JP2010085760A - Anti-glare film, polarizing plate, and image display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anti-glare film which has excellent abrasion resistance, anti-glare property and visibility in a bright room and is excellent from the view point of coating unevenness. <P>SOLUTION: The anti-glare film has an anti-glare layer having unevenness on the surface of a transparent plastic film base material and an abrasion resistant layer on the outermost surface of the anti-glare layer. The average film thickness of the abrasion resistant layer is 0.03-0.4 μm and the abrasion resistant layer is a cured material of a composition containing following (A), (B) and (C) components. The (A) component is an inorganic particles composed essentially of silicon oxide having 1-300 nm average particle diameter, the (B) component is an ionization radiation curing resin and the (C) component is a cross-linkable high molecular thickener. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

  Antiglare films with an antiglare hard coat layer laminated on a transparent plastic film substrate are like liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode ray tube display devices (CRT). In various pixel display devices, they are disposed on the surface of a display in order to prevent a decrease in contrast due to reflection of external light or reflection of an image due to surface scattering.

  In recent years, with the price reduction of liquid crystal televisions and the like, image display devices equipped with such an antiglare film have been widely used. In connection with this, the scene where the anti-glare film mounted is exposed to various environments with the image display apparatus is increasing. In particular, it is handled like a CRT television whose surface is glass, and there is an increased risk of scratching the surface of the liquid crystal display device. Therefore, the antiglare film disposed on the outermost surface of the liquid crystal display device is required to have high physical strength (such as scratch resistance) in addition to the high visibility improving effect that has been conventionally required.

  In order to obtain high physical strength, a hard coating layer with a film thickness of 10 μm or more is laminated on a cellulose acylate film by applying a curable composition containing a photocurable resin and an organic solvent, drying, and photocuring. An antireflection film has been proposed (see, for example, Patent Document 1).

  Moreover, a film thickness is 15-35 micrometers by apply | coating, drying, and photocuring the curable composition containing the resin particle of 6-15 micrometers of average particle diameters, a curable resin, and the organic solvent on a cellulose acylate film. An antiglare film having a high surface hardness obtained by laminating an antiglare layer has been proposed (see, for example, Patent Document 2).

  The anti-glare layer having a large film thickness is effective for preventing scratches generated by the force applied perpendicularly to the surface of the display screen, but not effective for scratches generated by the force parallel to the surface. .

  Moreover, the method of coating the thin film containing a silica particle on the layer which has a fine unevenness | corrugation on the surface is disclosed (for example, refer patent document 3). However, since this method contains silica particles of 1 μm or more in the thin film layer, surface scattering is strong, and whitishness may appear strong when observed in a bright room.

  On the other hand, in order to improve the film thickness uniformity without causing problems such as coating unevenness, it is possible to adjust the viscosity of the coating solution by adding a polymer compound to the hard coat layer or antiglare layer. Generally known (see, for example, Patent Document 4). However, when coexisting with silica particles, simple addition of a polymer compound causes white haze-like surface unevenness locally, and is visible in a relatively bright bright room environment where a solar light source is inserted. In some cases, white haze-like surface unevenness may become apparent.

  Furthermore, an antiglare film is disclosed in which a fine particle-containing cured resin layer containing inorganic or organic fine particles and a clear cured resin layer not containing fine particles are laminated in this order on a plastic film substrate (see, for example, Patent Document 5). ). However, further improvements in surface scratch resistance have been desired.

  On the other hand, an antiglare film in which an antiglare layer and a low refractive index layer containing a fluorine binder are laminated in this order on a plastic film substrate is generally known (for example, see Patent Document 6). However, generally, a fluorine binder has a weak cohesive force, and an antiglare film in which such a fluorine binder layer is laminated on the outermost surface has low scratch resistance, and an improvement thereof has been desired.

JP 2003-227902 A JP 2007-041533 A JP-A-7-290652 JP 2006-154770 A JP-A-10-325901 Japanese Patent Laid-Open No. 11-305010

  The present invention is to solve the above-mentioned conventional problems, to provide an antiglare film excellent in scratch resistance, antiglare property, visibility in a bright room, and excellent in terms of coating unevenness, An object of the present invention is to provide a polarizing plate including the antiglare film and an image display device having excellent scratch resistance and good visibility by including the polarizing plate.

As a result of intensive studies, the present inventors have found that the above problem can be solved by laminating a specific scratch-resistant layer on the antiglare property.
That is, the present inventors achieved the above object with the following configurations.

1. An antiglare film having an antiglare layer having irregularities on its surface on a transparent plastic film substrate, and having an abrasion resistant layer on the outermost surface of the antiglare layer, An antiglare film which is a cured product of a composition having an average film thickness of 0.03 to 0.4 μm and the scratch-resistant layer containing at least the following components (A), (B) and (C).
(A) Inorganic fine particles mainly composed of silicon oxide having an average particle diameter of 1 to 300 nm (B) Ionizing radiation curable resin (C) Crosslinkable polymer thickener 2. The crosslinkable polymer thickener is 2. The antiglare film as described in 1 above, which is a crosslinkable polymer containing a repeating unit represented by the following general formula (1).

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ¹ , or —CH ₂ COOR ¹ . Here, R ¹ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.
3. The antiglare film according to 2 above, wherein the (C) crosslinkable polymer thickener further comprises a repeating unit containing a group having an alicyclic structure in the side chain.
4. The antiglare film according to any one of the above 1 to 3, wherein the surface of the inorganic fine particles of the component (A) is surface-treated with a compound represented by the following general formula (2).
Formula _{^{(2) (R 10) m}} -Si (X) 4-m
(In the general formula (2), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3. .)
5. The antiglare film as described in any one of 1 to 4 above, wherein the scratch-resistant layer contains substantially no fluorine binder.
6. The antiglare film according to any one of 1 to 5 above, wherein a refractive index of the scratch-resistant layer is lower than a refractive index of the antiglare layer.
7. The antiglare film as described in any one of 1 to 6 above, wherein the antiglare layer contains at least one translucent resin and at least one light diffusing particle.
8. The antiglare film as described in 7 above, wherein the light diffusing particles have an average particle diameter of 5.5 to 15 μm and the antiglare layer has an average film thickness of 8 to 40 μm.
9. A polarizing plate having a polarizing film and protective films on both sides of the polarizing film, wherein at least one of the protective films is the antiglare film according to any one of 1 to 8 above.
10. An image display device having the antiglare film according to any one of 1 to 8 or the polarizing plate according to 9 above on an image display surface.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-glare film which is excellent in abrasion resistance, anti-glare property, and visibility in a bright room, and is excellent also in the viewpoint of the coating nonuniformity, and the polarizing plate containing this anti-glare film can be provided. . Further, by having the polarizing plate, it is possible to provide an image display device having excellent scratch resistance and good visibility.

  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.

The present invention is an antiglare film having an antiglare layer having irregularities on its surface on a transparent plastic film substrate, and having an scratch resistant layer on the outermost surface of the antiglare layer, the scratch resistant The average film thickness of the layer is 0.03 to 0.4 μm, and the anti-glare layer is a cured product of a composition containing at least the following components (A), (B), and (C): Related to film.
(A) Inorganic fine particles mainly composed of silicon oxide having an average particle diameter of 1 to 300 nm (B) Ionizing radiation curable resin (C) Crosslinkable polymer thickener

<Layer structure of antiglare film>
Regarding the layer structure of the present invention, at least one antiglare layer and an abrasion resistant layer on the outermost surface are provided. The antiglare layer may have a multilayer structure. Further, another functional layer may be laminated between the base film and the antiglare layer and / or between the antiglare layer and the scratch resistant layer. Examples of other functional layers include a hard coat layer, an antistatic layer, and an interference unevenness preventing layer.
The scratch-resistant layer may also function as another layer. Examples of these layers include an antireflection layer, a low refractive index layer, an antifouling layer, and an antistatic layer.

  In the present invention, it is preferable that the scratch-resistant layer also serves as a low-refractive index layer (antireflection layer) from the viewpoint of lowering the reflectance. In this case, a high-refractive index layer between the scratch-resistant layer and the antiglare layer, Alternatively, a configuration including a medium refractive index layer and a high refractive index layer is also a preferable embodiment.

The example of the preferable layer structure of the anti-glare film of this invention is shown below. In the following configuration, the base film refers to a support composed of a film.
・ Base film / Anti-glare layer / Abrasion resistant layer ・ Base film / Antistatic layer / Anti-glare layer / Abrasion resistant layer ・ Base film / Anti-glare layer / Abrasion resistant layer (also serves as a low refractive index layer) )
Base film / antiglare layer / antistatic layer / scratch resistant layerBase film / hard coat layer / antiglare layer / scratch resistant layerBase film / hard coat layer / antiglare layer / antistatic layer / Scratch resistant layer -Base film / hard coat layer / antistatic layer / antiglare layer / scratch resistant layer-Base film / antiglare layer / high refractive index layer / scratch resistant layer-Base film / anti-scratch Dazzle layer / Medium refractive index layer / High refractive index layer / Abrasion resistant layer Antistatic layer / Base film / Anti-glare layer / Medium refractive index layer / High refractive index layer / Abrasion resistant layer Prevention layer / Anti-glare layer / Medium refractive index layer / High refractive index layer / Abrasion resistant layer Antistatic layer / Base film / Anti-glare layer / High refractive index layer / Low refractive index layer / High refractive index layer / Anti-resistant layer Abrasion layer

<Abrasion resistant layer>
The average film thickness of the scratch resistant layer is 0.03 μm to 0.4 μm, more preferably 0.05 μm to 0.3 μm, and still more preferably 0.05 μm to 0.2 μm. By setting the film thickness of the scratch-resistant layer within this range, sufficient scratch resistance can be obtained while preventing uneven coating.

