JP2007233375A - Antireflection film, polarizing plate using the same, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent antireflection film with which tightness of black is obtainable, and to provide a high-grade polarizing plate with the antireflection film, or an image forming apparatus. <P>SOLUTION: The antireflection film has at least one hard coat layer (2) and a low refractive-index layer (5) having a refractive index of ≤1.47 as the outermost layer on a transparent support (1). The surface roughness Ra of the antireflection film is ≥0.03 μm and when it is assumed that average 5° specular reflectance is A and average integrated reflectance is B in a wavelength range of 450 nm to 650 nm, the relation of formula 1: B-A<4×Ra is satisfied. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antireflection film, a polarizing plate using the same, and an image display device. The antireflection film in the present invention is generally disposed on the outermost surface of the display device in order to improve display performance and protection performance of the display device (CRT, PDP, ELD, SED, LCD, etc.).

  In order to improve the display performance, there is a conventional antiglare hard coat film that prevents reflection of the external environment by scattering the reflected light of the external light on the film surface. For example, in Patent Document 1, fine particles are contained in the hard coat layer, the surface is provided with irregularities, and external light is scattered to reduce the glare of the screen. In Patent Documents 2 and 3, a low-refractive index layer is further provided on a string-proof hard coat film having a concavo-convex surface to further reduce external light reflection by light interference.

With this technology, visibility in a bright room environment has been improved to a certain level, but with the advancement of image display devices, there is a demand for displaying black when displaying black (= tightening of black). In particular, surface films satisfying this requirement have been demanded. For this reason, it was necessary to perform a design that maximizes the performance of the low refractive index layer / antiglare layer against black tightening. In addition, with the advancement of image display devices, the tolerance of image blurring and lowering of the front contrast due to the mounting of the surface film is narrowed, and a surface film that satisfies this requirement has been demanded.
JP 2000-338310 A JP 2002-196117 A JP 2003-161816 A

The present invention has been made for the above-described problems, and a first object of the present invention is to provide an excellent surface film (antireflection film) that can obtain good black tightening even in a bright room environment. ) To provide.
The second object of the present invention is to provide an excellent surface film (antireflection film) in which the image is not blurred (the front contrast is not lowered).
A third object of the present invention is to provide a high-quality polarizing plate or an image display device provided with the antireflection film.

As a result of intensive studies to solve the above-described problems, the present inventors have found that the above-described problems can be solved and the object can be achieved, and the present invention has been completed.
That is, the present invention achieves the object by the following configuration.
(1) In the antireflection film having at least one hard coat layer on the transparent support and a low refractive index layer having a refractive index of 1.47 or less as the outermost layer, the centerline average roughness Ra of the antireflection film is Reflection satisfying the relationship of the following formula 1 when the average value of 5 ° regular reflectance is A and the average value of integral reflectance is B in a wavelength region of 0.03 μm or more and 450 nm to 650 nm. Prevention film.
(Formula 1) B-A <4 · Ra
Ra: Centerline average roughness (μm)
(2) The antireflection film as described in (1) above, wherein the internal haze of the antireflection film is less than 36%.
(3) The antireflection film as described in (1) or (2) above, wherein the thickness of the hard coat layer is from 5 μm to 35 μm.
(4) A polarizing plate using the antireflection film according to any one of (1) to (3) as at least one of two protective films of a polarizing film.
(5) An image display device, wherein the antireflection film according to any one of (1) to (3) or the polarizing plate according to (4) is used on the outermost surface of a display.
(6) The image display device according to (5), wherein the image display device is a TV of 32 inches or more.

  With the film of the present invention, it was possible to provide an excellent antireflection film capable of providing display performance with black tightening even in a very bright bright room environment. In addition, a high-quality polarizing plate or an image display device provided with the antireflection film could be provided.

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

First, in the antireflection film of the present invention, in the wavelength region of 450 nm to 650 nm, when the average value of 5 ° regular reflectance is A and the average value of integrated reflectance is B, the relationship of the following formula 1 is satisfied There is a need.
(Formula 1) B-A <4 · Ra (Ra: centerline average roughness (μm))
Preferably, B−A <3 · Ra. It was found that when B-A is 4 · Ra or more, the blackness is lowered and the effect of the present invention cannot be obtained. In the present invention, the method for measuring the 5 ° regular reflectance and the integral reflectance will be described later.
In order to obtain an antireflection film that satisfies the requirements of the above (Equation 1), it is necessary to adjust the surface shape of the antireflection film (height of protrusions, frequency, etc.) to fall within a desired range. The following can be illustrated as a specific adjustment method.
1) When the layer thickness of the hard coat layer containing particles is smaller than the particle diameter (an example is shown in FIG. 10)
I) The protrusion height can be adjusted by controlling the difference between the particle diameter and the hard coat layer thickness.
II) The protrusion frequency can be adjusted by controlling the number of particles.
2) When the layer thickness of the hard coat layer containing particles is larger than the particle diameter (an example is shown in FIG. 11)
I) The height of the protrusion can be adjusted by controlling the surface energy difference (hydrophobicity difference) [particle aggregation degree adjustment] between the hard coat layer matrix (binder) and the particle surface, and the particle diameter.
II) The protrusion frequency can be adjusted by controlling the number of particles.
3) When the hard coat layer containing particles is further overcoated with a hard coat layer for adjustment, the protrusion height can be adjusted by the layer thickness of the hard coat layer (an example is shown in FIG. 12).

  Further, the roughness Ra (centerline average roughness) of the antireflection film of the present invention needs to be 0.03 μm or more. If Ra is less than 0.03 μm, the reflection of the image increases, and the effect of impairing visibility increases, which is not preferable. A preferable range of Ra is not particularly limited as long as it is 0.03 μm or more, but a range of 0.03 μm to 0.3 μm is preferable, and a range of 0.05 μm to 0.2 μm is more preferable. From the viewpoint of the size of the surface irregularities and the blackness, Ra preferably does not exceed 0.3 μm.

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

1- (1) Binder The film of the present invention can be formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. That is, a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer as a binder is coated on a transparent support, and the polyfunctional monomer or polyfunctional oligomer is formed by a crosslinking reaction or a polymerization reaction. be able to.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.
As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meta) of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate
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. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, (di) pentaerythritol triacrylate, (di) pentaerythritol pentaacrylate, (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate , Tripentaerythritol hexatriacrylate and the like. In the present specification, “(meth) acrylate”, “(meth) acrylic acid”, and “(meth) acryloyl” represent “acrylate or methacrylate”, “acrylic acid or methacrylic acid”, and “acryloyl or methacryloyl”, respectively. .

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

Two or more polyfunctional monomers may be used in combination.
Polymerization of these monomers having an ethylenically unsaturated group can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.
It is preferable to use a photopolymerization initiator for the polymerization reaction of the photopolymerizable polyfunctional monomer. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

1- (2) Polymer Binder In the present invention, a polymer or a crosslinked polymer can be used as the binder. The crosslinked polymer preferably has an anionic group. The polymer having a crosslinked anionic group has a structure in which the main chain of the polymer having an anionic group is crosslinked.

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

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

  The crosslinked structure is a structure in which two or more main chains are chemically bonded (preferably covalent bonds), but it is preferable to covalently bond three or more main chains. The crosslinked structure is preferably composed of a divalent or higher valent group selected from —CO—, —O—, —S—, a nitrogen atom, a phosphorus atom, an aliphatic residue, an aromatic residue, and combinations thereof.

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

The repeating unit of the polymer having a crosslinked anionic group may have both an anionic group and a crosslinked structure. Further, other repeating units (repeating units having neither an anionic group nor a crosslinked structure) may be contained.
Other repeating units are preferably a repeating unit having an amino group or a quaternary ammonium group and a repeating unit having a benzene ring. The amino group or the quaternary ammonium group has a function of maintaining the dispersed state of the inorganic particles, like the anionic group. The same effect can be obtained even when the amino group, quaternary ammonium group and benzene ring are contained in a repeating unit having an anionic group or a repeating unit having a crosslinked structure.
In a repeating unit having an amino group or a quaternary ammonium group, the amino group or quaternary ammonium group is directly bonded to the main chain of the polymer or bonded to the main chain through a linking group. The amino group or quaternary ammonium group is preferably bonded to the main chain as a side chain via a linking group. The amino group or quaternary ammonium group is preferably a secondary amino group, a tertiary amino group or a quaternary ammonium group, more preferably a tertiary amino group or a quaternary ammonium group. The group bonded to the nitrogen atom of the secondary amino group, tertiary amino group or quaternary ammonium group is preferably an alkyl group, preferably an alkyl group having 1 to 12 carbon atoms, Is more preferably an alkyl group of 1 to 6. The counter ion of the quaternary ammonium group is preferably a halide ion. The linking group that connects the amino group or quaternary ammonium group to the polymer main chain is a divalent group selected from -CO-, -NH-, -O-, an alkylene group, an arylene group, and combinations thereof. Preferably there is. When the polymer having a crosslinked anionic group contains a repeating unit having an amino group or a quaternary ammonium group, the ratio is preferably 0.06 to 32% by mass, and 0.08 to 30% by mass. It is more preferable that it is 0.1 to 28% by mass.

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

Examples of the structural unit for imparting crosslinking reactivity include units represented by the following (A), (B), and (C).
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate and glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): a group having a crosslinkable functional group separately from a group that reacts with the functional group of (A) or (B) in the molecule and a structural unit of (A) or (B) above. Examples of the structural unit to be obtained include (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).

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

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

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

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

  The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group). These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%. Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.

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

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

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

1- (4) Organosilane compound At least one of the layers constituting the film of the present invention contains at least one of a hydrolyzate of an organosilane compound and / or a partial condensate thereof in the coating solution forming the layer. It is preferable from the viewpoint of scratch resistance that it contains a kind of component, a so-called sol component (hereinafter sometimes referred to as such).
In particular, in an antireflection film, it is particularly preferable that both the low refractive index layer and the functional layer contain a sol component in order to achieve both antireflection ability and scratch resistance. This sol component is condensed by a drying and heating process after coating the coating solution to form a cured product and becomes a part of the binder of the above layer. Moreover, when this hardened | cured material has a polymerizable unsaturated bond, the binder which has a three-dimensional structure is formed by irradiation of actinic light.

