JP2006328367A - Hardenable composition, hardened film, antireflection film, polarizing plate and liquid crystal display apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hardenable composition and a hardened film with a high antireflection property capable of forming an antireflection film with excellent scratch resistant and antifouling durability. <P>SOLUTION: A hardening composition which comprises (A) at least one of a hydrolysate of an organosilane with mass average molecular weight of 500-10,000 in terms of ethylene glycol and its condensation reaction product, (B) a fluoro resin with mass average molecular weight of ≥5,000 in terms of polystyrene and having a fluoroalkyl structure and a polysiloxane structure, and (C) at least one of a silane coupling agent represented by a predetermined general formula or its hydrolysate and its condensation reaction product. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition and a cured film useful for forming an antireflection film having excellent durability. Further, an antireflection film excellent in durability formed from the curable composition and the cured film, a polarizing plate using such an antireflection film on a protective film of a polarizing film, and an antireflection film or a polarizing plate The present invention relates to an image display device arranged on an image display surface.

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

Such an antireflection film has a low refractive index layer having an appropriate film thickness on the outermost surface on the support, optionally between the support and the low refractive index layer, a high refractive index layer, a medium refractive index layer, It can be produced by forming a hard coat layer or the like. In order to realize a low reflectance, a material having a refractive index as low as possible is desired for the low refractive index layer.
Further, since the antireflection film is used on the outermost surface, it is expected to function as a protective film for the display device. High transmittance, high physical strength (scratch resistance, etc.), chemical resistance, dust resistance, antifouling property, weather resistance (wet heat resistance, light resistance, etc.) are required.

Since the antireflection film is usually disposed on the outermost surface, high scratch resistance and antifouling properties are required. Patent Document 1 discloses a technique for improving scratch resistance by using a fluorine compound having a fluoroalkyl structure and a polysiloxane structure in a low refractive index layer. However, it is difficult to obtain sufficient scratch resistance only by the technique described in this document.
It is also difficult to obtain sufficient antifouling properties.

WO 2004/046247 A1

An object of the present invention is to provide a curable composition and a cured film that can form an antireflection film having high antireflection properties and excellent scratch resistance and antifouling durability.
Moreover, the further objective of this invention is to provide the antireflection film excellent in the above properties, and to provide a polarizing plate and an image display device using the antireflection film.

As a result of intensive studies, the present inventor has found that the above object of the present invention can be achieved by an antireflection film having the following constitution, a polarizing plate, and an image display device using the same.
1. At least one of hydrolyzate of organosilane having a weight average molecular weight in terms of ethylene glycol of 500 to 10,000 and a condensation reaction product of the hydrolyzate (A), and having a weight average molecular weight in terms of polystyrene of 5000 or more, Fluorine-containing resin (B) having an alkyl structure and a polysiloxane structure, and at least a silane coupling agent represented by the general formula (1) or a hydrolyzate of the silane coupling agent and a condensation reaction product of the hydrolyzate A curable composition containing any one of (C).
Formula _{^{(1) :( R a) m}} -Si (X a) 4-m
(However, X ^a is a hydroxyl group or a hydrolyzable group. R ^a is a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkenyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, A substituent having at least one of a carbamoyl group and an acylamino group, m is an integer represented by 1 ≦ m ≦ 3.

2. 2. The curing according to 1 above, wherein the organosilane in the hydrolyzate of the organosilane and the condensation reaction product of the hydrolyzate (A) is a compound represented by the general formula (2). Sex composition.
General formula (2): ( ^Rb ) _m- Si ( ^Xb ) _4-m
(However, ^Xb is a hydroxyl group or a hydrolyzable group. ^Rb represents an unsubstituted alkyl group or an unsubstituted aryl group. M is an integer represented by 0 ≦ m ≦ 3.)
3. 3. The curable composition according to 1 or 2 above, wherein R ^a is a substituent having at least one of an epoxy group, an acyloxy group, and an acylamino group.
4). Wherein R ^a is The curable composition according to any one of the above 1 to 3, characterized in that the substituent having an acryloyloxy group.
5. 5. The curable composition as described in any one of 1 to 4 above, which comprises inorganic fine particles (D) having an average particle diameter of 5 nm to 100 nm.
6). 6. The curable composition according to 5 above, wherein the inorganic fine particles (D) have pores having an average pore diameter of 0.01 nm to 90 nm in at least one of the inside and the surface.
7). The curable composition as described in any one of 1 to 6 above, wherein the fluorine atom content in the curable composition is 5 to 60% by mass.
8). Furthermore, the curable composition in any one of said 1-7 characterized by containing a crosslinkable compound and an acid generator.
9. A cured film obtained by curing the curable composition according to any one of 1 to 8 above by at least one of heat and ionizing radiation.