  The refractive index of the scratch-resistant layer is preferably lower than the refractive index of the antiglare layer, preferably 1.40 to 1.52, more preferably 1.42 to 1.52. More preferably, it is from 45 to 1.51. By setting the refractive index of the scratch-resistant layer within this range, it can also function as a low-reflectance layer, the reflectance can be suppressed, and reflection of external light can be further suppressed. Further, by limiting the lower limit to this range, scratches are not noticeable even when the scratch-resistant layer is peeled off.

  While the refractive index of the scratch-resistant layer is in the above range, the difference from the refractive index of the adjacent lower layer is preferably 0.02 to 0.10. When there is a difference in refractive index, the reflectance of the surface can be further suppressed by utilizing the light interference effect by setting the film thickness to 0.08 μm to 0.12 μm. Further, by limiting the upper limit of the refractive index difference to this range, the scratches are not noticeable even when the scratch-resistant layer is peeled off.

The scratch-resistant layer of the present invention is a curable composition containing at least the following components (A), (B), and (C) (a composition for forming a scratch-resistant layer; (Also referred to as a composition).
(A) Inorganic fine particles mainly composed of silicon oxide having an average particle size of 1 to 300 nm (B) Ionizing radiation curable resin (C) Crosslinkable polymer thickener The following is a description of the curable composition of the present invention. Each component will be described in detail.

<(C) Crosslinkable polymer thickener>
The composition for forming a scratch-resistant layer of the present invention contains a crosslinkable polymer thickener as component (C).
The thickener here means that the viscosity of the liquid increases by adding it, and the increase in the viscosity of the coating liquid by addition is preferably 0.05 to 50 mPa · s, More preferably, it is 0.10-20 mPa * s, Most preferably, it is 0.10-10 mPa * s. The addition amount of the crosslinkable polymer thickener of the present invention is preferably 0.2 to 10 mass% per solid content of the scratch-resistant layer from the viewpoint of increasing the viscosity, and 0.5 to 7 mass from the viewpoint of the film thickness. % Is more preferable, and 1 to 5% by mass is particularly preferable.

  The crosslinkable polymer thickener of the present invention is a function as a viscosity modifier of a coating composition for controlling coating leveling and a dispersant for adjusting the aggregation stability of silica particles in the drying process. It refers to a compound having a function and a function that is fixed in the film at the time of a cured film after coating and suppresses uneven surface distribution.

  A preferred crosslinkable polymer thickener is a crosslinkable polymer containing a repeating unit represented by the following general formula (1). In another preferred embodiment, the polymer contains a crosslinkable polymer containing a repeating unit represented by the following general formula (1) and a compound containing two or more ethylenically unsaturated groups in the same molecule. And a curable composition that cures by polymerizing both the ring-opening polymerizable group and the ethylenically unsaturated group.

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ¹ , or —CH ₂ COOR ¹ . R ¹ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.

(Crosslinkable polymer containing a repeating unit represented by the general formula (1))
The crosslinkable polymer containing the repeating unit represented by the general formula (1) will be described in detail. In the general formula (1), a ¹ and a ² represent a hydrogen atom, an aliphatic group, preferably an alkyl group having 1 to 4 carbon atoms, —COOR ¹ , or —CH ₂ COOR ¹ .
R ¹ represents a hydrocarbon group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
L is a single bond or a divalent linking group, preferably a single bond, -O-, an alkylene group, an arylene group, * -COO-, * -CONH-, * -OCO-, or * -NHCO-. (Here, * means linking to the main chain on the * side).
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group. The monovalent group containing a ring-opening polymerizable group is a monovalent group having a ring structure in which ring-opening polymerization proceeds by the action of a cation, anion, radical, etc. Among them, cationic ring-opening polymerization of a heterocyclic compound Is preferred. Preferred monovalent groups containing a ring-opening polymerizable group include a vinyloxy group or a monovalent group containing an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a lactone ring, a carbonate ring, an oxazoline ring or the like. Among them, a monovalent group including an epoxy ring, an oxetane ring and an oxazoline ring is particularly preferable, and a monovalent group including an epoxy ring is most preferable.
When P represents an ethylenically unsaturated group, preferred ethylenically unsaturated groups include acryloyl group, methacryloyl group, styryl group, and vinyloxycarbonyl group.
These groups may further have a substituent.

The crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention is preferably synthesized simply by polymerizing a corresponding monomer. In this case, radical polymerization is the simplest and preferable as the polymerization reaction.
Although the preferable specific example of the repeating unit represented by General formula (1) below is shown, this invention is not limited to these.

  Moreover, as a more preferable example among the repeating units represented by the general formula (1) of the present invention, P is preferably a monovalent group including an ethylenically unsaturated group, and includes an acryloyl group, a methacryloyl group, and a styryl group. A monovalent group is more preferable, and a monovalent group including an acryloyl group is more preferable. Although the preferable specific example of the repeating unit represented by General formula (1) below is shown, this invention is not limited to these.

  The crosslinkable polymer containing a repeating unit represented by the general formula (1) of the present invention may be a copolymer containing a repeating unit other than the general formula (1). In particular, when it is desired to control the Tg or hydrophilicity / hydrophobicity of the crosslinkable polymer, or to control the content of the ring-opening polymerizable group of the crosslinkable polymer, it can be a copolymer containing a repeating unit other than the general formula (1). . As a method for introducing the repeating unit other than the general formula (1), a method of introducing the corresponding monomer by copolymerization is preferable.

When the repeating unit other than the general formula (1) is introduced by copolymerizing a corresponding vinyl monomer, the monomer preferably used is derived from acrylic acid or α-alkyl acrylic acid (for example, methacrylic acid). Esters or amides (for example, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, acrylamide, 2-acrylamide-2) -Methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetone acrylamide, acryloylmorpholine, N-methylol acrylamide, N-methylol methacrylamide, alkyl ester (Meth) acrylate (as alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), 2-hydroxyethyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-methyl-2-nitropropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxymethoxyethyl (meth) Acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, octafluoropentyl (meth) acrylate, cyclohexyl (Meth) acrylate, cyclopentyl (meth) acrylate, 2-isobornyl (meth) acrylate, 2-norbornylmethyl (meth) acrylate, 5-norbornen-2-ylmethyl (meth) acrylate, 3-methyl-2-nor Bornylmethyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.), acrylic acid or α-alkyl acrylic acid (acrylic acid) Methacrylic acid, itaconic acid, etc.), vinyl esters (eg vinyl acetate), esters derived from maleic acid or fumaric acid (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleimides (N-Fe Lumaleimide, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (eg butadiene, cyclopentadiene, isoprene), aromatic vinyl compounds (eg styrene, p-chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylpyrrolidone, N-vinyloxazolidone, N-vinylsuccinimide, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide , N-vinyl-N-methylacetamide, 1-vinylimidazole, 4-vinylpyridine, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene chlora De, vinyl alkyl ethers (e.g. methyl vinyl ether), ethylene, propylene, 1-butene, isobutene and the like. Two or more of these vinyl monomers may be used in combination. Vinyl monomers other than these are listed in Research Disclosure No. Those described in 19551 (1980, July) can be used.
In the present invention, esters derived from acrylic acid or methacrylic acid, amides, and aromatic vinyl compounds are particularly preferably used vinyl monomers.

  As the repeating unit other than the general formula (1), a repeating unit having a ring-opening polymerizable group or a reactive group other than the ethylenically unsaturated group can also be introduced. In particular, if you want to increase the hardness of the hard coat layer, or if you want to improve the adhesion between layers when using another functional layer on the substrate or hard coat, a copolymer containing reactive groups other than ring-opening polymerizable groups The method is preferable. As a method for introducing a repeating unit having a reactive group other than the ring-opening polymerizable group, a method of copolymerizing a corresponding vinyl monomer (hereinafter referred to as “reactive monomer”) is simple and preferable.

  Although the preferable specific example of a reactive monomer is shown below, this invention is not limited to these.

