactured by Shimadzu Corporation, vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, An electric current of 20 mA) was performed, and the elements contained from the outermost surface to a depth of about 10 nm were examined. N / C or S / C on the glass plate side was a, N / C or S / C on the opposite side was b, and a / b was determined.

(Evaluation of antireflection film)
Various characteristics of the antireflection film were evaluated by the following methods. The results are shown in Table 3.

(1) Measurement of surface resistance value After placing the sample under the conditions of 25 ° C and 60% RH for 2 hours, the surface resistance value was measured by the circular electrode method under the same conditions. It is shown as a common logarithm (log SR) of the surface resistance value.

(2) Adhesion of dust The transparent support side of the antireflection film is attached to the surface of a CRT (KV-25DS65, manufactured by Sony Corporation), and 1 ft ³ (legal feet) of 0.5 μm or more dust and tissue paper waste. It was used for 24 hours in a room (25 ° C., 60% RH) having 1 to 2 million pieces per unit. The number of adhering dust and tissue paper waste per 100 cm ^{2 of the} antireflection film is measured, and the average value of each result is less than 50, the case of 50 to 199 is ○, the case of 200 to 500 Was evaluated as Δ, and when more than 500, ×.

(3) Steel wool scratch resistance evaluation By using a rubbing tester and performing a rubbing test under the following conditions, it can be used as an index of scratch resistance. Evaluation environmental conditions: 25 ° C., 60% RH Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., GELAID No. 0000) Wrap around a scraper tip (1 cm × 1 cm) of a tester that comes into contact with the sample and fix the band. 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 oily black ink was applied to the back side of the rubbed sample and visually observed with reflected light to evaluate scratches on the rubbed portion.
◎: Even when viewed very carefully, no scratches are visible. ○: When viewed very carefully, slightly weak scratches are visible.
×: Scratches can be seen without looking carefully.

(4) Specular Reflectance A spectrophotometer V-550 (manufactured by JASCO Corporation) is equipped with an adapter ARV-474, and in the wavelength range of 380 to 780 nm, the specular reflection with an output angle of 5 ° at an incident angle of 5 °. The average reflectance of 450 to 650 nm was calculated. A sample having an average reflectivity of less than 1% is marked with ◎, a sample with a mean reflectivity of 1 to 3% is marked with よ り 大 き い, and a sample with a mean reflectivity of over 3% is marked with ×.

  The hard coat films of Examples 1 to 3 had high antistatic properties, a small amount of dust adhesion, and excellent scratch resistance. On the other hand, the hard coat film of Comparative Example 1 was excellent in scratch resistance, but had low antistatic properties and a large amount of dust.

  The antireflection films of Examples 4 to 11 in which the low refractive index layer is formed on the hard coat layer have high antistatic properties and a small amount of dust. Furthermore, it showed excellent antireflection performance with excellent scratch resistance and low reflectance. On the other hand, the antireflection films of Comparative Examples 2, 3, 5, 6, and 8 were excellent in antireflection performance and scratch resistance, but had low antistatic properties and a large amount of dust. The antireflection films of Comparative Examples 4 and 7 were excellent in antistatic properties but poor in scratch resistance.

  The antireflection films of Examples 12 to 15 in which the middle refractive index layer, the high refractive index layer, and the low refractive index layer are formed in this order on the hard coat layer have high antistatic properties and a small amount of dust. Furthermore, it was excellent in scratch resistance, had a very low reflectance, had a neutral reflection color, and exhibited excellent antireflection performance. On the other hand, the antireflection films of Comparative Examples 9 and 10 were excellent in antireflection performance, but had low antistatic properties and a large amount of dust adhesion. The antireflection film of Comparative Example 11 was excellent in antistatic properties but poor in scratch resistance.

  In the antireflection film of Example 5, the antireflection film of Comparative Example 12 was produced using p-toluenesulfonic acid instead of CP-2 in HC-4. The log SR was 13.2, and the dust adhesion was x. Furthermore, the film of Examples 1 to 15 was changed from an environment of 25 ° C. and 60% RH to an environment of 25 ° C. and 30% RH, and the increase in log SR after 2 hours was within one. The increase in log SR of the film of Example 12 was 2.0, and the humidity dependency was large.