10. An antireflection film in which a hard coat layer is provided directly or via another layer on a transparent support, and an antireflection layer is further laminated on the hard coat layer,
The hard coat layer comprises a resin composition curable by at least one of heat and ionizing radiation, a silane coupling agent represented by the general formula (1), a hydrolyzate of the silane coupling agent, and its hydrolysis Formed by a cured film comprising a curable composition containing at least one of the condensation reaction products of decomposition products,
And the said antireflection layer is formed by the cured film of said 9, The antireflection film characterized by the above-mentioned.
Formula _{^{(1) :( R a) m}} -Si (X a) 4-m
(However, ^Xa is a hydroxyl group or a hydrolyzable group, and ^Ra is a halogen atom, hydroxyl group, mercapto group, carboxyl group, epoxy group, alkenyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group. A substituent having at least one acylamino group, m is an integer represented by 1 ≦ m ≦ 3.)

11. 11. The antireflection film as described in 10 above, wherein the cured composition forming the hard coat layer contains a leveling agent.
12 12. The antireflection film as described in 11 above, wherein the leveling agent is a fluorine compound and / or a silicone compound.
13. The curable composition forming the hard coat layer contains a compound composed of a fluoroaliphatic group-containing monomer represented by the following general formula (3), according to any one of 10 to 12 above. Antireflection film.
General formula (3)

(In General Formula (3), R ⁰ represents a hydrogen atom, a halogen atom or a methyl group, L represents a divalent linking group, and n represents an integer of 1 to 18.)
14 The photoelectron spectrum intensity ratio Si / C in the 80% lower layer from the outermost surface and the outermost surface of the antireflection layer is at least twice as large as the 80% lower layer in the outermost surface. Antireflection film.
15. 15. The antireflection film as described in any one of 10 to 14 above, wherein the haze due to surface scattering is 3% or less, and the 60 ° glossiness is 60% to 120%.
16. 15. The antireflection film as described in any one of 10 to 14 above, wherein the haze due to surface scattering is 3.5% or more and the 60 ° gloss is 20% to 80%.
17. The antireflection film as described in any one of 10 to 16 above, further comprising a transparent antistatic layer containing a conductive material, wherein the antireflection film has a surface resistance value logSR of 12 or less.
18. The antireflection film as described in any one of 10 to 17 above, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after 192 hours exposure to 10.10 ppm ozone is 400 g or more.

19. A polarizing plate, wherein the antireflection film according to any one of 10 to 18 is used for at least one of a protective film of a polarizing film.
20. Polarized light characterized in that the antireflection film according to any one of the above 10 to 18 is used for one of the protective films of the polarizing film, and the optical compensation film having optical anisotropy is used for the other of the protective films of the polarizing film. Board.
21. 19. An image display device, wherein the antireflection film as described in any one of 10 to 18 or the polarizing plate as described in 19 or 20 is disposed on an image display surface.
22. 22. The image display as described in 21 above, wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, OCB, and ECB modes. apparatus.

According to the present invention, it is possible to provide an antireflection film that has high antireflection properties and is excellent in anti-scratching properties and antifouling properties against dust such as dust.
Furthermore, by using these antireflection films, it is possible to provide a polarizing plate protective film, a polarizing plate, and an image display device having the above characteristics.

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.

1. Curable composition and cured film The curable composition of the present invention is at least one of a hydrolyzate of organosilane having a mass average molecular weight of 500 to 10,000 in terms of ethylene glycol and a condensation reaction product of the hydrolyzate (A ), A fluorine-containing resin (B) having a weight average molecular weight in terms of polystyrene of 5000 or more and having a fluoroalkyl structure and a polysiloxane structure, and a silane coupling agent represented by the general formula (1) or this silane coupling It contains at least one of the hydrolyzate of the agent and the condensation reaction product of the hydrolyzate (C). Hereinafter, each component (A)-(C) is demonstrated.

(Hydrolyzate of organosilane, condensation reaction product (A))
The organosilane in component (A) is preferably a compound represented by the following general formula (2). By containing the compound represented by the general formula (2) in the curable composition, an antireflection film having excellent fingerprint adhesion and wiping properties can be obtained.
General formula (2): ( ^Rb ) _m- Si ( ^Xb ) _4-m
In the general formula (2), R ^b represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, a t-butyl group, a sec-butyl group, a decyl group, and a hexadecyl group. 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.

In the general formula (2), ^Xb 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 and the like), and R ^2. COO group (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO group and C ₂ H ₅ COO group), preferably an alkoxy group, particularly preferably. Is a methoxy group or an ethoxy group.
m represents an integer of 0 to 3. When R ^b or X ^b there are a plurality, it may be different even multiple R ^b or X ^b respectively the same. m is preferably 0-2.