<Preferable specific example of reactive monomer>
Hydroxyl group-containing vinyl monomers (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, allyl alcohol, hydroxypropyl acrylate, hydroxypropyl methacrylate, etc.), isocyanate group-containing vinyl monomers (eg, isocyanatoethyl acrylate, isocyanatoethyl methacrylate, etc.), N -Methylol group-containing vinyl monomers (for example, N-methylol acrylamide, N-methylol methacrylamide, etc.), carboxyl group-containing vinyl monomers (for example, acrylic acid, methacrylic acid, itaconic acid, carboxyethyl acrylate, vinyl benzoate), alkyl halides Vinyl monomers (eg chloromethylstyrene, 2-hydroxy-3-chloropropyl methacrylate), acids Water-containing vinyl monomers (eg maleic anhydride), formyl group-containing vinyl monomers (eg acrolein, methacrolein), sulfinic acid group-containing vinyl monomers (eg potassium styrenesulfinate), active methylene-containing vinyl monomers (eg acetoacetoxyethyl) Methacrylate), amino group-containing monomers (for example, allylamine), alkoxysilyl group-containing monomers (for example, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltrimethoxysilane), and the like.

  In the crosslinkable polymer containing the repeating unit represented by the general formula (1) of the present invention, the proportion of the repeating unit represented by the general formula (1) is 25% by mass or more and 100% by mass or less, preferably 50%. It is 100 mass% or more. When the repeating unit other than the general formula (1) does not have a crosslinking reactive group, the hardness decreases if the content is too large, and when it has a crosslinking reactive group, the hardness may be maintained, but curing shrinkage may occur. May become large and brittleness may deteriorate. In particular, when using a copolymer of an alkoxysilyl group-containing monomer (for example, methacryloyloxypropyltrimethoxysilane) and a repeating unit represented by the general formula (1), the molecular weight decreases such as dehydration and dealcoholization during the crosslinking reaction. When accompanied, curing shrinkage tends to increase. General formula (1) in the case of introducing a repeating unit having a crosslinking reactive group that undergoes a crosslinking reaction with a decrease in molecular weight into a crosslinkable polymer containing a repeating unit represented by the general formula (1) of the present invention. ) Is preferably 70% by mass or more and 99% by mass or less, more preferably 80% by mass or more and 99% by mass or less, and particularly preferably 90% by mass or more and 99% by mass or less.

  The preferred molecular weight range of the crosslinkable polymer thickener (preferably the crosslinkable polymer containing the repeating unit represented by the general formula (1)) is from 1,000 to 1,000,000, more preferably from 3,000 to 200,000 in terms of mass average molecular weight. It is as follows. Most preferably, it is 5000 or more and 100,000 or less. In addition, the said mass mean molecular weight is measured by GPC method and is a polystyrene conversion value.

The crosslinkable polymer in the crosslinkable polymer thickener of the present invention is replaced with the substituent P in the general formula (1) in addition to the repeating unit (z mol%) represented by the general formula (1). A repeating unit (x mol%) introduced with a group X having an alicyclic structure and a repeating unit (y mol%) introduced with a group Y having an acidic group in place of the substituent P in the general formula (1) Is preferred. Furthermore, it may contain a repeating unit (1 mol%) in which another group R is introduced instead of the substituent P in the general formula (1). In addition, a plurality of groups represented by the general formula (1) and a group into which X, Y, and R are introduced may be combined.
When the group X having an alicyclic structure is introduced, the dispersibility of the silica particles during coating and drying is improved, and white haze can be suppressed. The group Y having an acidic group is introduced from the viewpoint of compound synthesis.
In the crosslinkable polymer containing the substituent P and the repeating unit in which the substituent P is replaced with X, Y, or R, the repeating unit z mol% represented by the general formula (1) is 25% by mass or more and 100% or less. Preferably, 50% by mass or more and 100% or less is more preferable.
The content x mol% of the repeating unit having the substituent X in the crosslinkable polymer is preferably 10 mol% to 70 mol%, more preferably 20 mol% to 60 mol%, from the viewpoint of white haze suppression. Further, the content y mol% of the repeating unit having the substituent Y is preferably 10 mol% to 50 mol%, more preferably 20 mol% to 40 mol%, and the content l of the repeating unit having the substituent R is l. The mol% is preferably 0 mol% to 15 mol%, more preferably 1 mol% to 5 mol%.

(Group having alicyclic structure in side chain: X)
Next, the group having an alicyclic structure represents an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, Examples thereof include an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, and a tricyclopentanyl group. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, a tricyclopentenyl group, and the like. Is preferred.

  Examples of the monomer containing a group having an alicyclic structure in the side chain include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like (meth) acrylates. , Vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Next, specific examples of the monomer containing a group having an alicyclic structure in the side chain include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-1-adamantyl, (meth) acrylic acid-3-ethyladamantyl, (meth) acrylic acid-3-methyl-5-ethyl -1-adamantyl, (meth) acrylic acid-3,5,8-triethyl-1-adamantyl, (meth) acrylic acid-3,5-dimethyl-8-ethyl-1-adamantyl, (meth) acrylic acid 2- Methyl-2-adamantyl, (meth) acrylic acid 2-ethyl-2-adamantyl, (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid Kutahydro-4,7-mentanoinden-5-yl, (meth) acrylate octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylate-1-menthyl, (meth) acrylate tricyclo Decyl, (meth) acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo [ 4.1.0] heptyl, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, (meth) And cyclohexyl acrylate. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 1-menthyl, (meth) acrylic acid tricyclodecyl, etc. are preferable, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, ( Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

  Furthermore, specific examples of the monomer containing a group having an alicyclic structure in the side chain include compounds represented by the following general formula (3) or (4). Here, in the general formulas (3) and (4), x represents 1 or 2, and R represents hydrogen or a methyl group. m and n each independently represent 0-15. Among general formulas (3) and (4), x = 1 or 2, m = 0 to 8, and n = 0 to 4 are preferable, and m = 1 to 4 and n = 0 to 2 are more preferable. Preferable specific examples of the compound represented by the general formula (3) or (4) include the following compounds D-1 to D-5 and T-1 to T-8.

As the monomer containing a group having an alicyclic structure in the side chain, an appropriately produced monomer may be used, or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A , H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M and the like. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

(Group having acidic group in side chain: Y)
There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. The content is preferably 5% or more, and more preferably 10% or more.

  The monomer having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like (meth) Acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer having an acidic group in the side chain can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate. Esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone A mono (meth) acrylate etc. are mentioned. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  As said commercial item, Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB-1, NK ester CBX-1, manufactured by Kyoeisha Oil Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

(Other monomer: R)
The other monomer is not particularly limited, and examples thereof include (meth) acrylic acid ester having no alicyclic structure, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl group and the like. And the like.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  The group having an alicyclic structure in the side chain of the general formula (1) (z mol%) of the present invention: X (x mol%), the group having an acidic group: Y (y mol%), and other groups ( Specific examples of the compound containing R) (1 mol%) include compounds selected from the following groups.

(Compounds containing two or more ethylenically unsaturated groups in the same molecule)
A compound containing two or more ethylenically unsaturated groups in the same molecule that can be used in the present invention will be described. Preferred types of ethylenically unsaturated groups are allyloyl group, methacryloyl group, styryl group, and vinyl ether group, particularly preferably methacryloyl group or acryloyl group, and particularly preferably acryloyl group. Although the compound containing an ethylenically unsaturated group should just have two or more ethylenically unsaturated groups in a molecule | numerator, More preferably, it is three or more. Among them, a compound having an acryloyl group is preferable, and a compound called a polyfunctional acrylate monomer having 2 to 6 acrylate groups in the molecule or a molecule called urethane acrylate, polyester acrylate or epoxy acrylate. An oligomer having several acrylate groups and a molecular weight of several hundred to several thousand can be preferably used. Specifically, the same thing as the polyfunctional monomer as described in <Binder> which comprises the abrasion-resistant layer mentioned later is mentioned.
These polymerizable compounds are preferably used in combination with a polymerization initiator, and specific examples thereof include those described in <Photopolymerization initiator> described later.

<Inorganic fine particles mainly composed of silicon oxide of scratch-resistant layer>
The curable composition of the present invention contains inorganic fine particles mainly composed of silicon oxide having an average particle diameter of 1 to 300 nm as component (A). In the present invention, inorganic fine particles mainly composed of silicon oxide mean inorganic fine particles containing 50% by mass or more of silicon oxide. It is preferable to contain 70 mass% or more of silicon oxide, and it is especially preferable to contain 90 mass% or more.

  The content of the inorganic fine particles is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and further preferably 20 to 50% by mass based on the solid content of the scratch-resistant layer from the viewpoint of imparting scratch resistance.

  The inorganic fine particles of the present invention can be used by modifying the surface and dispersing them in an organic solvent. From the viewpoint of compatibility with other components and dispersibility, the dispersion medium is preferably an organic solvent, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene, Aromatic hydrocarbons such as toluene and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

The number average particle diameter of the inorganic fine particles of the present invention is 1 nm to 300 nm, preferably 3 nm to 150 nm, and most preferably 10 nm to 100 nm. By setting it as the said range, coexistence with abrasion resistance and black tightening can be aimed at. The number average particle diameter can be determined as an average of 500 particles in terms of a sphere equivalent by observing inorganic fine particles with a transmission electron microscope. The number average particle diameter is preferably a particle having monodispersibility.
Various surfactants and amines may be added to improve the dispersibility of the particles.