The organosilane compound is preferably one represented by the following general formula 1.
General formula 1: (R < ¹ >) _m- Si (X) _4-m
In the general formula 1, R ¹ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. As an alkyl group, a C1-C30 alkyl group is preferable, More preferably, it is C1-C16, Most preferably, it is a C1-C6 thing. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.
X represents a hydroxyl group or a hydrolyzable group, for example, an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group or an ethoxy group), a halogen atom (for example, Cl, Br, I or the like). ) And R ² COO (R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably An alkoxy group, particularly preferably a methoxy group or an ethoxy group.
m represents an integer of 1 to 3, and preferably 1 or 2.

When R ¹ or X there is a plurality, the plurality of R ¹ or X may be different even in the same, respectively.
The substituent contained in R ¹ is not particularly limited, but a halogen atom (fluorine, chlorine, bromine, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl, ethyl, i-propyl, propyl, t-butyl etc.), aryl groups (phenyl, naphthyl etc.), aromatic heterocyclic groups (furyl, pyrazolyl, pyridyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, hexyloxy etc.), aryloxy (phenoxy etc.) ), Alkylthio groups (methylthio, ethylthio, etc.), arylthio groups (phenylthio, etc.), alkenyl groups (vinyl, 1-propenyl, etc.), acyloxy groups (acetoxy, acryloyloxy, methacryloyloxy, etc.), alkoxycarbonyl groups (methoxycarbonyl, ethoxy) Carbonyl, etc.), aryloxy Carbonyl groups (phenoxycarbonyl, etc.), carbamoyl groups (carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-methyl-N-octylcarbamoyl, etc.), acylamino groups (acetylamino, benzoylamino, acrylicamino, methacrylamino) Etc.), and these substituents may be further substituted.
R ¹ is preferably a substituted alkyl group or a substituted aryl group.
The compound represented by the general formula 1 is preferably an organosilane compound having a vinyl polymerizable substituent represented by the following general formula 2.
General formula 2

In the above general formula 2, R ₂ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred.
Y represents a single bond or * -COO-**, * -CONH-** or * -O-**, preferably a single bond, * -COO-** or * -CONH-**, * -COO-** is more preferable, and * -COO-** is particularly preferable. * Represents a position bonded to ═C (R ₂ ) —, and ** represents a position bonded to L.

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

l represents a number satisfying an expression of l = 100−m, and m represents a number from 0 to 50. As for m, the number of 0-40 is more preferable, and the number of 0-30 is especially preferable.
R _{3 to} R ₅ are preferably a halogen atom, a hydroxyl group, an unsubstituted alkoxy group, or an unsubstituted alkyl group. R _{3 to} R ₅ are more preferably a chlorine atom, a hydroxyl group, or an unsubstituted alkoxy group having 1 to 6 carbon atoms, more preferably a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methoxy group.
R ₆ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom, or a chlorine atom. Examples of the alkyl group include a methyl group and an ethyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an alkoxycarbonyl group. A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom, and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom, and a chlorine atom are more preferable, and a hydrogen atom and a methyl group Is particularly preferred. R ₇ has the same meaning as R ^{1 in} formula 1 above, more preferably a hydroxyl group or an unsubstituted alkyl group, still more preferably a hydroxyl group or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydroxyl group or a methyl group.
When a plurality of R ₄ , R ₅ and R ₇ are present, each may be the same or different.

  Two or more compounds of the general formula 1 may be used in combination. In particular, the compound of the general formula 2 is synthesized using one or two compounds of the general formula 1 as starting materials. Specific examples of the starting materials of the compound represented by Formula 1 and the compound represented by Formula 2 are shown below, but are not limited thereto.

    M-48 Methyltrimethoxysilane

Of these, (M-1), (M-2), and (M-25) are particularly preferable as the organosilane containing a polymerizable group.
In order to obtain the effect of the present invention, the content of the organosilane containing the vinyl polymerizable group in the hydrolyzate of organosilane and / or its partial condensate is preferably 30% by mass to 100% by mass, The mass% is more preferably 100% by mass, and more preferably 70% by mass to 95% by mass. By setting the content of the organosilane containing the vinyl polymerizable group to 30% by mass or more, a solid content is not generated, the liquid is not turbid, and the pot life is not deteriorated. Further, the molecular weight is easily controlled (the molecular weight does not increase), and various physical properties such as scratch resistance are improved, which is preferable.
When synthesizing the compound represented by the general formula 2, (M-1) and (M-2) as the organosilane containing the vinyl polymerizable group, (MM) as the organosilane having no vinyl polymerizable group. It is preferable to use one of each of −19) to (M-21) and (M-48) in combination with the above amounts.

  It is preferable to suppress volatility of the hydrolyzate of organosilane of the present invention and / or its partial condensate in order to stabilize the performance of the coated product. Specifically, volatilization per hour at 105 ° C. The amount is preferably 5% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

The sol component used in the present invention is prepared by hydrolysis and / or partial condensation of the organosilane.
In the hydrolysis condensation reaction, 0.05 to 2.0 mol, preferably 0.1 to 1.0 mol of water is added to 1 mol of the hydrolyzable group (X), and the presence of the catalyst used in the present invention is present. Under stirring at 25-100 ° C.

In at least one of the hydrolyzate of organosilane of the present invention and the partial condensate thereof, the mass average molecular weight of either the hydrolyzate of organosilane containing a vinyl polymerizable group or the partial condensate thereof is less than 300. When this component is removed, 450 to 20000 is preferable, 500 to 10,000 is more preferable, 550 to 5000 is still more preferable, and 600 to 3000 is still more preferable.
Of the components having a molecular weight of 300 or more in the hydrolyzate of organosilane and / or its partial condensate, the component having a molecular weight of more than 20000 is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is 3 mass% or less. A cured film obtained by curing a curable composition containing such a hydrolyzate of organosilane and / or a partial condensate thereof by setting a component having a molecular weight of more than 20000 to 10% by mass is transparent. And adhesion to the substrate are improved.

Here, the mass average molecular weight and the molecular weight are converted into polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) and solvent THF and differential refractometer detection. The content is the area% of the peak in the molecular weight range when the peak area of the component having a molecular weight of 300 or more is defined as 100%.
The dispersity (mass average molecular weight / number average molecular weight) is preferably 3.0 to 1.1, more preferably 2.5 to 1.1, still more preferably 2.0 to 1.1, and 1.5 to 1. 1 is particularly preferred.

The ²⁹ Si-NMR analysis of the hydrolyzate and partial condensate of the organosilane of the present invention can confirm the state in which X in the general formula 1 is condensed in the form of -OSi.
At this time, when three bonds of Si are condensed in the form of -OSi (T3), when two bonds of Si are condensed in the form of -OSi (T2), one bond of Si is- When the condensation is performed in the form of OSi (T1), and the case where Si is not condensed at all (T0), the condensation rate α is expressed by the formula (II): α = (T3 × 3 + T2 × 2 + T1 × 1) / 3 / (T3 + T2 + T1 + T0)
The condensation rate is preferably 0.2 to 0.95, more preferably 0.3 to 0.93, and particularly preferably 0.4 to 0.9.
When the condensation rate is 0.2 or more, sufficient curability is exhibited, and when it is 0.95 or less, the interaction with the binder polymer, the resin substrate, the inorganic fine particles, and the like can be enhanced.

The hydrolyzate and partial condensate of the organosilane compound used in the present invention will be described in detail.
The hydrolysis reaction of organosilane and the subsequent condensation reaction are generally carried out in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, butyric acid, maleic acid, citric acid, formic acid, methanesulfonic acid and toluenesulfonic acid; sodium hydroxide, potassium hydroxide and ammonia Inorganic bases such as triethylamine, organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum, tetrabutoxyzirconium, tetrabutyltitanate, dibutyltin dilaurate; and metals such as Zr, Ti or Al as the central metal Metal chelate compounds and the like; F-containing compounds such as KF and NH ₄ F may be mentioned.
The said catalyst may be used independently or may use multiple types together.

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

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

Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone and cyclohexanone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. The concentration of the solid content in the reaction is not particularly limited, but is usually in the range of 1% to 100%.

In the reaction, 0.05 to 2 mol, preferably 0.1 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, in the presence or absence of the above solvent, and the catalyst. It is carried out by stirring at 25-100 ° C. in the presence.
In the present invention, an alcohol represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and the general formula R ⁴ COCH ₂ COR ⁵ (where R ⁴ is the number of carbon atoms) 1 to 10 alkyl groups, R5 represents an alkyl group having 1 to 10 carbon atoms or a compound represented by an alkoxy group having 1 to 10 carbon atoms) and is selected from Zr, Ti or Al. It is preferable to perform hydrolysis by stirring at 25 to 100 ° C. in the presence of at least one metal chelate compound having a metal as a central metal.
Alternatively, when an F-containing compound is used as a catalyst, the F-containing compound has the ability to completely proceed with hydrolysis and condensation, so the degree of polymerization can be determined by selecting the amount of water to be added, and any molecular weight can be set Therefore, it is preferable. That is, in order to adjust the organosilane hydrolyzate / partial condensate having an average degree of polymerization M, (M-1) mol of water may be used with respect to M mol of hydrolyzable organosilane.

Metal chelate compounds (wherein, ^{R 3} represents an alkyl group having 1 to 10 carbon atoms) Formula ^R 3 OH alcohol and ^R 4 COCH ₂ COR ⁵ (wherein represented by, ^{R 4} is C 1 -C To 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms), and is selected from Zr, Ti, and Al. Any metal having a metal as a central metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 , Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 , and Al (OR ³ ) _r1 (R ⁴ Those selected from the group of compounds represented by COCHCOR ⁵ ) _r2 are preferred, and they serve to promote the condensation reaction of the hydrolyzate and partial condensate of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. Further, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent 0 or a positive integer determined so as to be p1 + p2 = 4, q1 + q2 = 4, and r1 + r2 = 3, respectively.

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

  The metal chelate compound is preferably used in a proportion of 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, and still more preferably 0.5 to 10% by mass with respect to the organosilane compound. When the metal chelate compound is used within the above range, the condensation reaction of the organosilane compound is fast, the durability of the coating film is good, and the hydrolyzate and partial condensate of the organosilane compound and the metal chelate compound are contained. The storage stability of the composition is good.