  It is preferable that at least one of hydrolysis and condensation reaction of organosilane is performed in the presence of a catalyst. Catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as oxalic acid, acetic acid, formic acid, methanesulfonic acid and toluenesulfonic acid; inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia; triethylamine, Examples include organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, etc., but the production stability of a sol solution containing a hydrolyzate of organosilane and a condensation reaction product of the hydrolyzate From the viewpoint of the storage stability of the sol solution, in the present invention, at least one of an acid catalyst (inorganic acids, organic acids) and a metal chelate compound is used.

As the inorganic acid, hydrochloric acid, sulfuric acid, and organic acid preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less. As the organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant in water of 3.0 or less is more preferable, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferable, An organic acid having an acid dissociation constant of 2.5 or less is more preferable, methanesulfonic acid, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.
The amount of the acid catalyst used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group when the acid catalyst is an inorganic acid, and the acid catalyst is an organic acid. However, when water is added, the optimal amount used is 0.01 to 10 mol%, preferably 0.1 to 5 mol%, based on the hydrolyzable group. When substantially no water is added, it is 1 to 500 mol%, preferably 10 to 200 mol%, more preferably 20 to 200 mol%, still more preferably 50 to 50 mol% with respect to the hydrolyzable group. 150 mol%, particularly preferably 50 to 120 mol%. The reaction is carried out by stirring at 25 to 100 ° C., but is preferably controlled by the reactivity of organosilane.

When a metal chelate compound is used for the formation of an organosilane hydrolyzate and a condensation reaction, the metal chelate compound is represented by the general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms). and alcohols of the general formula ^R 4 COCH ₂ COR ⁵ (wherein, ^{R 4} represents an alkyl group having 1 to 10 carbon atoms, ^{R 5} is alkoxy having 1 to 10 carbon alkyl group or a C 1 to 10 carbon atoms And at least one metal chelate compound having a metal selected from Zr, Ti and Al as a central metal, wherein the compound represented by (1) is a ligand.

  As the metal chelate compound, a compound having a metal selected from Zr, Ti or Al as a central metal can be preferably used. Two or more metal chelate compounds may be used in combination. Specific examples of metal chelate compounds include tri-n-butoxyethyl acetoacetate zirconium, di-n-butoxybis (ethyl acetoacetate) zirconium, n-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (n-propyl acetoacetate). Zirconium chelate compounds such as zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diisopropoxy Titanium chelate compounds such as bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxy Cetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetate) And aluminum chelate compounds such as acetate) aluminum.

  Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

The hydrolysis and condensation reaction of the organosilane can be performed without a solvent or in a solvent. When a solvent is used, the concentration of the hydrolyzate of organosilane and the partial condensate thereof can be appropriately determined. As the solvent, an organic solvent is preferably used in order to uniformly mix the components. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The solvent preferably dissolves the organosilane and the catalyst. In addition, it is preferable in the process that an organic solvent is used as a coating solution or a part of the coating solution, and those that do not impair the solubility or dispersibility when mixed with other materials such as a fluorine-containing polymer are preferable.

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

  Specific examples of aromatic hydrocarbons include benzene, toluene, xylene and the like. Specific examples of ethers include tetrahydrofuran and dioxane. Specific examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, Specific examples of esters such as diisobutyl ketone include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate. These organic solvents can be used alone or in combination of two or more. The concentration of the solid content relative to the solvent in the reaction is not particularly limited, but is usually in the range of 1% by mass to 90% by mass, and preferably in the range of 20% by mass to 70% by mass.

  In the hydrolysis and condensation reaction, usually 0.3 to 2 mol, preferably 0.5 to 1 mol of water is added to 1 mol of the hydrolyzable group of the organosilane, and in the presence or absence of the solvent. Below, it is carried out by stirring at 25-100 ° C. When the hydrolyzable group is an alkoxy group and the acid catalyst is an organic acid, since the carboxyl group or sulfo group of the organic acid supplies protons, the amount of water added can be reduced, such as the alkoxy group of organosilane. The amount of water added to 1 mol of the hydrolyzable group is 0 to 2 mol, preferably 0 to 1.5 mol, more preferably 0 to 1 mol, and particularly preferably 0 to 0.5 mol. When alcohol is used as the solvent, it is also preferred that substantially no water is added.

The hydrolyzate of organosilane as the component (A) or the condensation reaction product thereof may be a chain or may have a three-dimensional network structure.
The mass average molecular weight of the hydrolyzate of organosilane or the condensation reaction product thereof is preferably 500 to 10,000 in terms of mass average molecular weight in terms of ethylene glycol. When the mass average molecular weight is in the above range, the Si component of component (A) is unevenly distributed on the surface of the low refractive index layer, and the scratch resistance and antifouling property of the low refractive index layer can be sufficiently secured. Moreover, there exists an advantage that the applicability | paintability and storage stability of a curable composition are maintained because a mass mean molecular weight exists in the said range. The mass average molecular weight in terms of ethylene glycol of the hydrolyzate of organosilane or the condensation reaction product thereof is more preferably 800 to 9000, further preferably 1000 to 8000.
The mass average molecular weight was measured in terms of ethylene glycol by solvent (DMF) and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). The molecular weight expressed.