  In the present invention, it is preferable to use inorganic fine particles having at least two different number average particle diameters. It is more preferable to use inorganic fine particles having two kinds of number average particle diameters of 5 nm to 20 nm and number average particle diameters of 20 nm to 100 nm. At this time, the inorganic fine particles having a number average particle diameter of 5 nm to 20 nm are the main components (51% by mass to 90% by mass, preferably 60% by mass to 90% by mass, more preferably 70% by mass to 90% by mass. % Or less).

  Examples of products that are commercially available as silicon oxide fine particle dispersions (for example, silica particles) include colloidal silica, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., MA-ST-MS, IPA-ST, IPA-ST. -MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA -ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., Catalyst Chemical Industry Co., Ltd. Examples include hollow silica. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

The inorganic fine particles have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, preferably a spherical shape or a hollow shape. In order to lower the refractive index of the scratch-resistant layer, it is also preferable to use hollow silica fine particles. The specific surface area of the inorganic fine particles (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, more preferably 30 to 150 m ² / g, and most preferably 50 to 100 m ² / g. g.

<Surface treatment agent>
The surface treatment agent represented by the following general formula (2) that can be used for the surface treatment of the inorganic fine particles of the present invention will be described in detail.

Formula _{^{(2) (R 10) m}} -Si (X) 4-m

In the general formula (2), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl, decyl, hexadecyl and the like. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group. Examples of the hydrolyzable group include an alkoxy group (an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group), a halogen atom (for example, Cl, Br, I, etc.), and R ^2. COO groups (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO groups and C ₂ H ₅ COO groups), preferably alkoxy groups, particularly preferably. Is a methoxy group or an ethoxy group.
m represents an integer of 1 to 3. When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively. m is preferably 1 or 2, particularly preferably 1.
Moreover, the compound shown below as an example in case X is shown as a group which can be hydrolyzed is also preferable.

(R ¹⁰ ) ₃ —Si— (X) —Si— (R ¹⁰ ) ₃

Here, R ¹⁰ has the same meaning as R ¹⁰ above, and X represents a hydrolyzable group. Examples of X include -O- and -NH-.

The substituent contained in R ¹⁰ is not particularly limited, but is a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), hydroxyl group, mercapto group, carboxyl group, epoxy group, alkyl group (methyl group, ethyl group, i -Propyl group, propyl group, t-butyl group etc.), aryl group (phenyl group, naphthyl group etc.), aromatic heterocyclic group (furyl group, pyrazolyl group, pyridyl group etc.), alkoxy group (methoxy group, ethoxy group) , I-propoxy group, hexyloxy group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), arylthio group (phenylthio group, etc.), alkenyl group (vinyl group, 1-propenyl group) Etc.), acyloxy groups (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), alkoxycarbonyl groups (me Toxylcarbonyl group, ethoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), carbamoyl group (carbamoyl group, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-methyl-N-octylcarbamoyl group) Etc.), acylamino groups (acetylamino group, benzoylamino group, acrylamino group, methacrylamino group, etc.) and the like, and these substituents may be further substituted. In the present specification, even if a hydrogen atom is replaced by a single atom, it is treated as a substituent for convenience.
When there are a plurality of R ¹⁰ , at least one is preferably a substituted alkyl group or a substituted aryl group. Among these, the substituted alkyl group or substituted aryl group preferably further has a vinyl polymerizable group. In this case, the compound represented by the general formula (2) is a vinyl polymerizable compound represented by the following general formula (5). It can be expressed as an organosilane compound having a substituent.

In the general formula (5), R ³ 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. R ³ is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And methyl groups are particularly preferred.
Y represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

  L is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (for example, an ether group, an ester group, an amide group) inside. A substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon number 6 An arylene group of ˜20, an alkylene group having 3 to 10 carbon atoms having a linking group inside, an unsubstituted alkylene group, an unsubstituted arylene group, and an alkylene group having an ether linking group or an ester linking group inside are further included. An unsubstituted alkylene group and an alkylene group having an ether linking group or an ester linking group therein are 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.

n represents 0 or 1. When there are a plurality of Xs, the plurality of Xs may be the same or different. n is preferably 0.
R ¹⁰ has the same meaning as R ^{10 in} formula (2), preferably a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and more preferably an unsubstituted alkyl group or an unsubstituted aryl group.
X has the same meaning as X in formula (2), preferably a halogen, a hydroxyl group or an unsubstituted alkoxy group, more preferably a chlorine, a hydroxyl group or an unsubstituted alkoxy group having 1 to 6 carbon atoms, a hydroxyl group or a carbon number. 1-3 alkoxy groups are more preferable, and a methoxy group is particularly preferable.

  Two or more compounds of the general formula (2) may be used in combination. Specific examples of the compound represented by the general formula (2) are shown below, but the present invention is not limited thereto.

In addition, disiloxane-based and disilazane-based compounds can also be used as the surface treatment agent. For example, hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3 -Divinyltetramethyldisiloxane, hexaethyldisiloxane, 3-glycidoxypropylpentamethyldisiloxane, hexamethyldisilazane, hexaethyldisilazane and the like.
Among these specific examples, (M-1), (M-2) and the like are particularly preferable. Further, the compounds of A, B, and C described in Reference Example of Japanese Patent No. 3474330 are also preferable because of excellent dispersion stability. In the present invention, the amount of the organosilane compound represented by the general formula (2) is not particularly limited, but is preferably 1% by mass to 300% by mass, more preferably 3% by mass to 100% by mass, per inorganic fine particle. %, Most preferably 5% by mass to 50% by mass. It is preferably 1 to 300 mol%, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol% per normal concentration (Formol) based on hydroxyl groups on the surface of the inorganic oxide. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also increased during coating film formation. It is also preferable to use a plurality of types of organosilane compounds in combination, and a plurality of types of compounds can be added simultaneously, or the addition time can be shifted for reaction. Also, it is preferable to add a plurality of types of compounds after making them into partial condensates in advance because the reaction control is easy.

<Ionizing radiation curable resin (B)>
The curable composition of this invention contains the ionizing radiation curable resin which is (B) component. The ionizing radioactive resin is cured to become a binder for the scratch-resistant layer of the present invention.

<Binder>
The binder of the scratch-resistant layer of the present invention can form the ionizing radiation curable resin as the component (B) by a crosslinking reaction or a polymerization reaction using ionizing radiation.

  The curable composition of the present invention is obtained by applying a composition containing a polyfunctional monomer or polyfunctional oligomer as an ionizing radiation curable resin on a transparent substrate film, and having a polyfunctional monomer or polyfunctional oligomer having a polymerizable group. It can be formed by a crosslinking reaction or a polymerization reaction.

  Examples of the polymerizable group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

  It is preferable that the curable composition of this invention does not contain the component used as a fluorine-type binder. Fluorine-based binders generally have low cohesive strength and reduce scratch resistance.

  Specific examples of the polyfunctional monomer having a polymerizable group include (meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate; (Meth) acrylic diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate; pentaerythritol (Meth) acrylic acid diesters of polyhydric alcohols such as di (meth) acrylate; 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane, 2-2-2bis {4- (actyl Proxy-polypropoxy) phenyl} ethylene or propylene oxide adduct (meth) acrylic acid diesters such as propane; and the like.

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

Among the above, esters of polyhydric alcohol and (meth) acrylic acid are preferable, and polyfunctional monomers having three or more (meth) acryloyl groups in one molecule are more 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.

Two or more polyfunctional monomers may be used in combination.
Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation in the presence of a photo radical initiator. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.

  The content of the ionizing radiation curable resin (B) is preferably 10 to 85% by mass, more preferably 23 to 89% by mass, and further preferably 45 to 75% by mass based on the solid content of the scratch-resistant layer.

<Photopolymerization initiator>
Examples of the photo radical polymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides (JP-A No. 2001-139663, etc.), 2 , 3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfoniums, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins and the like.

  Examples of the acetophenones include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxy-dimethylphenylketone, 1-hydroxy-dimethyl-p-isopropylphenylketone, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-4-methylthio-2-morpholinopropiophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4-phenoxydichloroacetophenone, 4-t -Butyl-dichloroacetophenone.

Examples of the 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. included.
Examples of benzophenones include benzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone, 4,4'-dimethylaminobenzophenone (Michler 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”. Organic borates. For example, the compounds described in JP-A-2002-116539, paragraph numbers [0022] to [0027] can be mentioned.
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 thereof include organoboron transition metal coordination complexes such as ionic complexes with cationic dyes.

Examples of the phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
Examples of the 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 No. 2000-80068 are particularly preferable.
Examples of onium salts include aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts.

Specific examples of the active halogens include Wakabayashi et al., “Bull Chem. Soc. Japan”, 42, 2924 (1969), US Pat. No. 3,905,815, and JP-A-5-27830. No., M.C. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group: s-triazine compounds.
More 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.
These initiators may be used alone or in combination.

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

  The photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass and more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.

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

  The binder content of the curable compound, the photopolymerization initiator, and the photosensitizer is preferably 30 to 95% by mass, and preferably 40 to 90% by mass, based on the solid content of the curable composition. More preferably, it is especially preferable that it is 50-80 mass%.