In addition to the composition containing the sol component and the metal chelate compound, at least one of a β-diketone compound and a β-ketoester compound is preferably added to the coating solution used in the present invention. This will be further described below.
In the present invention, at least one of a β-diketone compound and a β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ is used as a stability improver for the composition used in the present invention. It works. That is, by coordinating with a metal atom in the metal chelate compound (a compound of at least one of zirconium, titanium and aluminum compounds), condensation of hydrolyzate and partial condensate of organosilane compound by these metal chelate compounds It is considered that the action of accelerating the reaction is suppressed and the action of improving the storage stability of the resulting composition is achieved. R ⁴ and R ⁵ constituting the β- diketone compound and β- ketoester compound are the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the β-diketone compound and β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate- sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, 2,4-nonane-dione , 5-methyl-hexane-dione and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and β-ketoester compounds can be used alone or in admixture of two or more. In the present invention, the β-diketone compound and the β-ketoester compound are preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. By setting it as 2 mol or more, the storage stability of the composition obtained becomes favorable.

  The content of the hydrolyzate and partial condensate of the organosilane compound is preferably small in the case of a relatively thin antireflection layer and large in the case of a thick hard coat layer or antiglare layer. The content is preferably 0.1 to 50% by mass, and preferably 0.5 to 30% by mass based on the total solid content of the containing layer (added layer), considering the effect, refractive index, film shape / surface shape, and the like. More preferred is 1 to 15% by mass.

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

<Photoinitiator>
As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (such as those described in JP-A-2001-139663) 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, etc. It is done.
Examples of acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1-hydroxy Cyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t- Butyl-dichloroacetophenone is included.

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

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

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

Specific examples of the active halogens include Wakabayashi et al. “Bull Chem. Soc Japan Vol. 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-5-27830, M. P. Hutt “Journal of Heterocyclic Chemistry”, Vol. More preferable examples include s-triazine derivatives in which at least one mono, di, or trihalogen-substituted methyl group is bonded to the s-triazine ring, and specific examples include S-triazine and oxathiazole compounds. 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s Triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-styrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3-Br-4-di (ethyl acetate) amino) phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-trihalomethyl-5- (p-methoxyphenyl) -1,3 4-oxadiazole, specifically No. 1-No. 8, compounds Nos. 1 to 17 of p443 to p444 of JP-A-60-239736, Nos. 1 to 19 of US-4701399, and the like are particularly preferable.
Examples of inorganic complexes include bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium.
Examples of coumarins include 3-ketocoumarin.

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

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

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

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

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

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

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

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

  The crosslinkable compound is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, and still more preferably 10 to 30% by mass with respect to the monomer or polymer binder.

1- (7) Curing Catalyst In the film of the present invention, radicals and acids generated by irradiation with ionizing radiation or heat can be used as a curing catalyst for promoting curing.

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

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

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

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

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

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

The refractive index of the binder (translucent resin) and translucent particles in the present invention is preferably 1.45 to 1.70, more preferably 1.48 to 1.65. In order to set the refractive index within the above range, the type and amount ratio of the binder and the light-transmitting particles may be appropriately selected. How to select can be easily known experimentally in advance.
In the present invention, the difference in refractive index between the binder and the translucent particles (the refractive index of the translucent particles−the refractive index of the binder) is preferably 0.001 to 0.030 as an absolute value, More preferably, it is 0.001-0.020, More preferably, it is 0.001-0.015. When this difference is 0.030 or less, problems such as film character blur, a decrease in dark room contrast, and surface turbidity do not occur.

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

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

  The average particle diameter of the translucent particles is preferably 0.5 to 10 μm, more preferably 2.0 to 8.0 μm. When the average particle size is 0.5 μm or more, the light scattering angle distribution does not spread to a wide angle, which is preferable because it does not cause character blur on the display. On the other hand, when the thickness is 10 μm or less, it is not necessary to increase the thickness of the layer to be added, and problems such as curling and cost increase do not occur.

  Moreover, you may use together and use 2 or more types of translucent particle | grains from which a particle diameter differs.

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

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

The particle size distribution of the translucent particles is preferably monodisperse particles in terms of haze value and control of diffusibility, and uniformity of the coated surface. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of the coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1% or less. Yes, more preferably 0.01% or less. Particles having such a particle size distribution are also effective means of classification after preparation or synthesis reaction, and particles having a desired distribution can be obtained by increasing the number of classifications or increasing the degree of classification. .
It is preferable to use a method such as an air classification method, a centrifugal classification method, a sedimentation classification method, a filtration classification method, or an electrostatic classification method for classification.

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

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

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

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

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

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

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

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

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

<Low refractive index particles>
The inorganic particles contained in the low refractive index layer desirably have a low refractive index, and examples thereof include fine particles of magnesium fluoride and silica. In particular, silica fine particles are preferable in terms of refractive index, dispersion stability, and cost.
The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
Here, the average particle diameter of the inorganic particles is measured by a Coulter counter.

  It is preferable to make the particle diameter of the silica fine particles in the above range from the viewpoint of the effect of improving the scratch resistance, the fine irregularities on the surface of the low refractive index layer, the appearance such as black tightening, the integrated reflectance, and the like. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.

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

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

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

The hollow silica fine particles preferably have a refractive index of 1.15 to 1.40, more preferably 1.17 to 1.35, and most preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica particles. At this time, when the radius of the void in the particle is a and the radius of the particle outer shell is b, the porosity x represented by the following formula (VIII) is preferably 10 to 60%, more preferably 20 to 60%. Most preferably, it is 30 to 60%. If hollow silica particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. From the viewpoint of scratch resistance, a low refractive index of 1.15 or more. Rate particles are preferred.
(Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100

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

The coating amount of the hollow silica is ^preferably from ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . By making it 1 mg / m ² or more, the effect of lowering the refractive index and improving the scratch resistance is increased, and by making it 100 mg / m ² or less, fine irregularities cannot be formed on the surface of the low refractive index layer. Appearance such as tightening and integrated reflectance are improved.
The average particle diameter of the hollow silica is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, if the thickness of the low refractive index layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
By setting the particle size of the silica fine particles within the above range, the ratio of the cavity portion is increased and the refractive index can be lowered. Further, fine irregularities cannot be formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are improved. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m ² / g, more preferably 30~120m ² / g, most preferably 40~90m ² / g. The surface area can be obtained by the BET method using nitrogen.

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

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

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

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

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

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

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

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

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

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

When the inorganic particles are silica, the use of a coupling agent is particularly preferred. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, silane coupling treatment is particularly effective.
The above coupling agent is used as a surface treatment agent for the inorganic filler of the low refractive index layer in advance for surface treatment prior to the preparation of the layer coating solution, and is added as an additive during the preparation of the layer coating solution. It is preferable to make it contain in a layer.
The silica fine particles are preferably dispersed in the medium in advance before the surface treatment in order to reduce the load of the surface treatment.
Specific examples of the surface treatment agent and the surface treatment catalyst that can be preferably used in the present invention include organosilane compounds and catalysts described in International Publication No. 2004/017105.

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

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

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of the dispersant preferably used in the present invention are shown below, but the dispersant for the present invention is not limited thereto. Unless otherwise specified, it represents a random copolymer.

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

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

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

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

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

1- (14) Surfactant In the film of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, point defect, etc., either a fluorine-based or silicone-based surfactant, or Both of them are preferably contained in the coating composition for forming the hard coat layer and the light diffusion layer. In particular, a fluorine-based surfactant can be preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects appears at a smaller addition amount. Productivity can be improved by giving high-speed coating suitability while improving surface uniformity.

Preferable examples of the fluorosurfactant include a fluoroaliphatic group-containing copolymer (sometimes abbreviated as “fluorine polymer”), and the fluoropolymer includes the following monomer (i): An acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable with the acrylic resin, the methacrylic resin characterized by containing a corresponding repeating unit, or a repeating unit corresponding to the monomer (ii) below: Copolymers are useful.
(I) Fluoroaliphatic group-containing monomer represented by the following general formula A

In the general formula A, R ¹¹ represents a hydrogen atom or a methyl group, X represents an oxygen atom, a sulfur atom or —N (R ¹² ) —, m is an integer of 1 to 6 and n is an integer of 2 to 4. To express. R ¹² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically a methyl group, an ethyl group, a propyl group or a butyl group, preferably a hydrogen atom or a methyl group. X is preferably an oxygen atom.

(Ii) a monomer represented by the following general formula (b) copolymerizable with the above (i):

In the general formula (b), R ¹³ represents a hydrogen atom or a methyl group, Y represents an oxygen atom, a sulfur atom or —N (R ¹⁵ ) —, R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, specifically Specifically, it represents a methyl group, an ethyl group, a propyl group, or a butyl group, preferably a hydrogen atom or a methyl group. Y is an oxygen atom, -N (H) -, and -N (CH ₃₎ - are preferred.
R ¹⁴ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms which may have a substituent. Examples of the substituent for the alkyl group represented by R ¹⁴ include a hydroxyl group, an alkylcarbonyl group, an arylcarbonyl group, a carboxyl group, an alkyl ether group, an aryl ether group, a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a nitro group, and a cyano group. , Amino groups and the like, but not limited thereto. Examples of the linear, branched or cyclic alkyl group having 4 to 20 carbon atoms include a butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and undecyl group which may be linear or branched. , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group, eicosanyl group, etc., and monocyclic cycloalkyl groups such as cyclohexyl group, cycloheptyl group and bicycloheptyl group, bicyclodecyl group, tricycloundecyl group, A polycyclic cycloalkyl group such as a tetracyclododecyl group, an adamantyl group, a norbornyl group, a tetracyclodecyl group, or the like is preferably used.

The amount of the fluoroaliphatic group-containing monomer represented by the general formula (a) used in the fluoropolymer used in the present invention is 10 mol% or more based on each monomer of the fluoropolymer, preferably Is 15 to 70 mol%, more preferably in the range of 20 to 60 mol%.
The preferred weight average molecular weight of the fluoropolymer used in the present invention is preferably 3000 to 100,000, more preferably 5,000 to 80,000.
Furthermore, the preferable addition amount of the fluoropolymer used in the present invention is in the range of 0.001 to 5% by mass, preferably in the range of 0.005 to 3% by mass, and more preferably, with respect to the coating solution. It is the range of 0.01-1 mass%. When the addition amount of the fluorine-based polymer is 0.001% by mass or more, a sufficient effect is obtained, and when it is 5% by mass or less, the coating film is sufficiently dried and the performance as a coating film is achieved. (For example, reflectivity and scratch resistance) are improved.