(Fluorine-containing resin having fluoroalkyl structure and polysiloxane structure (B))
The fluororesin (B) is obtained by hydrolyzing a compound having a fluoroalkyl structure with any one of the general formula (1) and the general formula (2) (preferably a compound represented by the following general formula (5)). It can be obtained by at least one of condensation reactions.
Formula _{(5) :( Rf-L 1} ) n -Si (X 1) 4-n

In general formula (5), Rf represents a linear, branched or cyclic fluorinated alkyl group having 1 to 20 carbon atoms or a fluorinated aromatic group having 6 to 14 carbon atoms. Rf is preferably a linear, branched or cyclic fluoroalkyl group having 3 to 10 carbon atoms, and more preferably a linear fluoroalkyl group having 4 to 8 carbon atoms.
L ₁ represents a divalent linking group having 10 or less carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group which may have a linking group (for example, ether, ester, amide) inside. The alkylene group may have a substituent, and preferable substituents in that case include a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group.
X ₁ has the same meaning as X ^{a in} formula (1), 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 C 1-3 alkoxy group is more preferable, and a methoxy group is particularly preferable.

Among the fluorine-containing silane coupling agents represented by the general formula (5), the fluorine-containing silane coupling agent represented by the following general formula (6) is preferable.
Formula _{(6): C n F 2n} + 1 - (CH 2) m -Si (X 2) 3
In general formula (6), n represents an integer of 1 to 10, and m represents an integer of 1 to 5. n is preferably 4 to 10, m is preferably 1 to 3, and X ₂ represents a methoxy group, an ethoxy group, or a chlorine atom.

  When the compound of the general formula (2) is used for forming the fluororesin, the compound of the general formula (2) is preferably tetramethoxysilane or tetraethoxysilane.

  Solvents, catalysts, and reaction conditions used in the hydrolysis and condensation reaction to obtain the fluorine-containing resin are the same as those described in the hydrolyzate of organosilane and the condensation reaction product (A) of the hydrolyzate, Catalyst and reaction conditions can be applied.

  There is no particular limitation on the reaction ratio of any one of the general formulas (1) and (2) of the fluororesin and the general formula (5), but the general formulas (1) and / or (2): The general formula (5) is preferably 1 to 10: 1, and more preferably 2 to 10: 1.

  The fluororesin (B) preferably has at least one of a hydroxyl group and an epoxy group. At least one of the hydroxyl group and epoxy group of the fluororesin (B) is a hydrolyzate of organosilane and a condensation reaction product (A) of the hydrolyzate, and a polysiloxane structure of the fluororesin (B). Accordingly, the film strength of the low refractive index layer is increased, and the scratch resistance can be further improved. The hydroxyl group or epoxy group may be introduced into the fluoroalkyl structure or may be introduced into the polysiloxane structure. A hydroxyl group or an epoxy group can be introduced by copolymerizing a compound having these functional groups.

The fluororesin (B) may have a chain shape or may have a three-dimensional network structure. Moreover, as for the mass average molecular weight of a fluorine-containing resin (B), it is preferable that the mass average molecular weight by polystyrene conversion is 5000 or more, It is more preferable that it is 5000-100000, It is further more preferable that it is 5000-50000. When the mass average molecular weight is 5000 or more, the scratch resistance of the low refractive index layer can be sufficiently secured. On the other hand, when the mass average molecular weight is 100,000 or less, the coating property and the storage stability of the curable composition are maintained.
The weight average molecular weight is a molecular weight expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). is there.

(Silane coupling agent represented by the general formula (1) or its hydrolyzate / condensation reaction product (C))
The curable composition of the present invention contains (C) at least one of a silane coupling agent represented by the following general formula (1) or a hydrolyzate of the silane coupling agent and a condensation reaction product of the hydrolyzate. To do. By using the compound represented by the general formula (1) as the silane coupling agent, an antireflection film excellent in adhesion, particularly interfacial adhesion can be obtained.
Formula _{^{(1) :( R a) m}} -Si (X a) 4-m

Although in the general formula (1) no particular restriction on the substituents contained in R ^a, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an 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 group (acetoxy group, acryloyloxy group, methacryloyloxy group, etc.), al Xyloxycarbonyl group (methoxycarbonyl 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. 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.
R ^a is any one of a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and an acylamino group. It is preferably a substituent having the above group, more preferably a substituent having any one of an epoxy group, an acyloxy group and an acylamino group, and particularly preferably an acryloyloxy group.

In the general formula (1), when there are ^a plurality of R ^{a s} , 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 (1) is a vinyl polymerizable compound represented by the following general formula (4). It can be expressed as an osilane coupling agent having a substituent.