<Anti-fouling agent>
In addition to the scratch-preventing effect of the scratch-resistant layer of the present invention, it is also a preferred embodiment that the scratch-resistant layer has antifouling properties. Therefore, such a function can be added by adding a polysiloxane-based or fluorine-based antifouling agent to the curable composition of the present invention. Among these, in the present invention, a polysiloxane antifouling agent is preferable, and a silicon antifouling agent having an unsaturated double bond group is particularly preferable.

  The addition amount of the antifouling agent is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and particularly preferably 0.1 to 5% by mass based on the total solids of the scratch-resistant layer.

  Examples of the polysiloxane antifouling agent having an unsaturated double bond group include a monomer having a siloxane group by a reaction such as polydimethylsiloxane and (meth) acrylic acid. Specific examples of the terminal (meth) acrylate siloxane compound include X-22-164A, X-22-164B, X-22-164C, X-22-2404, X-22-174D, X-22-8201, And X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd.).

<Organic solvent>
The curable composition for forming the scratch resistant layer preferably contains an organic solvent. From the viewpoint of compatibility with other components and dispersibility, for example, alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

0.5-30 mass% is preferable, as for the solid content density | concentration of a curable composition, 1-20 mass% is more preferable, and 2-10 mass% is especially preferable.
It is preferable that the scratch-resistant layer contains substantially no fluorine binder.

<Configuration of antiglare layer>
The antiglare layer in the present invention may be any layer as long as it has a fine uneven shape on the surface, but preferably contains at least one light transmissive resin and at least one light diffusing particle.

  The antiglare layer in the present invention preferably contains light diffusing particles having an average particle diameter of 2 μm to 20 μm. The light diffusing particles are preferably translucent particles having an average particle size of 5 μm to 15 μm, and more preferably translucent particles having an average particle size of 5.5 μm to 15 μm.

  As an aspect of the antiglare layer of the present invention, a coating liquid containing translucent particles having an average particle diameter of 5.5 μm to 15 μm, matrix forming components (such as monomers for binder) and an organic solvent is applied, dried and cured. Preferably, the layer is

  The coating solution for forming the antiglare layer includes, for example, main monomers for matrix-forming binders that are raw materials for a light-transmitting polymer formed by curing with ionizing radiation, the light-transmitting particles having the specific particle diameter, and a polymerization initiator. Preferably, it contains a polymer compound for adjusting the viscosity of the coating solution, an inorganic fine particle filler for curling reduction and refractive index adjustment, a coating aid and the like.

  The thickness of the antiglare layer is preferably 8 μm to 40 μm, more preferably 10 μm to 35 μm, and most preferably 11 μm to 25 μm. When the thickness is less than 8 μm, the surface irregularities become too large when the light-transmitting particles described below are used, and the black tightening deteriorates, and when it exceeds 40 μm, the surface irregularities become small and the antiglare property is insufficient.

<Translucent particles of antiglare layer>
The average particle size of the particles is preferably 5.5 μm to 15 μm, more preferably 6.0 μm to 12 μm, and even more preferably 6.0 μm to 10 μm.

In the present invention, the antiglare layer can be formed of one kind of translucent particle, but it is more preferably formed of two kinds of particles having the same average particle size and different refractive indexes. In the present invention, the translucent particles are dispersed in a coating solution for forming an antiglare layer and applied, dried and cured to form an antiglare layer. The average particle diameter of the translucent particles refers to the primary particle diameter regardless of whether two or more particles are present adjacent to each other in the coating film or independently. However, agglomerated inorganic particles having a primary particle size of about 0.1 μm are dispersed as secondary particles in the coating solution in a size that satisfies the particle size of the present application, and then applied to the secondary particles. Magnitude.
In this invention, it is excellent in stability of the surface shape after preserve | saving a coating liquid as the average particle diameter of particle | grains is said range. In addition, the screen is excellent in blackening and has an appropriate anti-glare property.

  In the present invention, in order to achieve excellent antiglare property and black tightening simultaneously, in addition to the above, the ratio (φ / t) of the average particle size φ of the translucent particles and the film thickness (t) of the antiglare layer is important. φ / t is preferably 0.3 to 0.7, and more preferably 0.35 to 0.65. Especially preferably, it is 0.4-0.6. If φ / t is too large, the surface roughness is strong and the appearance tends to deteriorate, and if it is too small, the black tightening tends to decrease.

  In the present invention, it is necessary to adjust the refractive index of the particles and the matrix in order to obtain the necessary internal scattering properties. The refractive index difference between at least one kind of particles and the matrix is preferably 0.02 to 0.5, more preferably 0.02 to 0.20, and most preferably 0.03 to 0.15. When two kinds of particles are included, the difference in refractive index between the particles is preferably 0.02 to 0.20, and more preferably 0.02 to 0.10.

  When two kinds of particles are included, it is also preferable that one has a refractive index lower than that of the matrix and one has a higher refractive index than that of the matrix. For example, particles having a high refractive index preferably have a refractive index of 1.54 to 1.70, more preferably 1.55 to 1.60, and particles having a low refractive index preferably have a refractive index of 1.44 to 1.53. More preferably, it is 1.46 to 1.52. Control of internal scattering and surface shape is facilitated by the difference in refractive index between the two types of particles. Further, the stability of the surface shape after storing the coating solution is improved.

  The reason why the stability of the surface shape is improved before and after storage of the coating solution is not clear, but is estimated as follows. When particles having different refractive indexes are used, the surface state is different, so that the aggregation and dispersion behavior in the matrix is also different. Coexistence of particles that are slightly different in particle size and difficult to agglomerate with particles that are prone to agglomeration, so that particle agglomeration does not progress during storage of the coating solution and the surface morphology of the applied antiglare layer is stable. Is realized. For example, when a general-purpose polyfunctional acrylate compound is used as a matrix-forming binder, when resin particles having a refractive index of translucent particles of 1.54 or more are used, the tendency of the particles to agglomerate is strong. The surface shape changes easily. By mixing particles having different particle sizes, it is possible to suppress the growth of the size of the aggregates and to stabilize the surface shape. In addition, by mixing particles having a refractive index of 1.53 or less, which has a small aggregating property of the particles themselves, the growth of the aggregates can be more effectively suppressed, and the stabilization of the surface morphology is achieved.

  The amount of particles added is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and most preferably 3 to 40% by mass in the total solid content of the light scattering layer. When the particles are in this ratio, the effect of reducing the variation of the surface morphology of the coating film accompanying the change with time of the coating solution is excellent.

  The particles can be selected from the particles described below according to the desired refractive index and average particle size.

  In the present invention, resin particles and / or inorganic fine particles are used as the translucent particles.

  Specific examples of the resin particles include, for example, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, crosslinked polystyrene particles, crosslinked methyl methacrylate-methyl acrylate copolymer particles, crosslinked acrylate-styrene copolymer particles, Preferred examples include resin particles such as melamine / formaldehyde resin particles and benzoguanamine / formaldehyde resin particles. Of these, crosslinked styrene particles, crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, and the like are preferable. Furthermore, the surface of these resin particles is a so-called surface-modified particle in which a compound containing a fluorine atom, a silicon atom, a carboxyl group, a hydroxyl group, an amino group, an sulfonic acid group, a phosphoric acid group or the like is chemically bonded, or a nano particle such as silica or zirconia. The particle | grains which couple | bonded the size inorganic particle to the surface are also mentioned preferably. Moreover, inorganic fine particles can also be used as the translucent particles. Specific examples of the inorganic fine particles include silica particles and alumina particles, and silica particles are particularly preferably used.

  In the present invention, when the refractive index of the matrix is 1.54 or less, and particularly preferably the refractive index is 1.53 or less, from the viewpoint of cost, it is difficult to notice uneven coating or interference unevenness. Are preferably crosslinked polymethyl methacrylate particles, crosslinked methyl methacrylate-styrene copolymer particles, and silica particles. When using crosslinked methyl methacrylate-styrene copolymer particles, the copolymerization ratio of styrene is preferably 50% or more and 90% or less.

  As the shape of the particle, either a true sphere or an irregular shape can be used. The particle size distribution is preferably monodisperse particles because of the haze value, controllability of diffusibility, and uniformity of the coated surface. For example, when a particle having a particle size of 20% or more than the average particle size is defined as a coarse particle, the proportion of the coarse particle 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 obtained by classification after a normal synthesis reaction, and particles having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

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

  In the antiglare film of the present invention, the haze value resulting from surface scattering is preferably 0 to 10%, more preferably 0.5 to 5%. By setting the surface haze to this range, an antiglare film excellent in blackening can be obtained. The haze value resulting from internal scattering is preferably 8 to 90%, more preferably 10 to 40%, and most preferably 10 to 30%. By setting the internal haze in this range, it is possible to practically satisfy the two performances of lowering the surface contrast and preventing glare. These hazes can be adjusted by adjusting the type and amount of the light-transmitting particles.

<Binder for matrix formation of antiglare layer>
Although it does not specifically limit as a binder which forms the matrix which forms an anti-glare layer, It is preferable that it is a translucent polymer which has a saturated hydrocarbon chain or a polyether chain as a main chain after hardening by ionizing radiation etc. Moreover, it is preferable that the main binder polymer after hardening has a crosslinked structure.