  Examples of the specific structure of the fluoropolymer composed of the fluoroaliphatic group-containing monomer represented by the general formula (i) are shown below, but this is not restrictive. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

However, the use of such a fluoropolymer reduces the surface energy of the antiglare layer due to segregation of functional groups containing F atoms on the surface of the antiglare layer, resulting in low refraction on the antiglare layer. When the rate layer is overcoated, there arises a problem that the antireflection performance deteriorates. This is presumably because minute unevenness that cannot be visually detected in the low refractive index layer deteriorates because the wettability of the curable composition used for forming the low refractive index layer deteriorates. To solve such problems, by adjusting the structure and amount of the fluorine-based polymer, the surface energy of the antiglare layer preferably in ^{20mN · m -1 ~50mN · m -1} , more preferably it was found that it is effective to control the ^{30mN · m -1 ~40mN · m -1} . In order to realize the surface energy as described above, F / C, which is a ratio of a peak derived from a fluorine atom and a peak derived from a carbon atom, measured by X-ray photoelectron spectroscopy is 0.1 to 1.5. is required.

  Alternatively, by selecting a fluorine-based polymer that is extracted by the solvent that forms the upper layer when the upper layer is applied, it is not unevenly distributed on the lower layer surface (= interface), so that the adhesion between the upper layer and the lower layer is provided. The surface energy of the antiglare layer before coating the low refractive index layer can be reduced by maintaining the surface uniformity even at high speed coating and preventing the decrease in surface free energy that can provide an antireflection film with high scratch resistance. The purpose can also be achieved by controlling the range. Examples of such materials include an acrylic resin, a methacrylic resin, and a vinyl monomer copolymerizable therewith, containing a repeating unit corresponding to a fluoroaliphatic group-containing monomer represented by the following general formula C And a copolymer.

(Iii) A fluoroaliphatic group-containing monomer represented by the following general formula C

In the general formula C, R ²¹ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. X ² represents an oxygen atom, a sulfur atom or —N (R ²² ) —, more preferably an oxygen atom or —N (R ²² ) —, and still more preferably an oxygen atom. m is an integer from 1 to 6 (more preferably from 1 to 3, more preferably 1), and n is an integer from 1 to 18 (more preferably from 4 to 12, and even more preferably from 6 to 8). Represents. R ²² represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group. X2 is preferably an oxygen atom.
In addition, two or more kinds of fluoroaliphatic group-containing monomers represented by the general formula C may be contained in the fluorine-based polymer as constituent components.

(Iv) a monomer represented by the following general formula d copolymerizable with the above (iii)

In the general formula D, R ²³ represents a hydrogen atom, a halogen atom or a methyl group, more preferably a hydrogen atom or a methyl group. Y ² represents an oxygen atom, a sulfur atom or —N (R ²⁵ ) —, more preferably an oxygen atom or —N (R ²⁵ ) —, and still more preferably an oxygen atom. R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom or a methyl group.
In General Formula D, R ²⁴ may have a substituent, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkyl group including a poly (alkyleneoxy) group, and a substituent. Represents a good aromatic group (for example, a phenyl group or a naphthyl group). A linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or an aromatic group having 6 to 18 carbon atoms is more preferable, and a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms is more preferable. .

  Hereinafter, examples of specific structures of fluoropolymers containing a repeating unit corresponding to the fluoroaliphatic group-containing monomer represented by formula (c) are shown, but the present invention is not limited thereto. In addition, the number in a formula shows the molar ratio of each monomer component. Mw represents a mass average molecular weight.

1- (15) Thickener The film of the present invention may use a thickener to adjust the viscosity of the coating solution.
The term “thickener” as used herein means that the viscosity of the liquid is increased by adding it, and preferably 0.05 to 50 cP (0. 05 to 50 mPa.s), more preferably 0.10 to 20 cP (0.10 to 20 mPa.s), and most preferably 0.10 to 10 cP (0.10 to 10 mPa.s).

Examples of such thickeners include, but are not limited to:
Poly-ε-caprolactone poly-ε-caprolactone diol poly-ε-caprolactone triol polyvinyl acetate poly (ethylene adipate)
Poly (1,4-butylene adipate)
Poly (1,4-butylene glutarate)
Poly (1,4-butylene succinate)
Poly (1,4-butylene terephthalate)
polyethylene terephthalate)
Poly (2-methyl-1,3-propylene adipate)
Poly (2-methyl-1,3-propylene glutarate)
Poly (neopentyl glycol adipate)
Poly (neopentyl glycol sebacate)
Poly (1,3-propylene adipate)
Poly (1,3-propylene glutarate)
Polyvinyl butyral polyvinyl formal polyvinyl acetal polyvinyl propanal polyvinyl hexanal polyvinyl pyrrolidone polyacrylic ester polymethacrylic acid ester cellulose acetate cellulose propionate cellulose acetate butyrate

  In addition, smectite, fluorine tetrasilicon mica, bentonite, silica, montmorillonite and sodium polyacrylate described in JP-A-8-325491, ethyl cellulose, polyacrylic acid, organic clay described in JP-A-10-219136, and the like are known. Viscosity modifiers and thixotropic agents can be used.

1- (16) Coating solvent As a solvent used in the coating composition for forming each layer of the present invention, each component can be dissolved or dispersed, and a uniform surface is easily formed in the coating process and the drying process. Various solvents selected from the viewpoints of ensuring liquid storage stability and having an appropriate saturated vapor pressure can be used.
Two or more kinds of solvents can be mixed and used. In particular, from the viewpoint of drying load, it is preferable to use a solvent having a boiling point of less than 120 ° C. at normal pressure and room temperature as the main component in terms of planar stability due to an increase in the drying rate.

  Examples of the solvent having a boiling point of less than 120 ° C. include hydrocarbons such as hexane (boiling point 68.7 ° C.), heptane (98.4 ° C.), cyclohexane (80.7 ° C.), benzene (80.1 ° C.), Halogenated carbonization such as dichloromethane (39.8 ° C), chloroform (61.2 ° C), carbon tetrachloride (76.8 ° C), 1,2-dichloroethane (83.5 ° C), trichloroethylene (87.2 ° C) Hydrogens, diethyl ether (34.6 ° C), diisopropyl ether (68.5 ° C), dipropyl ether (90.5 ° C), tetrahydrofuran (66 ° C) and other ethers, ethyl formate (54.2 ° C), Esters such as methyl acetate (57.8 ° C.), ethyl acetate (77.1 ° C.), isopropyl acetate (89 ° C.), acetone (56.1 ° C.), 2-butanone (methyl ethyl) Ketones such as 79.6 ° C, the same as ketone, methanol (64.5 ° C), ethanol (78.3 ° C), 2-propanol (82.4 ° C), 1-propanol (97.2 ° C), etc. Alcohols, cyano compounds such as acetonitrile (81.6 ° C), propionitrile (97.4 ° C), carbon disulfide (46.2 ° C), toluene (110.6 ° C), dioxane (101.3 ° C) ° C), isobutyl acetate (118 ° C), 1-butanol (117.7 ° C), and the like. Of these, ketones and esters are preferable, and ketones are particularly preferable. Among the ketones, 2-butanone is particularly preferable.

  Examples of the solvent having a boiling point of 120 ° C. or higher include octane (125.7 ° C.), xylene (138 ° C.), tetrachloroethylene (121.2 ° C.), chlorobenzene (131.7 ° C.), and dibutyl ether (142.4 ° C.). , Cyclohexanone (155.7 ° C.), 2-methyl-4-pentanone (same as MIBK, 115.9 ° C.), N, N-dimethylformamide (153 ° C.), N, N-dimethylacetamide (166 ° C.), dimethyl And sulfoxide (189 ° C.).

  In the coating solvent, the proportion of the solvent having a boiling point of less than 120 ° C. in the total solvent is not particularly limited, but is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, More preferably, it is at least 100% by mass.

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

1- (18) Transparent support The support of the film of the present invention is not particularly limited, such as a transparent resin film, a transparent resin plate, a transparent resin sheet, and transparent glass. Transparent resin films include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone. Films, polyacrylic resin films, polyurethane resin films, polyester films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth) acrylonitrile films, and the like can be used.
Although the thickness of a 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.
Any width of the support can be used, but from the viewpoint of handling, yield, and productivity, a width of 100 to 5000 mm is usually used, preferably 800 to 3000 mm, and preferably 1000 to 2000 mm. More preferably. Although arbitrary things can be used also about a raw material roll length, the thing of 300-10000m is normally used from the point of handling, a yield, and productivity, and it is preferable that it is 500-7000m, and 1000-4000m. More preferably it is.
The surface of the 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. Is more preferable.

<Cellulose acylate film>
Among the various films described above, a cellulose acylate film having high transparency, optically low birefringence, easy production, and generally used as a protective film for polarizing plates is preferable.
For cellulose acylate films, various improvement techniques are known for the purpose of improving mechanical properties, transparency, flatness and the like, and the techniques described in the published technical reports 2001-1745 are known as the present invention. It can be used for the film.
In the present invention, among the cellulose acylate films, a cellulose triacetate film is particularly preferable, and it is preferable to use cellulose acetate having an acetylation degree of 59.0 to 61.5% for the cellulose acylate film. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation follows the measurement and calculation of the degree of acetylation in ASTM: D-817-91 (test method for cellulose acetate and the like).
The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more.
In addition, the cellulose acylate used in the present invention has a Mw / Mn (Mw is mass average molecular weight, Mn is number average molecular weight) value by gel permeation chromatography close to 1.0, in other words, a molecular weight distribution. Narrow is preferred. The specific value of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. preferable.

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

<Manufacture of cellulose acylate film>
The cellulose acylate film used in the present invention can be produced by a solution casting method (solvent casting method). In the solvent cast method, a film is produced using a solution (dope) in which cellulose acylate is dissolved in an organic solvent.

  The organic solvent is a solvent selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to contain. Two or more organic solvents may be mixed and used.