In the general formula (1), X ^a 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 and the like), and R ^2. COO group (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO group and C ₂ H ₅ COO group), preferably an alkoxy group, particularly preferably. Is a methoxy group or an ethoxy group.
m is an integer represented by 1 ≦ m ≦ 3. When R ^a or X ^a presence of a plurality, may be different even multiple R ^a or X ^a same respectively. m is preferably 0-2.

The silane coupling agent represented by the general formula (1) is preferably a compound represented by the following general formula (4). By using the compound represented by the general formula (4) as the silane coupling agent, an antireflection film having further excellent interface adhesion can be obtained.
General formula (4)

In the general formula (4), R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. As R ¹ ,
A hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom and a chlorine atom are preferable, a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom and a chlorine atom are more preferable, and a hydrogen atom and a methyl group are particularly preferable preferable.
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.

  In the general formula (4), L is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a linking group (eg, ether group, ester) A substituted or unsubstituted alkylene group having a group, an amide group), or a substituted or unsubstituted arylene group having a linking group therein, among them, a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, substituted Alternatively, an unsubstituted arylene group having 6 to 20 carbon atoms and an alkylene group having 3 to 10 carbon atoms having a linking group therein are preferable, an unsubstituted alkylene group, an unsubstituted arylene group, and an ether linking group or an ester linkage inside. An alkylene group having a group is more preferable, an unsubstituted alkylene group, and an alkylene group having an ether linking group or an ester linking group inside is particularly preferable. Masui. 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.

In the general formula (4), 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 ^{b 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.

  The solvent, catalyst, and reaction conditions used in the hydrolysis and condensation reaction to obtain a hydrolyzate of the silane coupling agent and a condensation reaction product of the hydrolyzate are the hydrolyzate of organosilane and the hydrolysis thereof. The solvents, catalysts, and reaction conditions already described in the condensation reaction product (A) can be applied.

The silane coupling agent represented by the general formula (1) or the hydrolyzate of the silane coupling agent and the condensation reaction product (C) of the hydrolyzate may be in a chain form or have a three-dimensional network structure. You may have. Moreover, it is preferable that the mass mean molecular weight by polystyrene conversion of this component (C) is 500-10000. Furthermore, it is preferable that it is 800-9000, and it is especially preferable that it is 1000-8000. When the mass average molecular weight is in the above range, the scratch resistance of the low refractive index layer can be sufficiently secured.
The weight average molecular weight is a molecular weight expressed in terms of polystyrene by solvent THF and differential refractometer detection using a GPC analyzer using columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation). is there.

(Inorganic fine particles (D))
The curable composition of the present invention can contain inorganic fine particles.
The average particle size of the inorganic fine particles is preferably 5 to 100 nm, more preferably 10 to 90 nm, and still more preferably 15 to 85 nm. Moreover, it is preferable to contain 5-80 mass% of inorganic fine particles with respect to solid content in a curable composition, More preferably, it is 10-70 mass%, More preferably, it is 15-65 mass%. If the content of the inorganic fine particles is not less than the lower limit, the scratch resistance can be effectively improved, and if the content is not more than the upper limit, fine irregularities can be formed on the surface of the low refractive index layer, black Therefore, the content of the inorganic fine particles is preferably within this range.

  The inorganic fine particles contained in the curable composition desirably have a low refractive index. Examples of such inorganic fine particles include magnesium fluoride and silica fine particles. In particular, silica fine particles are preferably used from the viewpoint of refractive index, dispersion stability, and cost. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. The average particle size of the inorganic fine particles is measured with a Coulter counter.

In order to further reduce the increase in the refractive index of the cured film formed of the curable composition, it is preferable to use silica fine particles having pores at least either inside or on the surface as inorganic fine particles. In particular, it is preferable to use hollow silica fine particles (hereinafter sometimes referred to as hollow particles). The hollow particles preferably have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and particularly preferably 1.17 to 1.30. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the silica component of the outer shell forming the hollow particles. The refractive index of the hollow particles is preferably 1.17 or more from the viewpoint of the strength of the particles and the scratch resistance of the low refractive index layer containing the hollow particles.
In addition, the refractive index of these hollow particles can be measured with an Abbe refractometer [manufactured by Atago Co., Ltd.], and is a value at 25 ° C. and D line.

The average pore diameter of the pores present (existing) in at least one of the inside and the surface is preferably 0.01 nm to 90 nm, more preferably 4 to 90 nm, still more preferably 4 to 80 nm. From the viewpoint of the refractive index and strength of the inorganic fine particles, the average pore diameter is preferably within the above range.
When the average pore diameter is 0.01 nm or more, the effect of lowering the refractive index is increased. Further, when the average pore diameter is 90 nm or less, the strength of the particles can be maintained, and excellent scratch resistance can be maintained.

  Inorganic fine particles are treated with physical surface treatment such as plasma discharge treatment or corona discharge treatment in order to stabilize the dispersion in the dispersion or coating solution, or to improve the affinity and binding properties with the binder component. Chemical surface treatment with a surfactant, a coupling agent, or the like may be performed.