  As the binder polymer having a saturated hydrocarbon chain as a main chain after curing, an ethylenically unsaturated monomer selected from compounds of the first group described below and a polymer thereof are preferable. Moreover, as a polymer which has a polyether chain as a principal chain, the epoxy-type monomer chosen from the compound of the 2nd group described below and the polymer by these ring-opening are preferable. Furthermore, a polymer of a mixture of these monomers is also preferable.

  In the present invention, as the first group of compounds, the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure is a (co) polymer of monomers having two or more ethylenically unsaturated groups. Is preferred. In order to obtain a high refractive index, the monomer structure preferably contains at least one selected from an aromatic ring, a halogen atom other than fluorine, a sulfur atom, a phosphorus atom, and a nitrogen atom.

  As a monomer having two or more ethylenically unsaturated groups used in a binder polymer for forming an antiglare layer, an ester of a polyhydric alcohol and (meth) acrylic acid {for example, ethylene glycol di (meth) Acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetrameta Relate, polyurethane polyacrylate, polyester polyacrylate}, vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinyl sulfone (eg, , Divinylsulfone), (meth) acrylamide (for example, methylenebisacrylamide) and the like.

  Furthermore, resins having two or more ethylenically unsaturated groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins And oligomers or prepolymers such as polyfunctional compounds such as polyhydric alcohols. Two or more of these monomers may be used in combination, and the resin having two or more ethylenically unsaturated groups is preferably contained in an amount of 10 to 100% based on the total amount of the binder.

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photoradical polymerization initiator or a thermal radical polymerization initiator. Accordingly, a coating solution containing a monomer having an ethylenically unsaturated group, a photo radical polymerization initiator or a thermal radical polymerization initiator, and particles, and if necessary, an inorganic filler, a coating aid, other additives, an organic solvent and the like. After coating the coating solution on a transparent support, it is cured by a polymerization reaction with ionizing radiation or heat to form an antiglare layer. It is also preferable to perform ionizing radiation curing and thermal curing together. Commercially available compounds can be used as the photo and thermal polymerization initiators, and they are described in “Latest UV Curing Technology” (p. 159, publisher: Kazuhiro Takahisa, publisher; Technical Information Association, 1991). Issued) and Ciba Specialty Chemicals catalog.

In the present invention, the epoxy compound described below is preferably used as the second group of compounds in order to reduce the curing shrinkage of the cured film. As these monomers having an epoxy group, monomers having two or more epoxy groups in one molecule are preferable, and examples thereof include JP-A Nos. 2004-264563, 2004-264564, and 2005-37737, Examples thereof include epoxy monomers described in JP-A-2005-37738, JP-A-2005-140862, JP-A-2005-140862, JP-A-2005-140863, and JP-A-2002-322430.
The monomer having an epoxy group is preferably contained in an amount of 20 to 100% by mass with respect to all binders constituting the layer in order to reduce curing shrinkage, more preferably 35 to 100% by mass, and more preferably 50 to 100% by mass. It is more preferable to contain.

Examples of photoacid generators that generate cations by the action of light for polymerizing epoxy monomers and compounds include ionic compounds such as triarylsulfonium salts and diaryliodonium salts, and nitrobenzyl esters of sulfonic acids. Non-ionic compounds and the like can be used, and various known photoacid generators such as compounds described in “Organic Materials for Imaging” published by Bunshin Publishing Co., Ltd. (1997) can be used. . Among these, a sulfonium salt or an iodonium salt is particularly preferable, and PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like are preferable as a counter ion.

  The polymerization initiator is preferably used in a range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the compound of the first group or the second group in the total amount of the polymerization initiator. Is more preferable.

<High molecular compound of antiglare layer>
The antiglare layer of the present invention may contain a polymer compound. By adding a polymer compound, curing shrinkage can be reduced, and the viscosity of the coating solution can be adjusted.

  The polymer compound has already formed a polymer when added to the coating solution. Examples of the polymer compound include cellulose esters (for example, cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose acetate Pionate, cellulose acetate butyrate, cellulose nitrate, etc.), urethane acrylates, polyester acrylates, (meth) acrylic acid esters (for example, methyl methacrylate / (meth) methyl acrylate copolymer, methyl methacrylate / (Meth) ethyl acrylate copolymer, methyl methacrylate / (meth) butyl acrylate copolymer, methyl methacrylate / styrene copolymer, methyl methacrylate / (meth) acrylic acid copolymer, polymethyl methacrylate Etc.), poly Resins such as styrene are preferably used.

  The polymer compound is preferably from 1 to 50% by mass, more preferably from 5 to 40%, based on the total binder contained in the layer containing the polymer compound, from the viewpoint of the effect on curing shrinkage and the effect of increasing the viscosity of the coating solution. It is preferable to contain in the range of mass%. Further, the molecular weight of the polymer compound is preferably from 30,000 to 400,000 in terms of mass average, more preferably from 50,000 to 300,000, and even more preferably from 50,000 to 200,000.

<Inorganic filler for antiglare layer>
In the antiglare layer of the present invention, an inorganic filler can be used depending on the purpose of adjusting the refractive index, adjusting the film strength, reducing the shrinkage of curing, and reducing the reflectance when a low refractive index layer is provided. For example, it is made of an oxide containing at least one metal element selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony, and the average particle size of primary particles is generally 0.2 μm or less, preferably It is also preferable to contain a fine high refractive index inorganic filler that is 0.1 μm or less, more preferably 0.06 μm or less and 1 nm or more.

  When it is necessary to lower the refractive index of the matrix in order to adjust the refractive index difference, a fine low refractive index inorganic filler such as silica fine particles or hollow silica fine particles can be used as the inorganic filler. The preferred particle size is the same as that of the fine high refractive index inorganic filler.

  The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.

  It is preferable that the addition amount of an inorganic filler is 10-90 mass% of the total mass of a light-scattering layer, More preferably, it is 20-80 mass%, Most preferably, it is 30-75 mass%.

  In addition, since the inorganic filler has a particle size sufficiently shorter than the wavelength of light, scattering does not occur, and the dispersion in which the filler is dispersed in the binder polymer has the property of an optically uniform substance.

<Surfactant of antiglare layer>
In the antiglare layer of the present invention, in order to ensure surface uniformity such as coating unevenness, drying unevenness, and point defects, in particular, either a fluorine-based surfactant or a silicone-based surfactant, or both are used for a light scattering layer. It is preferable to contain in the coating composition. In particular, a fluorine-based surfactant is preferably used because an effect of improving surface defects such as coating unevenness, drying unevenness, and point defects of the optical film of the present invention appears with a smaller addition amount.
The purpose is to increase productivity by giving high-speed coating suitability while improving surface uniformity. Preferable examples of the fluorine-based surfactant include compounds described in paragraph numbers 0049 to 0074 of JP2007-188070A.

  The preferable addition amount of the surfactant (particularly the fluorine-based polymer) used in the antiglare layer of the present invention is in the range of 0.001 to 5% by mass, preferably 0.005 to 3% by mass with respect to the coating solution. %, And more preferably in the range of 0.01 to 1% by mass. When the addition amount of the surfactant is 0.001% by mass or more, the effect is sufficient, and by setting the addition amount to 5% by mass or less, the coating film is sufficiently dried and good performance as a coating film (for example, reflection) Rate, scratch resistance).

<Organic solvent of coating solution for antiglare layer>
An organic solvent can be added to the coating composition for forming the antiglare layer.

  As an organic solvent, for example, in an alcohol system, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, isoamyl alcohol, 1-pentanol, n-hexanol, methyl amyl alcohol In the ketone system, methyl isobutyl ketone, methyl ethyl ketone, diethyl ketone, acetone, cyclohexanone, diacetone alcohol, etc., in the ester system, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, n-butyl acetate, Isoamyl acetate, n-amyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetate, methyl lactate, ethyl lactate, ether, acetal, 1,4 dioxane, te In hydrocarbons such as lahydrofuran, 2-methylfuran, tetrahydropyran, diethyl acetal, etc., hexane, heptane, octane, isooctane, ligroin, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, styrene, divinylbenzene, etc., halogen hydrocarbons In, carbon tetrachloride, chloroform, methylene chloride, ethylene chloride, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene, 1,1,1,2-tetrachloroethane In the case of polyhydric alcohols and derivatives thereof, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoacetate, diethylene glycol, In fatty acid systems such as lenglycol, dipropylene glycol, butanediol, hexylene glycol, 1,5-pentanediol, glycerin monoacetate, glycerin ethers, 1,2,6-hexanetriol, formic acid, acetic acid, propionic acid, In the case of nitrogen compounds such as entrained acid, isoentangled acid, isovaleric acid, and lactic acid, formamide, N, N-dimethylformamide, acetamide, acetonitrile, and the like, and in the case of sulfur compounds, dimethyl sulfoxide and the like can be mentioned.