  The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and —COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group. In the case of an organic solvent having two or more types of functional groups, the preferred number of carbon atoms may be within the range of the preferred number of carbon atoms specified above for the compound having any functional group.

Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.
Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.
Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

  Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogenated hydrocarbon hydrogen atoms replaced with halogen is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.

The cellulose acylate solution (dope) can be adjusted by a general method. A general method means processing at a temperature of 0 ° C. or higher (room temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly methylene chloride) as the organic solvent. A non-chlorinated solvent can also be used, and examples thereof include those described in JIII Journal of Technical Disclosure No. 2001-1745.
The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).
The solution can be prepared by stirring cellulose acylate and an organic solvent at room temperature (0 to 40 ° C.). High concentration solutions may be stirred under pressure and heating conditions. Specifically, cellulose acylate and an organic solvent are placed in a pressure vessel and sealed, and stirred while being heated to a temperature equal to or higher than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., more preferably 80 to 110 ° C.

Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially.
The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.
When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.
It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.
Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in the container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acetate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.
In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring.
The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture at 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this way, the mixture of cellulose acetate and organic solvent solidifies.
The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

Further, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acetate is dissolved in the organic solvent. The temperature can be raised by simply leaving it at room temperature or in a warm bath.
The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .
A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.
In addition, according to differential scanning calorimetry (DSC), a 20 mass% solution obtained by dissolving cellulose acetate (acetylation degree: 60.9%, viscosity average polymerization degree: 299) in methyl acetate by a cooling dissolution method was 33. There exists a quasi-phase transition point between a sol state and a gel state in the vicinity of ° C., and a uniform gel state is obtained below this temperature. Therefore, this solution needs to be maintained at a temperature equal to or higher than the pseudo phase transition temperature, preferably about the gel phase transition temperature plus about 10 ° C. However, this pseudo phase transition temperature varies depending on the degree of acetylation of cellulose acetate, the degree of viscosity average polymerization, the concentration of the solution, and the organic solvent used.

A cellulose acylate film is produced from the prepared cellulose acylate solution (dope) by a solvent cast method.
The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35%.
The surface of the drum or band is preferably finished in a mirror state. The casting and drying methods in the solvent casting method are described in U.S. Pat. No. 7,736892, JP-B Nos. 45-4554, 49-5614, and 62-1115035.
The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less.
After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band, and further dried by high-temperature air whose temperature is successively changed from 100 to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

A film can also be produced by casting two or more layers by a solvent casting method using a plurality of prepared cellulose acylate solutions (dope). In this case, the dope is cast on a drum or band and the solvent is evaporated to form a film. It is preferable to adjust the concentration of the dope before casting so that the solid content is 10 to 40% by mass. The surface of the drum or band is preferably finished in a mirror state.
When casting a plurality of cellulose acylate liquids of two or more layers, it is possible to cast a plurality of cellulose acylate solutions, and cellulose is supplied from a plurality of casting openings provided at intervals in the traveling direction of the support. A film may be produced while casting and laminating a solution containing an acylate. For example, in each publication such as JP-A Nos. 61-158414, 1-122419, 11-198285, etc. The described method is applicable. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-104813, It can be carried out by the methods described in JP-A Nos. 61-158413 and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high-low viscosity cellulose acylate solution is simultaneously extruded. A casting method may be used.

  Alternatively, using two casting ports, the film cast on the support is peeled off by the first casting port, and the second casting is performed on the side that is in contact with the support surface, so that the film is For example, it is a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port.

  Furthermore, in the present invention, the cellulose acylate solution is cast simultaneously with a solution for forming other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer, etc.) Simultaneous formation of the layer and film formation can also be carried out.

  In the case of a single-layer solution, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution to obtain the required film thickness. In this case, the stability of the cellulose acylate solution is poor and solids are generated. In many cases, however, it becomes a problem due to a failure or a poor flatness. As this solution, a plurality of cellulose acylate solutions are cast from a casting port. As a result, it is possible to extrude a highly viscous solution onto the support at the same time, not only can the flatness be improved and an excellent planar film can be produced, but also a concentrated cellulose acylate solution can be used to reduce the drying load. Reduction can be achieved and film production speed can be increased.

A plasticizer can be added to the cellulose acylate film in order to improve the mechanical properties or to improve the drying rate after casting during film production. As the plasticizer, phosphoric acid ester or carboxylic acid ester is used. Examples of phosphate esters include triphenyl phosphate (TPP), diphenyl biphenyl phosphate, and tricresyl phosphate (TCP). Representative examples of the carboxylic acid ester include phthalic acid esters and citric acid esters. Examples of phthalic acid esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), diphenyl phthalate (DPP) and diethyl hexyl phthalate (DEHP). Examples of citrate esters include triethyl O-acetylcitrate (OACTE) and tributyl O-acetylcitrate (OACTB). Examples of other carboxylic acid esters include butyl oleate, methylacetyl ricinoleate, dibutyl sebacate, and various trimellitic acid esters. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are preferably used. DEP and DPP are particularly preferred.
The addition amount of the plasticizer is preferably 0.1 to 25% by mass of the amount of cellulose acylate, more preferably 1 to 20% by mass, and most preferably 3 to 15% by mass.

  A degradation inhibitor (eg, antioxidant, peroxide decomposer, radical inhibitor, metal deactivator, acid scavenger, amine) may be added to the cellulose acylate film. The deterioration inhibitors are described in JP-A-3-199201, JP-A-597073, JP-A-5-194789, JP-A-5-271471, and JP-A-6-107854. The addition amount of the deterioration preventing agent is preferably 0.01 to 1% by mass of the solution (dope) to be prepared in consideration of the effect of the deterioration preventing agent and bleeding out (bleeding out) to the film surface. More preferably, the content is 0.01 to 0.2% by mass. Examples of particularly preferred deterioration inhibitors include butylated hydroxytoluene (BHT) and tribenzylamine (TBA).

In the cellulose acylate film, a retardation increasing agent can be used as necessary in order to adjust the retardation of the film. The retardation of the film is preferably 0 to 300 nm in the film thickness direction and 0 to 1000 nm in the in-plane direction.
An aromatic compound having at least two aromatic rings is preferable as the retardation increasing agent, and the aromatic compound is used in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of cellulose acylate. The aromatic compound is preferably used in the range of 0.05 to 15 parts by mass, and more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of cellulose acetate. Two or more aromatic compounds may be used in combination.
Details are described in Japanese Patent Application Laid-Open Nos. 2000-1111914, 2000-275434, 2002-236215, and International Publication No. 00/065384.

<Stretching treatment of cellulose acylate film>
The produced cellulose acylate film can further improve drying unevenness, film thickness unevenness caused by drying shrinkage, and surface unevenness by stretching treatment. The stretching treatment is also used for adjusting the retardation.
Although there is no limitation in particular in the method of the width direction extending | stretching process, the extending | stretching method by a tenter is mentioned as the example.
More preferably, the longitudinal stretching is performed in the longitudinal direction of the roll, and the longitudinal stretching is performed by adjusting the draw ratio of each pass roll (rotational ratio between the pass rolls) between the pass rolls that transport the roll film. Is possible.

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

2. The layer which comprises a film Although the film of this invention is obtained by mixing and coating said various compounds, it describes about the layer which comprises the film of this invention next.

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

  The refractive index of the hard coat layer in the present invention is preferably in the range of 1.48 to 2.00, more preferably 1.52 to 1, from the optical design for obtaining an antireflection film. .90, more preferably 1.55 to 1.80. In the present invention, since there is at least one low refractive index layer on the hard coat layer, it is preferable that the refractive index is in this range from the viewpoints of antireflection properties and the color of reflected light.

From the viewpoint of imparting sufficient durability and impact resistance to the film, the thickness of the hard coat layer is usually about 0.5 μm to 50 μm, preferably 2 μm to 35 μm, more preferably 5 μm. It is -35 micrometers, More preferably, it is 8 micrometers-35 micrometers, Most preferably, it is 20 micrometers-35 micrometers.
Further, the strength of the hard coat layer is preferably 2H or more, more preferably 3H or more, and further preferably 4H or more in the pencil hardness test. The most preferable is 5H or more, and in the hard coat film using the ionizing radiation curable binder in the present invention, 4H can be achieved with a thickness of 8 μm or more. 5H can be achieved with a thickness of 20 μm or more. Moreover, by setting it as 35 micrometers or less, it becomes favorable in terms of the brittleness of a film, curl, handling property, brittleness, etc.
Furthermore, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

The hard coat layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. For example, it may be formed by coating a coating composition containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer on a transparent support and subjecting the polyfunctional monomer or polyfunctional oligomer to a crosslinking reaction or a polymerization reaction. it can.
The functional group of the ionizing radiation curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. For the purpose of imparting internal scattering properties, the hard coat layer has matte particles having an average particle size of 0.5 to 10 μm, preferably 2 to 8.0 μm, such as inorganic compound particles or aggregates of inorganic compound fine particles, or The resin particles may be contained.

  The main object of the antireflection film of the present invention is to maximize black tightening, and the surface haze is preferably less than 5%, more preferably less than 3%. On the other hand, if there is no surface haze (≈0%), it is a smooth surface and the reflection of the image increases, so that the surface haze is preferably 0.1% or more in order not to deteriorate the visibility. That is, 0.1% or more and less than 5% is preferable.

  On the other hand, the internal haze is preferably less than 36%, more preferably less than 25%, still more preferably less than 15%, still more preferably less than 5%, and most preferably less than 1%. If there is an internal haze, the front brightness of the display is lowered, and the display image is darkly blurred. Therefore, it is preferable that there is no internal haze. The internal haze value is a value obtained by subtracting the surface haze value from the total haze value, and the measurement method will be described later.

2- (2) Antiglare Layer The antiglare layer is formed for the purpose of contributing to the film antiglare properties due to surface scattering and preferably hard coat properties for improving the scratch resistance of the film. In the film of the present invention, the antiglare layer may also serve as a hard coat layer.