(Crosslinkable compound)
A crosslinkable compound can be mix | blended with a curable composition. Examples of the crosslinkable compound include melamine resins, glycols, acrylic resins, azides, and isocyanates. Among these, melamine resins such as methylolated melamine, alkoxymethylated melamine, or derivatives thereof are preferable in view of storage stability of the curable composition. As for the usage-amount of a crosslinkable compound, 70 mass parts or less are preferable with respect to 100 mass parts of fluororesin (B). More preferably, it is 30 mass parts or less, More preferably, it is 5-30 mass parts.

(Acid generator)
An acid generator can be mix | blended with a curable composition. The acid generator is preferably one that dissolves uniformly in the curable composition, does not decompose the curable composition, and does not degrade the film transparency of the cured film. Examples of the acid generator include organic acids such as p-toluenesulfonic acid and benzoic acid, and photoacid generators such as triazine compounds. The use ratio of the acid generator is preferably 10 parts by mass or less with respect to 100 parts by mass of the fluorine compound (B). More preferably, it is 5 mass parts or less, More preferably, it is 0.1-5 mass parts.

  The acid generator is preferably a salt composed of an acid and an organic base. Examples of the acid include organic acids such as sulfonic acid, phosphonic acid, and carboxylic acid, and inorganic acids such as sulfuric acid and phosphoric acid. From the viewpoint of compatibility with the polymer, organic acids are more preferable, and sulfonic acid and phosphonic acid are more preferable. Sulphonic acid is most preferred. Preferred sulfonic acids include p-toluenesulfonic acid (PTS), benzenesulfonic acid (BS), p-dodecylbenzenesulfonic acid (DBS), p-chlorobenzenesulfonic acid (CBS), 1,4-naphthalenedisulfonic acid (NDS). ), Methanesulfonic acid (MsOH), nonafluorobutane-1-sulfonic acid (NFBS), etc., and any of them can be preferably used (the abbreviations in parentheses).

  The acid generator varies greatly depending on the basicity and boiling point of the organic base combined with the acid. The acid generator preferably used in the present invention will be described below from each viewpoint.

  The lower the basicity of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. However, if the basicity is too low, the storage stability becomes insufficient. Therefore, it is preferable to use an organic base having an appropriate basicity. When expressed using pKa of a conjugate acid as a basic index, the pKa of the organic base used in the present invention is preferably 5.0 to 10.5, more preferably 6.0 to 10.0, and 6. More preferably, it is 5-10.0. The value of pKa of organic base in aqueous solution is described in Chemistry Handbook Basic Edition (5th revised edition, edited by The Chemical Society of Japan, Maruzen, 2004) Volume II, pages II-334-340. An organic base having an appropriate pKa can be selected. In addition, a compound that can be presumed to have a pKa that is structurally appropriate even if not described in this document can be preferably used. Although the compound which has suitable pKa described in this literature in the following table | surface is shown, the compound which can be preferably used for this invention is not limited to these.

  The lower the boiling point of the organic base, the higher the acid generation efficiency during heating, which is preferable from the viewpoint of curing activity. Therefore, it is preferable to use an organic base having an appropriate boiling point. The boiling point of the base is preferably 120 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower.

Examples of the organic base that can be preferably used in the present invention include, but are not limited to, the following compounds. Figures in parentheses indicate boiling points.
b-3: pyridine (115 ° C), b-14: 4-methylmorpholine (115 ° C), b-20: diallylmethylamine (111 ° C), b-19: triethylamine (88.8 ° C), b-21 : T-butylmethylamine (67-69 ° C), b-22: dimethylisopropylamine (66 ° C), b-23: diethylmethylamine (63-65 ° C), b-24: dimethylethylamine (36-38 ° C) ), B-18: trimethylamine (3-5 ° C.).
In the present invention, a preferable boiling point of the organic base is 35 ° C. or more and 85 ° C. or less. If the temperature is higher than this, the scratch resistance deteriorates, and if it is lower than 35 ° C., the coating solution becomes unstable. The boiling point is more preferably 45 ° C. or higher and 80 ° C. or lower, and most preferably 55 ° C. or higher and 75 ° C. or lower.

  When used as the acid catalyst of the present invention, a salt composed of the acid and the organic base may be isolated and used, or the acid and the organic base may be mixed to form a salt in the solution, and the solution may be used. . Further, only one kind of acid or organic base may be used, or a plurality of kinds may be mixed and used. When the acid and the organic base are mixed and used, it is preferable that the equivalent ratio of the acid and the organic base is 1: 0.9 to 1.5, preferably 1: 0.95 to 1.3. Is more preferable, and 1: 1.0 to 1.1 is more preferable.