  Among organic solvents, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, acetone, toluene, xylene, ethyl acetate, 1-pentanol and the like are particularly preferable. In addition, an alcohol or a polyhydric alcohol solvent may be appropriately mixed with the organic solvent for the purpose of controlling cohesion. These organic solvents may be used alone or in combination, and the coating composition preferably contains 20% by mass to 90% by mass, and preferably 30% by mass to 80% by mass, as the total amount of the organic solvent. More preferably, it is most preferable to contain 40 mass%-70 mass%. In order to stabilize the surface shape of the antiglare layer, it is preferable to use a solvent having a boiling point of less than 100 ° C. and a solvent having a boiling point of 100 ° C. or more in combination.

<Curing of antiglare layer>
The anti-glare layer can be formed by applying a coating solution to a support, and then carrying out light irradiation, electron beam irradiation, heat treatment or the like to cause crosslinking or polymerization reaction. In the case of ultraviolet irradiation, ultraviolet rays emitted from light such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used. Curing with ultraviolet rays is preferably carried out by nitrogen purge or the like in an atmosphere having an oxygen concentration of 4% by volume or less, more preferably 2% by volume or less, and most preferably 0.5% by volume or less.

<Transparent plastic film substrate>
As the transparent plastic film substrate (transparent support) of the present invention, it is preferable to use a plastic film. Examples of the polymer forming the plastic film include cellulose acylate (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Film), polyamide, polycarbonate, polyester (eg, polyethylene terephthalate, polyethylene). Naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by ZEON CORPORATION), (meth) acrylic resin (ACRYPET VRL20A: product) Name, manufactured by Mitsubishi Rayon Co., Ltd., ring structure-containing acrylic resin described in JP-A No. 2004-70296 and JP-A No. 2006-171464), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable.

  The thickness of the transparent support can be generally about 25 μm to 1000 μm, preferably 25 μm to 250 μm, and more preferably 30 μm to 90 μm.

  Although the arbitrary width | variety of a transparent support body can be used, the thing of 100-5000 mm is normally used from the point of handling, a yield, and productivity, and it is preferable that it is 800-3000 mm, 1000-2000 mm More preferably it is. The transparent support can be handled in the form of a roll, and is usually 100 m to 5000 m, preferably 500 m to 3000 m.

  The surface of the transparent support is preferably smooth, and the average roughness Ra is preferably 1 μm or less, preferably 0.0001 to 0.5 μm, and 0.001 to 0.1 μm. More preferably.

  When the antiglare film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. Moreover, you may combine the optical film and polarizing plate of this invention. When the transparent support is triacetyl cellulose, triacetyl cellulose is used as a protective film for protecting the polarizing layer of the polarizing plate. Therefore, it is preferable in terms of cost to use the antiglare film of the present invention as it is for the protective film.

When the antiglare film of the present invention is used as it is as a protective film for a polarizing plate, it is preferable to carry out a saponification treatment after forming the outermost layer on the transparent support in order to sufficiently adhere it. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.

<Application method>
The antiglare film of the present invention can be formed by the following method, but is not limited to this method. First, a coating solution containing components for forming each layer is prepared. Next, a coating solution for forming an antiglare layer is applied onto the transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, or die coating. The microgravure coating method, the wire bar coating method, and the die coating method (see US Pat. No. 2,681,294 and JP-A-2006-122889) are more preferable, and the die coating method is particularly preferable.

  Thereafter, the monomer for forming the antiglare layer is polymerized and cured by light irradiation or heating. Thereby, an anti-glare layer is formed.

Next, a coating solution for forming a scratch-resistant layer is applied on the antiglare layer in the same manner, and light-irradiated to form a scratch-resistant layer. Thus, the antiglare film of the present invention is obtained.
When another functional layer is formed under the antiglare layer or between the antiglare layer and the scratch resistant layer, it can be formed using the same method as that for the antiglare layer.

<Polarizing plate>
The polarizing plate is mainly composed of two protective films that protect both the front and back sides of the polarizing film. The antiglare film of the present invention is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antiglare film of the present invention also serves as a protective film, the manufacturing cost of the polarizing plate can be reduced. Further, by using the antiglare film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.
A polarizing plate using the antiglare film of the present invention as one of the protective films of the polarizing film and an optical compensation film having optical anisotropy as the other of the protective films of the polarizing film is also preferable.
Examples of the optical compensation film include Wide View Film A 12B manufactured by FUJIFILM Corporation, and can be expected to have excellent antireflection performance, and excellent visibility and display quality.

The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, so that it is difficult for dust to enter between the polarizing film and the anti-glare film when bonded to the polarizing film, thus preventing point defects due to dust. It is valid.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

<Image display device>
The antiglare 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), cathode ray tube display devices (CRT), and surface electric field displays (SED). Can be applied. It is particularly preferably used for a liquid crystal display (LCD). Since the optical film of the present invention has a transparent support, it is used by bonding the transparent support side to the image display surface of the image display device.

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

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

(Coating solution for anti-glare layer and scratch-resistant layer)
The coating solutions for the antiglare layer and the scratch resistant layer used in this example are shown below.

Composition of coating liquid A-1 for anti-glare layer PET-30 65.0 g
Irgacure 127 3.0g
8μm crosslinked acrylic particles (30%) 20.0g
8μm cross-linked acrylic / styrene particles (30%) 52.6g
SP-13 0.2g
CAB 0.5g
MIBK 72.6g
MEK 32.5g

The coating solution for antiglare layer was filtered through a polypropylene filter having a pore size of 30 μm to prepare a coating solution.
The refractive index of the matrix after curing in the coating solution was 1.525.

  Here, the refractive index of the film of the antiglare layer excluding the translucent particles was directly measured with an Abbe refractometer. Further, the refractive index of the translucent particles is changed by changing the mixing ratio of two kinds of solvents having different refractive indexes selected from methylene iodide, 1,2-dibromopropane, and n-hexane. The turbidity was measured by dispersing an equal amount of translucent particles in the solvent, and the refractive index of the solvent when the turbidity was minimized was measured by an Abbe refractometer.

The refractive index of the particles was as follows.
8 μm crosslinked acrylic particles 1.500
8μm cross-linked acrylic / styrene particles 1.555

[Surface treatment of inorganic oxide fine particles]
<Preparation of Dispersion A-1>
Dispersion A is a silica fine particle sol (manufactured by Nissan Chemical Industries, Ltd., methanol silica sol, average particle size 12 nm, silica concentration 30%). Using Dispersion A, the solvent was replaced by distillation under reduced pressure at 25 ° C. while adding methyl ethyl ketone (MEK) so that the total liquid amount became substantially constant. Finally, silica dispersion A-1 was prepared by adjusting the solid content to 20%.

<Preparation of dispersion A-2>
8 parts of acryloyloxypropyltrimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate were mixed with 333 parts of silica fine particle sol (manufactured by Nissan Chemical Industries, Ltd., methanol silica sol, average particle size 12 nm, silica concentration 30%). Later, 9 parts of ion exchange water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added. The solvent was replaced by distillation under reduced pressure while adding MEK so that the total liquid volume was almost constant. Silica dispersion A-2 was prepared by adjusting the final solid content to 20%.

Composition of coating solution B-1 for scratch-resistant layer Silica dispersion A-1 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
PMMA 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of coating liquid B-2 for scratch resistant layer Silica dispersion A-1 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
Pst / PMMA = 30/70 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of coating liquid B-3 for scratch-resistant layer Silica dispersion A-1 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-1 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of coating liquid B-4 for scratch-resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-1 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of Coating Solution B-5 for Scratch Resistant Layer Silica Dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-2 1.0g
MEK 2064.2g
MMPG-Ac 551.4g

Composition of coating solution B-6 for scratch-resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-2 2.0g
MEK 2063.2g
MMPG-Ac 551.4g

Composition of coating liquid B-7 for scratch resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-2 5.0g
MEK 2060.2g
MMPG-Ac 551.4g

Composition of Coating Solution B-8 for Scratch Resistant Layer Silica Dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-2 7.0g
MEK 2058.2g
MMPG-Ac 551.4g

Composition of coating liquid B-9 for scratch-resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-3 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of coating liquid B-10 for scratch-resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-4 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

Composition of coating liquid B-11 for scratch-resistant layer Silica dispersion A-2 (20%) 169.5 g
Irgacure 127 3.4g
DPHA 67.6g
S-5 3.0g
MEK 2062.2g
MMPG-Ac 551.4g

  The scratch-resistant layer coating solution was filtered through a polypropylene filter having a pore size of 1 μm to prepare a coating solution. The refractive index after curing of the scratch-resistant layer formed by coating and curing the coating solution was 1.50.