As a method of forming the antiglare property, a method of laminating and forming a mat-shaped shaping film having fine irregularities on the surface as described in JP-A-6-16851, described in JP-A-2000-206317. The method of forming by curing shrinkage of ionizing radiation curable resin due to the difference in ionizing radiation dose, as described in JP 2000-338310 A, the mass ratio of good solvent to translucent resin is reduced by drying A method of forming unevenness on the coating film surface by solidifying the light-transmitting fine particles and the light-transmitting resin while gelling, and providing surface unevenness by external pressure as described in JP-A-2000-275404 There are known methods, and these known methods can be used.
The antiglare layer that can be used in the present invention preferably contains a binder capable of imparting hard coat properties, translucent particles for imparting antiglare properties, and a solvent as essential components. It is preferable that irregularities on the surface be formed by the protrusions of the protrusions themselves or protrusions formed by an aggregate of a plurality of particles.
The antiglare layer formed by dispersing the matte particles is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties.

As specific examples of the mat particles, inorganic particles such as silica particles and TiO2 particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. It is done. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
The shape of the mat particles can be either spherical or irregular. Two or more kinds of mat particles having different particle diameters may be used in combination.

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

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

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

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

The inorganic particles mainly composed of TiO ₂ used for the high refractive index layer and the medium refractive index layer are used for forming the high refractive index layer and the medium refractive index layer in the state of dispersion.
In the dispersion of the inorganic particles, the inorganic particles are dispersed in a dispersion medium in the presence of a dispersant.

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

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

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

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

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

2- (4) Low Refractive Index Layer In order to reduce the reflectance of the film of the present invention, it is necessary to use a low refractive index layer.

The refractive index of the low refractive index layer is 1.47 or less, preferably 1.20 to 1.47, more preferably 1.25 to 1.47, and 1.30 to 1.47. It is particularly preferred that
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 100 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. In order to improve the antifouling performance of the optical film, it is preferable that the contact angle of the surface with respect to water is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

  The curable composition for providing the low refractive index layer preferably contains (A) the above-mentioned fluoropolymer, (B) inorganic particles, and (C) an organosilane compound.

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

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

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

  The antistatic layer has a light transmittance of a wavelength of 550 nm of preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and preferably 70% or more. Most preferred.

2- (6) Antifouling Layer In the present invention, the outermost layer (for example, a low refractive index layer) may have a function as an antifouling layer. The antifouling layer lowers the surface energy of the antireflection layer and makes it difficult to attach hydrophilic or lipophilic stains.
The antifouling layer can be formed using a fluorine-containing polymer or an antifouling agent.
The thickness of the antifouling layer is preferably 2 to 100 nm, and more preferably 5 to 30 nm.

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

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

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

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

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

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

2- (9) Anti-curl layer The film of the present technology may be subjected to anti-curl processing. The anti-curl processing is to give the function of rounding with the surface on which it is applied inside, but by applying this processing, some surface processing is performed on one side of the transparent support and both sides are processed. It works to prevent curling with the surface facing inward when different degrees and types of surface treatment are applied.
The anti-curl layer may be provided on the side of the transparent support opposite to the side having the hard coat layer, anti-glare layer or anti-reflection layer, or an easy-adhesion layer may be provided on one side of the transparent support, for example. A mode in which an anti-curling process is applied to the surface is mentioned.

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

2- (10) Water Absorbing Layer A water absorbent can be used in the film of the present invention. The water absorbent can be selected from compounds having a water absorption function, mainly alkaline earth metals. Examples thereof include BaO, SrO, CaO, and MgO. Further, it can be selected from metal elements such as Ti, Mg, Ba, and Ca. The particle size of these absorbent particles is preferably 100 nm or less, and more preferably 50 nm or less.

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

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

When the hard coat layer (2) is applied on the support (1) and the low refractive index layer (5) is laminated as shown in a (FIG. 1), it can be suitably used as an antireflection film. The low refractive index layer (5) is formed by forming the low refractive index layer (5) on the hard coat layer (2) with a film thickness of about 1/4 of the wavelength of light, thereby reflecting the surface reflection by the principle of thin film interference. Can be reduced.
Moreover, even if a high refractive index layer (4) and a low refractive index layer (5) are laminated after applying a hard coat layer (2) on a support (1) as shown in FIG. It can use suitably as a prevention film. Further, as in c (FIG. 3), the order of the support (1), the hard coat layer (2), the medium refractive index layer (3), the high refractive index layer (4), and the low refractive index layer (5) By installing a layer structure, the reflectance can be reduced to 1% or less.

  In the constitutions a to c, the hard coat layer (2) can be an antiglare layer having antiglare properties. The antiglare property may be formed by the dispersion of mat particles (6) as shown in FIG. 4 or may be formed by surface shaping by a method such as embossing as shown in FIG. The antiglare layer formed by the dispersion of the mat particles (6) is composed of a binder and translucent particles dispersed in the binder. The antiglare layer having antiglare properties preferably has both antiglare properties and hard coat properties, and may be composed of a plurality of layers, for example, 2 to 4 layers.

In addition, interference unevenness (rainbow unevenness) prevention layer, antistatic layer (reduction of surface resistance value from the display side, etc.) may be provided between the transparent support and the surface side layer or the outermost layer. , If there is a problem with dust on the surface, etc.), another hard coat layer (when one hard coat layer or antiglare layer is insufficient in hardness), gas barrier layer, water absorption layer ( Moisture-proof layer), adhesion improving layer, antifouling layer (contamination preventing layer), and the like.
The refractive index of each layer constituting the antireflection film in the present invention has the following relationship:
It is preferable that the refractive index of the hard coat layer> the refractive index of the transparent support> the refractive index of the low refractive index layer. Moreover, when the structure of the antireflection film in the present invention is a structure in which the transparent support / hard coat layer / high refractive index layer / low refractive index layer are laminated in this order, the refractive index of each layer has the following relationship:
It is preferable that the refractive index of the low refractive index layer <the refractive index of the hard coat layer <the refractive index of the high refractive index layer.

4). Manufacturing Method The film of the present invention can be formed by the following method, but is not limited to this method.

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

<Physical properties of coating solution>
For coating solutions for forming layers with a dry film thickness of 200 nm or less, such as low refractive index layer, medium refractive index layer, high refractive index layer, antifouling layer, etc., the upper limit speed that can be applied is large due to the liquid properties. Since it is affected, it is necessary to control the liquid properties at the moment of application, particularly the viscosity and surface tension.
The viscosity is preferably 2.0 [mPa · sec] or less, more preferably 1.5 [mPa · sec] or less, and most preferably 1.0 [mPa · sec] or less. Since there are some coating solutions whose viscosity changes depending on the shear rate, the above value indicates the viscosity at the shear rate at the moment of coating. When a thixotropic agent is added to the coating solution and the coating solution is subjected to high shear, the viscosity is low, and when the coating solution is hardly sheared, if the viscosity is high, unevenness during drying is less likely to occur.
Moreover, although it is not a liquid physical property, the quantity of the coating liquid apply | coated to a transparent support body also affects the upper limit speed | rate which can be apply | coated. The amount of the coating solution applied to the transparent support is 2.0 to 5.0 [cm3].
/ M2]. Increasing the amount of the coating liquid applied to the transparent support is preferable because the upper limit of the application rate can be increased, but if the amount of the coating liquid applied to the transparent support is increased too much, the load on drying increases. It is preferable to determine the optimal amount of coating liquid to be applied to the transparent support depending on the liquid formulation and process conditions.
The surface tension is preferably in the range of 15 to 36 [mN / m]. It is preferable to reduce the surface tension by adding a leveling agent or the like because unevenness during drying is suppressed. On the other hand, if the surface tension is too low, the upper limit speed at which coating can be performed is reduced. Therefore, a range of 17 [mN / m] to 32 [mN / m] is more preferable, and 19 [mN / m] to 26 [mN / m]. mN / m] is more preferable.
In the antiglare layer containing translucent particles, it is preferable to adjust to a viscosity of 4 cP (4 mPa.s) or more, and further to adjust to a viscosity of 6 cP (6 mPa.s) or more from the viewpoint of preventing sedimentation of the particles. preferable.

<Filtration>
The coating solution used for coating is preferably filtered before coating. As the filter for filtration, it is preferable to use a filter having a pore diameter as small as possible within the range in which the components in the coating solution are not removed. For filtration, a filter having an absolute filtration accuracy of 0.1 to 50 μm is used, and a filter having an absolute filtration accuracy of 0.1 to 40 μm is preferably used. The thickness of the filter is preferably 0.1 to 10 mm, and more preferably 0.2 to 2 mm. In that case, the filtration pressure is preferably 1.5 MPa or less, more preferably 1.0 MPa or less, and further preferably 0.2 MPa or less.
The filtration filter member is not particularly limited as long as it does not affect the coating solution. Specifically, the same thing as the filter member of the wet dispersion of an inorganic compound is mentioned.
It is also preferable to ultrasonically disperse the filtered coating solution immediately before coating to assist defoaming and dispersion holding of the dispersion.

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

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

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

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

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

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

In order to supply the film of the present invention with high productivity, an extrusion method (die coating method) is preferably used. In particular, a die coater that can be preferably used in a region with a small wet coating amount (20 cm ³ / m ² or less) such as a hard coat layer or an antireflection layer will be described below.

<Die coater configuration>
FIG. 6 is a sectional view of a coater using a slot die suitable for the present invention. The coater 10 is applied to the web W supported by the backup roll 11 and continuously applied from the slot die 13 as a bead 14a to form a coating film 14b on the web W.

  Inside the slot die 13, a pocket 15 and a slot 16 are formed. The pocket 15 has a curved section and a straight section, and may be substantially circular as shown in FIG. 6, for example, or may be semicircular. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width. The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

  The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web W, and has a cross-sectional shape in the width direction of the slot die 13 similarly to the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web running direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. In the land 18, the upstream side in the traveling direction of the web W with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

7A and 7B show the cross-sectional shape of the slot die 13 in comparison with the conventional one. FIG. 7A shows the slot die 13 suitable for the present invention, and FIG. 7B shows the conventional slot die 30. . In the conventional slot die 30, the distance between the upstream lip land 31a and the web of the downstream lip land 31b is equal. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 of the present invention, the downstream side lip land length I _LO is shortened, so that application with a wet film thickness of 20 μm or less can be performed with high accuracy.