(solvent)
As the solvent used for the preparation of the curable composition, a solvent that can be dissolved without separating each component and the like can be used without particular limitation. Examples thereof include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl butyl acetate. Furthermore, for the purpose of improving the coatability and the stability of the solution, a poor solvent such as an alcohol can be used as long as each component does not precipitate.
The solution concentration of the curable composition is not particularly limited as long as it does not impair the solution stability. When a curable resin composition is used for the antireflection layer forming agent, it is necessary to form a thin film with high thickness accuracy. Therefore, it is usually 0.1 to 20% by mass, preferably about 0.5 to 10% by mass. It is easy to handle and preferable.

In addition, the cured composition to increase the storage stability of the curable composition, the general formula ^(7): It is preferred to add a solvent represented by R 4 COCH ₂ COR ^5. In the general formula (7), R ⁴ and R ⁵ are the same as R ⁴ and R ⁵ constituting the metal chelate compound.
The solvent represented by the general formula (7) is at least one of a β-diketone compound and a β-ketoester compound, and acts as a stability improver for the cured composition. That is, by coordinating with a metal atom in the metal chelate compound (a compound of at least one of zirconium, titanium and aluminum compounds), the components of the general formula (3) and the general formula (5) by these metal chelate compounds It is thought that it has the effect | action which suppresses the effect | action which accelerates | stimulates a condensation reaction and improves the storage stability of the composition obtained.

Specific examples of the β-diketone compound and β-ketoester compound represented by the general formula (7) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate. Acetic acid-n-butyl, acetoacetic acid-sec-butyl, acetoacetic acid-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane- Examples include dione, 2,4-nonane-dione, and 5-methyl-hexane-dione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and β-ketoester compounds can be used alone or in admixture of two or more.
In the present invention, the β-diketone compound and β-ketoester compound represented by the general formula (7) are used in total, preferably 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. . If the amount is too small, the storage stability of the resulting composition may be inferior, which is not preferable.

(Addition amount of each component)
In the curable composition of the present invention, the mixing ratio of the hydrolyzate or condensation reaction product (A) of organosilane and the fluororesin (B) is appropriately determined according to the use of the cured film obtained from the composition. Prepared. When the ratio of the hydrolyzate or condensation reaction product (A) of organosilane increases, the ratio of the fluororesin (B) decreases, and the refractive index of the cured film tends to increase or the antifouling property tends to decrease. . On the other hand, when the proportion of the organosilane hydrolyzate or condensation reaction product (A) decreases, the film strength of the low refractive index layer becomes weak and the scratch resistance tends to decrease. From these viewpoints, when the cured film is a low refractive index layer, the proportion of the hydrolyzate of organosilane and the condensation reaction product (A) of the hydrolyzate in the curable composition In general, the solid content is preferably 5 to 90% by mass with respect to the total of the decomposition product or condensation reaction product (A) and the fluororesin (B). More preferably, it is 30-75 mass%.

  In the curable composition of the present invention, the silane coupling agent or the hydrolyzate or condensation reaction product (C) of the silane coupling agent is 3 to 3 times the total of the component (A) and the component (B). It is preferable that it is 80 mass%. More preferably, it is 5-70 mass%, and 8-60 mass% is especially preferable.

(Fluorine atom content)
The fluorine atom content in the cured composition is preferably 5% by mass or more, and more preferably 5 to 60% by mass. Furthermore, it is preferable that it is 5-40 mass%, It is more preferable that it is 7-38 mass%, It is especially preferable that it is 10-30 mass%. When it is less than 5% by mass, the antifouling property of the low refractive index layer is lowered, and when it exceeds 60% by mass, the scratch resistance is lowered, which is not preferable.
In the present invention, the fluorine atom content in the cured composition was quantified by 600 MHz NMR (AVANCE 600 type manufactured by Bruker) ( ¹⁹ -NMR of an acetone-d6 solution with CF ₃ -Ph as an internal standard) (Quantitative) value.

(Fluorine atom content)
The fluorine atom content in the cured composition is preferably 5% by mass or more, and more preferably 5 to 60% by mass. Furthermore, it is preferable that it is 5-40 mass%, and it is especially preferable that it is 7-38 mass%. When it is less than 5% by mass, the antifouling property of the low refractive index layer is lowered, and when it exceeds 50% by mass, the scratch resistance is lowered, which is not preferable.
In the present invention, the fluorine atom content in the cured composition was quantified by 600 MHz NMR (AVANCE 600 type manufactured by Bruker) ( ¹⁹ -NMR of an acetone-d6 solution with CF ₃ -Ph as an internal standard) (Quantitative) value.

(Method for forming cured film)
As a curing means for the curable composition, it is preferable to use at least one of heat and ionizing radiation. As thermosetting temperature, 60-150 degreeC is preferable, 80-140 degreeC is more preferable, Especially preferably, it is 100-140 degreeC. If it exists in the said range, a base will be hard to deform | transform.
The thermosetting time is preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes, and particularly preferably 2 to 30 minutes. When it exists in the said range, productivity is not impaired.