(Preparation of polarizing plate)
80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Film Co., Ltd.), which was saponified by immersing in an aqueous solution of NaOH at 1.5 mol / L and 55 ° C. for 2 minutes, neutralizing and washing with water. Then, with the anti-reflection films of Examples and Comparative Examples that were similarly saponified, iodine was adsorbed on polyvinyl alcohol, and both sides of a polarizer prepared by stretching were bonded and protected to produce a polarizing plate.

(Production of liquid crystal display device)
Polarized light in which the polarizing plate and retardation film provided in the VA type liquid crystal display device (LC-37GS10, manufactured by Sharp Corporation) are peeled off, and the polarizing plate prepared above is attached to the product instead. It stuck so that it might correspond with a board, and the liquid crystal display device which has the antireflection film of an Example and a comparative example was produced. In addition, it affixed so that an antireflection film might become a visual recognition side.

  The polarizing plate with an antireflection film and the image display device of Examples prepared as described above are excellent in antireflection properties, dust resistance, and anti-resistance properties as compared with Comparative Examples, as in the case of the antireflection film attached thereto. Abrasion was shown.

Claims (16)

A layer formed from a composition comprising at least a binder, a conductive polymer compound having a hydrophilic group, and a fluoropolymer containing a fluoroaliphatic group and a hydrophilic group on a transparent substrate film (A The conductive polymer compound is present more on the opposite side of the transparent substrate film than on the transparent substrate film side in the thickness direction in the layer (A), and has a surface resistivity. Is an antistatic optical film having a value of 1 × 10 ¹² Ω / □ or less.   The hydrophilic group of the conductive polymer compound and the hydrophilic group of the fluorine-containing polymer are ionic groups, and the conductive polymer compound and the fluorine-containing polymer are ions that can be oppositely charged. The antistatic optical film according to claim 1, which has a functional group.   In the layer (A), the amount of the conductive polymer compound present on the transparent substrate film side surface is a, and the amount of the conductive polymer compound present on the surface opposite to the transparent substrate film is b. The antistatic optical film according to claim 1 or 2, wherein a / b is from 0 to 0.4.   4. The composition according to claim 1, wherein the composition forming the layer (A) contains 0.01 to 5% by mass of the conductive polymer compound based on the total solid content in the composition. 2. An antistatic optical film according to item 1.   The fluoropolymer containing a fluoroaliphatic group and a hydrophilic group comprises a monomer (1) containing a polymerizable functional group and a hydrophilic group, a functional group copolymerizable with the monomer, and a fluoroaliphatic group. It is a copolymer with the monomer (2) to contain, The antistatic optical film of any one of Claims 1-4. The antistatic optical film according to claim 5, wherein the monomer (2) containing the fluoroaliphatic group is represented by the following general formula [1].

(In the formula, R ¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom, or —N (R ² ) —, Z represents a hydrogen atom or a fluorine atom, and m represents an integer of 1 to 6. And n represents an integer of 2 to 4. R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) The fluoropolymer containing a fluoroaliphatic group and a hydrophilic group is a group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ] and salts thereof. The antistatic optical film according to claim 1, further comprising at least one hydrophilic group selected from the above, wherein the conductive polymer compound has a cationic group.   The antistatic optical film according to claim 7, wherein the cationic group of the conductive polymer compound is a quaternary ammonium salt.   The fluoropolymer containing a fluoroaliphatic group and a hydrophilic group has a quaternary ammonium salt as a hydrophilic group, and the conductive polymer compound has an anionic group. 2. An antistatic optical film according to item 1. The anionic group of the conductive polymer compound is at least one selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphono group [—PO (OH) ₂ ], and salts thereof. The antistatic optical film according to claim 9, which is a seed.   The antistatic optical film according to claim 1, wherein the conductive polymer compound further has a functional group capable of being covalently bonded to a functional group of the binder.   The antistatic optical film according to claim 1, wherein the layer (A) is a hard coat layer.   The antistatic optical film according to claim 12, which is an antireflection film having at least one layer having a refractive index smaller than that of the hard coat layer on the hard coat layer.   The antistatic film according to any one of claims 1 to 11, wherein the antireflection film has at least one optical interference layer, and at least one of the optical interference layers is the layer (A). Optical film.   It is a polarizing plate which has two protective films which protect both surfaces of a polarizing film and this polarizing film, Comprising: At least 1 sheet of this protective film is the antistatic optics of any one of Claims 1-14. A polarizing plate that is a film.   The image display apparatus which has the antistatic optical film of any one of Claims 1-14, or the polarizing plate of Claim 15 in the outermost surface of a display.