The land length I _UP of the upstream lip land 18a is not particularly limited, but is preferably used in the range of 500 μm to 1 mm. The land length I _LO of the downstream lip land 18b is not less than 30 μm and not more than 100 μm, preferably not less than 30 μm and not more than 80 μm, more preferably not less than 30 μm and not more than 60 μm. When the land length I _LO of the downstream lip is 30 μm or more, the edge or land of the tip lip is hardly chipped, and streaks are hardly generated in the coating film. In addition, the setting of the wet line position on the downstream side becomes easy, and the coating liquid is difficult to spread on the downstream side. It has been conventionally known that the spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface.

Further, the downstream lip land 18b has an overbite shape closer to the web W than the upstream lip land 18a. Therefore, the degree of decompression can be lowered, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream side lip land 18b and the web W of the upstream side lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less. When the slot die 13 has an overbite shape, the gap GL between the tip lip 17 and the web W indicates the gap between the downstream lip land 18b and the web W.

FIG. 8 is a perspective view showing a slot die and its periphery in a coating process suitable for the present invention.
On the opposite side of the web W in the direction of travel, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression can be adjusted. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and the gaps G _B and G between the back plate 40a and the web W, and between the side plate 40b and the web W, respectively. _S exists.
FIG. 9 is a cross-sectional view showing the vacuum chamber 40 and the web W that are close to each other. The side plate and the back plate may be integrated with the chamber main body as shown in FIG. 9, or may be structured to be fastened to the chamber with screws or the like so that the gap can be changed as appropriate. In any structure, the portions actually opened between the back plate 40a and the web W and between the side plate 40b and the web W are defined as gaps G _B and G _S , respectively. The gap G _B between the back plate 40a and the web W of the decompression chamber 40, when the vacuum chamber 40 is placed under the web W and the slot die 13 as shown in FIG. 8, the uppermost end of the back plate 40a to the web W Indicates the gap.

Is preferably placed in the gap G _B between the back plate 40a and the web W is larger than the gap G _L between the end lip 17 and the web W of the slot die 13, beads vicinity due to the eccentricity of the backup roll 11 thereby The change in the degree of decompression can be suppressed. For example, when the gap _{G L} between the end lip 17 and the web W of the slot die 13 is 30μm or more 100μm or less, the gap _{G B} between the back plate 40a and the web W is preferably 100μm or 500μm or less.

<Material and accuracy>
The longer the length of the tip lip on the traveling direction side of the web in the web traveling direction, the more disadvantageous it is for bead formation.If this length varies between arbitrary locations in the slot die width direction, It becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.
Further, when the material of the tip lip of the slot die is made of a material such as stainless steel, the length of the slot die tip lip in the web running direction is set to 30 to 100 μm as described above. Even within this range, the accuracy of the tip lip may not be satisfied. Therefore, in order to maintain high processing accuracy, it is preferable to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less. Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.
In order to realize high-precision coating, the length of the land on the web traveling direction side of the tip lip and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of these two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness of the tip lip and the backup roll is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

<Application speed>
By achieving the accuracy of the backup roll and the tip lip as described above, the coating method preferably used in the present invention has high film thickness stability during high-speed coating. Furthermore, since the coating method is a pre-weighing method, it is easy to ensure a stable film thickness even during high-speed coating. With respect to a coating solution of a low coating amount, the coating method can be applied at high speed with good film thickness stability. Although application is possible by other application methods, the dip coating method inevitably causes vibration of the application liquid in the liquid receiving tank, and stepped unevenness is likely to occur. In the reverse roll coating method, stepped unevenness is likely to occur due to eccentricity and deflection of the roll related to coating. Moreover, since these coating methods are post-measuring methods, it is difficult to ensure a stable film thickness. From the viewpoint of productivity, it is preferable to apply at a rate of 50 m / min or more using the die coating method.

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

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

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

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

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

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

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

  The time for irradiating with ionizing radiation is preferably 0.7 seconds or longer and 60 seconds or shorter, and more preferably 0.7 seconds or longer and 10 seconds or shorter. By setting it as 0.7 second or more, the curing reaction is completed and sufficient curing can be performed. Moreover, since it is not necessary to maintain low-oxygen conditions for a long time by setting it as 60 seconds or less, it is excellent in the viewpoint that the enlargement of an installation can be avoided and a lot of inert gas is unnecessary.

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

  As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

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

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

  In curing, the film surface is preferably heated at 60 ° C. or higher and 170 ° C. or lower. By setting the temperature to 60 ° C. or higher, sufficient curing can be achieved, and by setting the temperature to 170 ° C. or lower, deformation of the support can be prevented. Furthermore, this preferable temperature is 60 degreeC-100 degreeC. The film surface refers to the film surface temperature of the layer to be cured. The time for the film to reach the temperature is preferably 0.1 second or more and 300 seconds or less from the start of UV irradiation, and more preferably 10 seconds or less. The above time range is preferable from the viewpoint of promoting the reaction of the curable composition forming the film, the optical performance of the film, and the scale of the equipment.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As the polarizing film, a known polarizing film or a polarizing film cut out from a long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction may be used. A long polarizing film whose absorption axis is neither parallel nor perpendicular to the longitudinal direction is produced by the following method.
That is, a polarizing film stretched by applying tension while holding both ends of a continuously supplied polymer film by a holding means, stretched at least 1.1 to 20.0 times in the film width direction, The progress of the film is such that the difference between the moving speeds in the longitudinal direction of the holding device is within 3%, and the angle formed by the film moving direction at the exit of the step of holding both ends of the film and the substantial stretching direction of the film is inclined by 20 to 70 °. The film can be produced by a stretching method in which the direction is bent while holding both ends of the film. In particular, those inclined by 45 ° are preferably used from the viewpoint of productivity.

The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.
Of the two protective films of the polarizer, the film other than the antireflection film is preferably an optical compensation film having an optical compensation layer comprising an optically anisotropic layer. The optical compensation film (retardation film) can improve the viewing angle characteristics of the liquid crystal display screen.
A known film can be used as the optical compensation film, but the optical compensation film described in JP-A-2001-100042 is preferable in terms of widening the viewing angle.

5). Form of use of the present invention The film of the present invention is used in image display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD) and cathode ray tube display devices (CRT). The film or polarizing plate of the present invention can be used on the outermost surface of a known display such as LCD, PDP, ELD, or CRT.

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

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

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

<VA mode>
In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.
The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625) (2) Liquid crystal cell (SID97, Digest of Tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) A liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).

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

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

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

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

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

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

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

6). Various characteristic values Various measurement methods related to the present invention and preferable characteristic values are shown below.

6- (1) Reflectance The 5 ° regular reflectance referred to in the present invention means that a spectrophotometer “V-550” [manufactured by JASCO Corporation] is fitted with an adapter “ARV-474” and 380 to 780 nm. In this wavelength region, the specular reflectivity at an output angle of -5 ° at an incident angle of 5 ° is measured, and the average specular reflectivity of 450 to 650 nm is measured. The integrated reflectance is the integrated reflection at an incident angle of 5 ° in the wavelength range of 380 to 780 nm by attaching the adapter “ILV-471” to the spectrophotometer “V-550” [manufactured by JASCO Corporation]. The rate is measured, and is the average integrated reflectance of 450 to 650 nm therein.

6- (2) Surface Roughness Centerline average roughness (Ra) was measured according to JIS-B0601.

6- (3) Haze The total haze of the film of the present invention is the haze value defined in JIS-K7105. Based on the measurement method defined in JIS-K7361-1, manufactured by Nippon Denshoku Industries Co., Ltd. A value automatically measured as haze = (diffused light / total transmitted light) × 100 (%) measured using a turbidimeter “NDH-1001DP” was used. Note that the total haze = surface haze + internal haze, and the internal haze is measured by overcoating the same material as the outermost layer so that the surface roughness (surface haze) of the hard coat film is eliminated. Is required. The surface haze is a value obtained by subtracting the internal haze from the total haze.

6- (4) Hardness <Pencil hardness>
The strength of the film of the present invention can be evaluated by a pencil hardness test according to JIS-K5400.

6- (5) Brittleness test (crack resistance)
Crack resistance is an important characteristic for preventing crack defects by handling such as film application, processing, cutting, adhesive application, and application to various objects.
A film sample is cut into 35 mm x 140 mm, left to stand for 2 hours at a temperature of 25 ° C and a relative humidity of 60%, and then the curvature diameter at which cracks start to occur when rolled into a cylinder is measured to evaluate surface cracks. can do.

6- (6) Performance of liquid crystal display device Hereinafter, a method for evaluating characteristics and a preferable situation when the film of the present invention is used on a display device will be described.
The polarizing plate on the viewing side provided in the liquid crystal display device (32 "TV: W32-L7000, manufactured by Hitachi, Ltd.) using an IPS liquid crystal cell is peeled off, and the film or polarizing plate of the present invention is applied instead. The surface was pasted on the viewing side through an adhesive, and the liquid crystal display device was displayed in black in a 1000 lux bright room, evaluated visually, and the following determination was made.
《Black Tightening》
◎: There is no whiteness caused by external light, and the display is very black (pass)
○: Display with no blackening due to external light and black (pass)
△: Display with a feeling of whiteness due to external light and reduced black tightening (failed)
×: Display of strong whiteness caused by external light and no black tightening (failed)
[Reflection of fluorescent light]
○: I don't mind the reflection of fluorescent lights (pass)
X: Reflection of fluorescent light is a major problem (failed)
<< Bokeh of display image >> ~ Due to the effect of internal haze 5: Display image is very clear (pass)
4.5: intermediate between 4 and 5. Display image is clear (pass)
4: Display image is very clear (pass)
3.5: intermediate between 3 and 4. Display image is clear (pass)
3: Display image is clear (pass)
2: Display image is slightly blurred (failed)
1: The display image is blurred and has a problem (failed)

  The present invention will be described in the following examples, but the present invention is not limited thereto.