The compounds used are shown below.
PET-30: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate [manufactured by Nippon Kayaku Co., Ltd.]
DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd.]
8 μm cross-linked acrylic particles (30%): 30 wt% MIBK dispersion with an average particle size of 8.0 μm [manufactured by Soken Chemical Co., Ltd., prepared by dispersing at 10,000 rpm for 20 minutes with a Polytron disperser)
8 μm cross-linked acrylic / styrene particles (30%): 30 wt% MIBK dispersion with an average particle size of 8.0 μm [manufactured by Sekisui Plastics Co., Ltd., prepared by dispersing at 10,000 rpm for 20 minutes with a Polytron disperser)
Irgacure 127: Polymerization initiator [Ciba Specialty Chemicals Co., Ltd.]
CAB: cellulose acetate butyrate (number average molecular weight 40000)
PMMA: Polymethyl methacrylate (number average molecular weight of about 40,000)
Pst / PMMA: 30/70 = polystyrene / polymethyl methacrylate copolymer (number average molecular weight of about 40000)
MIBK: methyl isobutyl ketone MEK: methyl ethyl ketone MMPG-Ac: propylene glycol monomethyl ether acetate

  SP-13: Fluorine-based surfactant (used after dissolving as a 10% by mass solution of MEK)

S-1: A mass average molecular weight Mw having the repeating unit (A-1) of 32,000 was used.
S-2: A mass average molecular weight Mw having the repeating unit (A-30) of 45,000 was used.
S-3: The one having a mass average molecular weight Mw having the repeating unit P-10 of 18000 was used.
S-4: A mass average molecular weight Mw having the repeating unit P-13 of 13000 was used.
S-5: A mass average molecular weight Mw having the repeating unit P-23 of 14,000 was used.

[Example 1: Production of antiglare film samples 101 to 115]
(1) Coating of anti-glare layer An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Film Co., Ltd.) is unwound in roll form, and coating solution A-1 for the anti-glare layer is used. In the die coating method using a slot die described in Example 1 of JP-A-2006-122889, coating was performed under the condition of a conveyance speed of 30 m / min, drying at 60 ° C. for 150 seconds, and oxygen concentration under nitrogen purge was about 0. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) at 1%, ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 100 mJ / cm ² were applied to cure and wind up the coating layer. . The coating amount was adjusted so that the film thickness of each antiglare layer was 13 μm.

(2) Coating of scratch-resistant layer The triacetyl cellulose film coated with the antiglare layer is unwound again, and the coating solution for scratch-resistant layer is conveyed by a die coating method using the slot die. After coating at 30 m / min and drying at 90 ° C. for 75 seconds, an air-cooled metal halide lamp (made by Eye Graphics Co., Ltd.) having an oxygen concentration of 0.01 to 0.1% and 240 W / cm under a nitrogen purge was used. The film is irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 240 mJ / cm ² , the coating amount is adjusted so as to have the film thickness shown in Table 1, a scratch-resistant layer is formed, wound up, and an antiglare film Was made.
In the sample of sample No. 101, the scratch-resistant layer was not laminated.

(Saponification treatment of antiglare film)
The following processing was performed on the samples 101 to 115 produced above. A 1.5 mol / L aqueous sodium hydroxide solution was prepared and kept at 55 ° C. A 0.01 mol / L dilute sulfuric acid aqueous solution was prepared and kept at 35 ° C. The produced optical film was immersed in the aqueous sodium hydroxide solution for 2 minutes and then immersed in water to sufficiently wash away the aqueous sodium hydroxide solution. Subsequently, after being immersed in the above-mentioned dilute sulfuric acid aqueous solution for 1 minute, it was immersed in water to sufficiently wash away the dilute sulfuric acid aqueous solution. Finally, the sample was thoroughly dried at 120 ° C. In this manner, saponified antiglare films (101 to 115) were produced.

(Preparation of polarizing plate)
A polarizing film was prepared by adsorbing iodine to a stretched polyvinyl alcohol film. Next, a saponified antiglare film (101 to 115) was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive so that the cellulose triacetate side of the antiglare film was the polarizing film side. Further, an 80 μm-thick triacetylcellulose film (TAC-TD80U, manufactured by Fuji Film Co., Ltd.), which was immersed in a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes and then neutralized and washed, was polyvinyl alcohol. Using a system adhesive, the polarizing film was pasted on the side opposite to the side on which the antiglare film was pasted. In this way, polarizing plates (HK-01) to (HK-15) with an antiglare film were produced.

(Evaluation of anti-glare film)
The obtained items were evaluated for the following items. The results are shown in Table 1.

(1) Evaluation of coating unevenness Cut out the anti-glare film into a sheet of A4 size, paste a PET film with a black adhesive on the back, and visually observe under the three-wavelength fluorescent lamp 500 lux and 1000 lux according to the following criteria. evaluated. A slight unevenness can be detected when evaluated at 1000 lux. Five A4 sheets were observed to evaluate the frequency of occurrence of unevenness.

A: Unevenness is not observed even when observed under 1000 lux.
○: Under 1000 lux, coating unevenness is recognized with one A4 sheet, but under 500 lux, no unevenness is observed.
○ Δ: Coating unevenness is observed with one A4 sheet under 500 lux.
(Triangle | delta): The coating nonuniformity is recognized by two A4 sheets under 500 lux.
X: Coating unevenness is observed with 3 or more A4 sheets under 500 lux.

(2) Evaluation of white haze failure The anti-glare film was cut out into a sheet of A4 size, a PET film with a black adhesive was pasted on the back side of the scratch-resistant layer, and a solar light source (manufactured by Celic Corp., artificial sun irradiation) The reflected light from the lamp (SALAX) was visually observed, and the occurrence frequency of white haze-like failures that occurred locally was evaluated according to the following criteria.

A: No white haze failure is observed on five A4 sheets.
○: Although white haze failure is slightly observed in several places in the evaluation of five A4 sheets, it is a level at which there is no practical problem.
X: The occurrence of white haze failure is observed on all five A4 sheets.

(3) Steel Wool (SW) Scratch Resistance Evaluation A rubbing test was performed on the surface of the scratch resistant layer of the antiglare film using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Gelade No. 0000) was wound around the rubbing tip (1 cm × 1 cm) of a tester that was in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.

A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
X: There are scratches that can be seen at first glance.

From the results shown in Table 1, the following is clear. The antiglare layer has the scratch-resistant layer of the present invention, and the scratch-resistant layer contains (A) silicon oxide fine particles, (B) ionizing radiation resin, and (C) a crosslinkable polymer thickener. When the film thickness is from 0.05 to 0.4 μm, it has excellent visibility and no scratch resistance due to wind unevenness and local white haze due to aggregation of silica particles. A film can be obtained. In particular, as a crosslinkable polymer thickener, when a crosslinkable polymer containing a repeating unit having an alicyclic structure in the side chain and a repeating unit having an acidic group in the side chain (sample No. 113 to 115), The suppression effect of white haze failure was remarkable. It can also be seen that the addition amount of the crosslinkable thickener is preferably 3% by mass or more per total solid content of the scratch-resistant layer from the viewpoint of coating unevenness and scratch resistance.
Further, transmittance and reflection of TN, STN, IPS, VA, and OCB modes equipped with the produced polarizing plates (HK-04) to (HK-07) and (HK-09) to (HK-15) of the present invention The semi-transparent liquid crystal display device was excellent in antireflection performance and had extremely excellent visibility and display quality.

Claims (10)

An antiglare film having an antiglare layer having irregularities on its surface on a transparent plastic film substrate, and having an scratch resistant layer on the outermost surface of the antiglare layer, the average film of the scratch resistant layer An antiglare film which is a cured product of a composition having a thickness of 0.03 to 0.4 μm and the scratch-resistant layer containing at least the following components (A), (B) and (C).
(A) Inorganic fine particles mainly composed of silicon oxide having an average particle diameter of 1 to 300 nm (B) Ionizing radiation curable resin (C) Crosslinkable polymer thickener The antiglare film according to claim 1, wherein the crosslinkable polymer thickener is a crosslinkable polymer containing a repeating unit represented by the following general formula (1).

In general formula (1), a ¹ and a ² may be the same or different and each represents a hydrogen atom, an aliphatic group, —COOR ¹ , or —CH ₂ COOR ¹ . Here, R ¹ represents a hydrocarbon group.
P represents a monovalent group containing a ring-opening polymerizable group or an ethylenically unsaturated group.
L represents a single bond or a divalent linking group.   The antiglare film according to claim 2, wherein the (C) crosslinkable polymer thickener further comprises a repeating unit containing a group having an alicyclic structure in the side chain. The antiglare film according to any one of claims 1 to 3, wherein the surface of the inorganic fine particles of the component (A) is surface-treated with a compound represented by the following general formula (2).
Formula _{^{(2) (R 10) m}} -Si (X) 4-m
(In the general formula (2), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3. .)   The antiglare film according to any one of claims 1 to 4, wherein the scratch-resistant layer does not substantially contain a fluorine binder.   The antiglare film according to any one of claims 1 to 5, wherein a refractive index of the scratch-resistant layer is lower than a refractive index of the antiglare layer.   The antiglare film according to any one of claims 1 to 6, wherein the antiglare layer contains at least one kind of translucent resin and at least one kind of light diffusing particles.   The antiglare film according to claim 7, wherein an average particle diameter of the light diffusing particles is 5.5 to 15 µm, and an average film thickness of the antiglare layer is 8 to 40 µm.   The polarizing plate which has a polarizing film and a protective film on both sides of this polarizing film, Comprising: At least one of this protective film is a polarizing plate which is an anti-glare film in any one of Claims 1-8.   The image display apparatus which has the anti-glare film in any one of Claims 1-8, or the polarizing plate of Claim 9 in an image display surface.