(Coating of antiglare hard coat layer)
(Example sample 1)
50 parts by mass of a commercially available ultraviolet curable resin (PETA, Nippon Kayaku, refractive index: 1.51), 2 parts by mass of a photopolymerization initiator (manufactured by Ciba Geigy, trade name: Irgacure 184), and an average particle size of 3. 1 part by mass of 5 μm acrylic-styrene beads (manufactured by Soken Chemical, refractive index: 1.55), 6 parts by mass of styrene beads (manufactured by Soken Chemical, refractive index: 1.60) having an average particle diameter of 3.5 μm, Using these as a solvent, an antiglare hard coat layer coating solution was prepared by mixing with toluene / methyl isobutyl ketone / cyclohexanone = 25/25/25 parts by mass. This coating solution was applied on a triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd., trade name: TD-80U, thickness: 80 μm), dried at 70 ° C. for 1 minute, and then irradiated with ultraviolet rays (100 mJ / cm ² ). Then, an anti-glare hard coat layer having a thickness of about 5 μm was applied.

(Preparation of sol solution)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. After that, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution. The mass average molecular weight was 1800, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. The condensation rate α calculated from 29Si-NMR measurement was 0.88. Further, from the gas chromatography analysis, no acryloxypropyltrimethoxysilane as a raw material remained.

(Preparation of coating solution 1 for low refractive index layer)
Fluoropolymer A (6%) 13.0g
MEK-ST-L (30%) 1.0 g
0.5g of the above sol solution
MEK 5.0g
Cyclohexanone 0.5g

  The solution was stirred and then filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution for a low refractive index layer.

The compounds used are shown below.
Fluoropolymer A: 80 g of fluorinated polymer described in JP-A No. 11-189621, Example 1, Cymel 303 20 g as a curing agent (Nippon Cytec Industries Co., Ltd., Catalyst 4050 2.0 g as a curing catalyst (Japan) Cytec Industries Co., Ltd. dissolved in MEK to 6% [refractive index 1.44, solid content concentration 6%]
MEK-ST-L: Colloidal silica dispersion [MEK-ST particle size difference, average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.]
KBM-5103: Silane coupling agent (acryloxypropyltrimethoxysilane) [manufactured by Shin-Etsu Chemical Co., Ltd.]

(Coating of low refractive index layer)
The triacetylcellulose film coated with the hard coat layer is unwound again, and the low refractive index layer coating solution is a micro gravure roll having a gravure pattern of 200 lines / inch and a depth of 30 μm, and a doctor blade. , Coated at a transfer speed of 20 m / min, dried at 120 ° C. for 75 seconds, further dried for 10 minutes, and then air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) at 240 W / cm under a nitrogen purge. ) Was irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 240 mJ / cm ² to form a low refractive index layer having a thickness of 100 nm, and wound to obtain Example Sample 1. The refractive index of the low refractive index layer was 1.43.

  Samples prepared in exactly the same manner as Example Sample 1 except that the formulation is changed as shown in Table 1 are referred to as Examples 2 to 21 samples and Comparative Examples 1 to 4 samples. In Example Samples 19 to 21, the styrene-acrylic particles used in Example Sample 1 were removed, and the styrene particles were formed into amorphous silica particles (silica fine particle aggregates on the order of several tens of nanometers with a secondary average particle diameter. Was changed to 3 μm).

    Whether the average value A (%) of the 5 ° regular reflectance of the obtained antireflection film, the average value B (%) of the integrated reflectance, the surface roughness Ra, and the requirements of (Equation 1) of the present invention are satisfied. (Whether (BA) / Ra is less than 4), internal haze, pencil hardness, and the performance of the above 6- (6) liquid crystal display device. The results are also shown in Table 1. The black tightening evaluation “−” in Comparative Examples 3 and 4 means that black tightening has not been evaluated.

Table 1 shows the following.
(1) An antireflection film in which Ra is 0.03 μm or more and the difference (B−A) between integrated reflectance (B) and 5 ° regular reflectance (A) is lower than 4 times Ra is excellent. It is more preferable that it is lower than 3 times Ra.
(2) The internal haze is preferably less than 36%, more preferably less than 25%, still more preferably less than 15%, still more preferably less than 5%, and most preferably less than 1%. The blur is also reduced, and a very suitable antireflection film can be provided.
(3) From the viewpoint of film toughness (pencil hardness), the thickness of the hard coat layer is preferably 5 μm or more, more preferably 8 μm or more (4H or more), and further preferably 20 μm or more (5H or more). However, increasing the thickness to 40 μm is not preferable in terms of brittleness and handling properties, and the upper limit is preferably set to about 35 μm.

  Moreover, with respect to each of the example samples 8 to 9 and 19 to 21, the example samples 8 to 9 and 19 to 19 to 19 except that the low refractive index layer coating solution 1 is changed to the following low refractive index layer coating solution 2 Samples produced in exactly the same manner as Example 21 were designated as Example Samples 22 to 23 and 24-26, and the refractive index of the low refractive index layer was further reduced (refractive index = 1.38), so the reflectivity itself was The image display device with an antireflection film was obtained, which is low and further suppresses the reflection of a fluorescent lamp.

Composition of coating liquid 2 for low refractive index layer DPHA 1.5 g
FP-1 (2.0%) 5.5g
Hollow silica (18.2%) 20.0g
RMS-033 0.7g
Irgacure 907 0.2g
Sol solution 6.0g
MEK 305.0g
Cyclohexanone 9.0g

The compounds used are shown below.
DPHA: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd.]
FP-1: Fluorine-based surface modifier (dissolved to 2.0% by mass by dissolving the exemplified compound FP-1 in the text with MEK)
Hollow silica: Hollow silica sol [CS-60 IPA, refractive index 1.31, average particle size 60 nm, shell thickness 10 nm, solid content concentration 18.2%, manufactured by Catalyst Kasei Kogyo Co., Ltd.] was subjected to surface modification with KBM-5103. Surface modification rate vs. 30% by mass of silica
RMS-033: Reactive silicone [manufactured by Gelest Co., Ltd.]
・ Irgacure 907: Photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd.]

  Further, Example Samples 8 to 9 and 19 to 21 are the same as Example Samples 8 to 9 and 19 to 21, except that the low refractive index layer coating solution 1 is changed to the following low refractive index layer coating solution 3. Samples produced in exactly the same manner as Example 21 were designated as Example Samples 27 to 28 and 29 to 31, and the refractive index of the low refractive index layer was further reduced (refractive index = 1.35), so the reflectance itself. The image display device with an antireflection film was further improved, and the reflection of fluorescent light was greatly suppressed.

Composition of coating solution 3 for low refractive index layer Fluoropolymer B (6%) 25.0 g
Hollow silica (18.2%) 20.0g
RMS-033 0.7g
Irgacure 907 0.2g
MEK 100.0g
Cyclohexanone 3.0g
The compounds used are shown below.
Fluoropolymer B: Ethylene unsaturated group-containing fluoropolymer (fluorine polymer (A-1) described in Production Example 3 of JP-A-2005-89536) diluted with MIBK and adjusted to 6.0% by mass ( Refractive index 1.35)

In addition to 32 inches, the samples were pasted on 23-inch, 26-inch, and 42-inch TVs, respectively, and the evaluation conditions (the liquid crystal display device was set to black display in a 1000 lux bright room). As a result of evaluation by visual evaluation and determination, the effect of the present invention was confirmed at any size, but the effect of the present invention was particularly noticeable on a TV of 32 inches or more. This can be said to be due to the fact that the black size improvement of the present invention has become more effective because the screen size becomes larger and it becomes more susceptible to the influence of ambient light.
This TV size result was confirmed in the same manner in other liquid crystal modes (TN, VA, OCB, ECB).

It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is a schematic sectional drawing which shows typically preferable embodiment of the film of this invention. It is sectional drawing of the coater 10 using the slot die 13 which implemented this invention. (A) shows the cross-sectional shape of the slot die 13 of the present invention, and (B) shows the cross-sectional shape of the conventional slot die 30. It is a perspective view which shows the slot die 13 of the application | coating process which implemented this invention, and its periphery. It is sectional drawing which shows the pressure reduction chamber 40 and the web W which are adjoining. (The back plate 40a is integrated with the main body of the chamber 40) It is a schematic diagram which shows the relationship between the hard-coat layer and particle | grains of the antireflection film of this invention. (When the thickness of the hard coat layer containing particles is smaller than the particle size) It is a schematic diagram which shows the relationship between the hard-coat layer and particle | grains of the antireflection film of this invention. (When the thickness of the hard coat layer containing particles is larger than the particle size) It is a schematic diagram which shows the relationship between the hard-coat layer and particle | grains of the antireflection film of this invention. (When the hard coat layer containing particles is further overcoated with a hard coat layer)

Explanation of symbols

(1) Support (2) Hard coat layer (3) Medium refractive index layer (4) High refractive index layer (5) Low refractive index layer 10 Coater 11 Backup roll W Web 13 Slot die 14 Coating liquid 14a Bead 14b Coating film 15 Pocket 16 Slot 16a Slot opening 17 Tip lip 18 Land 18a Upstream lip land 18b Downstream lip land I Land length of _UP upstream lip land 18a _LO Land length of downstream lip land 18b LO Over bit length (Difference in distance between the downstream lip land 18b and the web W of the upstream lip land 18a)
A gap between the _GL tip lip 17 and the web W (a gap between the downstream lip land 18b and the web W) 30 Conventional slot die 31a Upstream lip land 31b Downstream lip land 32 Pocket 33 Slot 40 Decompression chamber 40a Back plate 40b Side plate the gap between the gap _{G S} side plate 40b and the web W between 40c screws _{G B} back plate 40a and the web W

Claims (6)

In the antireflection film having at least one hard coat layer on the transparent support and a low refractive index layer having a refractive index of 1.47 or less as the outermost layer, the centerline average roughness Ra of the antireflection film is 0.03 μm. An antireflection film satisfying the relationship of the following formula 1 when the average value of 5 ° regular reflectance in the wavelength region of 450 nm to 650 nm is A and the average value of integrated reflectance is B.
(Formula 1) B-A <4 · Ra
Ra: Centerline average roughness (μm)   The antireflection film according to claim 1, wherein the internal haze of the antireflection film is less than 36%.   The antireflection film according to claim 1 or 2, wherein the thickness of the hard coat layer is 5 µm or more and 35 µm or less.   The polarizing plate which used the antireflection film in any one of Claims 1-3 for at least one of the two protective films of a polarizing film.   The image display apparatus which used the antireflection film in any one of Claims 1-3, or the polarizing plate of Claim 4 for the outermost surface of a display.   The image display device according to claim 5, wherein the image display device is a TV of 32 inches or more.

Images