In the curing means using ionizing radiation, the ionizing radiation is preferably irradiated in an atmosphere having an oxygen concentration of 3% by volume or less. More preferably, it is 1 volume% or less, More preferably, it is 0.1 volume% or less. In order to reduce the oxygen concentration more than necessary, a large amount of inert gas is required, which is not preferable from the viewpoint of production cost. As a means for reducing the oxygen concentration, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another inert gas, particularly preferably with nitrogen (nitrogen purge). It is.
When using a curing means using ionizing radiation, it is particularly preferable to perform curing by irradiating with ionizing radiation for 0.2 seconds or more in an atmosphere having an oxygen concentration of 3% by volume or less. The irradiation time is preferably from 0.2 second to 60 seconds, more preferably from 0.3 second to 10 seconds from the start of irradiation. If it is less than 0.2 seconds, the curing reaction cannot be completed and sufficient curing may not be performed.

2. Antireflection film The antireflection film of the present invention has a hard coat layer provided directly or via another layer on a transparent support, and further an antireflection layer is laminated on the hard coat layer.
Hereinafter, each layer constituting the antireflection film will be described.

[Antireflection layer (low refractive index layer)]
The antireflection layer (low refractive index layer) is formed from a cured film made of the curable composition 1 described above.
The refractive index of the low refractive index layer is preferably 1.20 to 1.46, more preferably 1.25 to 1.40, and particularly preferably 1.25 to 1.38.
The thickness of the low refractive index layer is preferably 50 to 200 nm, and more preferably 70 to 120 nm. The haze of the low refractive index layer is preferably 3% or less, more preferably 2% or less, and most preferably 1% or less. The specific strength of the low refractive index layer is preferably H or higher, more preferably 2H or higher, and most preferably 3H or higher in a pencil hardness test under a 500 g load.
Moreover, in order to improve the antifouling performance of the antireflection film, it is preferable that the contact angle of water with respect to the surface is 90 degrees or more. More preferably, it is 95 degrees or more, and particularly preferably 100 degrees or more.

[Hard coat layer]
The hard coat layer includes a resin composition curable by at least one of heat and ionizing radiation, a silane coupling agent represented by the general formula (1), a hydrolyzate of the silane coupling agent, and a hydrolysis thereof. It forms with the cured film which consists of a curable composition containing the at least any one of the condensation reaction material of a thing.

(Resin composition)
Examples of the resin composition that can be cured by at least one of heat and ionizing radiation include those containing an ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable. Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable.

Specific examples of the photopolymerizable polyfunctional monomer having a photopolymerizable functional group include esters of polyhydric alcohol and (meth) acrylic acid [for example, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, Hexanediol 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, , 3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polyacrylate], ethylene oxide modified products and caprolactone modified products of the above esters, vinylbenzene and its derivatives [eg, 1,4-divinylbenzene, 4-vinylbenzoic acid- 2-acryloyl ethyl ester, 1,4-divinylcyclohexanone], vinyl sulfone (eg, divinyl sulfone), acrylamide (eg, methylene bisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination.
The photopolymerizable polyfunctional monomer is preferably polymerized using a photopolymerization initiator and a photosensitizer, and the photopolymerization reaction is preferably carried out by ultraviolet irradiation after the hard coat layer is applied and dried.

In order to impart resistance to brittleness, at least one of oligomers and polymers having a mass average molecular weight of 500 or more may be added to the hard coat layer. Examples of the oligomer and polymer include (meth) acrylate-based, cellulose-based, and styrene-based polymers, urethane acrylate, and polyester acrylate. Preferable examples include polyglycidyl (meth) acrylate and polyallyl (meth) acrylate having a functional group in the side chain.

  The content of at least one of the oligomer and the polymer in the hard coat layer is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 35 to 65% with respect to the total mass of the hard coat layer. % By mass.

(Leveling agent)
The hard coat layer preferably uses various leveling agents for the purpose of preventing unevenness. Examples of the leveling agent include an acrylic leveling agent, a vinyl leveling agent, a fluorine leveling agent, and a silicone leveling agent, and a fluorine leveling agent or a silicone leveling agent is preferable.
The leveling agent is preferably an oligomer or a polymer rather than a low molecular compound. The fluorine leveling agent and the silicone leveling agent will be described later.
When a leveling agent is added to the hard coat layer, the leveling agent is quickly unevenly distributed on the surface of the coated liquid film, and the leveling agent is unevenly distributed on the surface even after the hard coat layer is dried. The surface energy is reduced by the leveling agent.
Therefore, it is preferable that the surface energy of the hard coat layer is low from the viewpoint of preventing unevenness of the hard coat layer.

  The surface tension of the coating solution for the hard coat layer is preferably in the range of 15 to 40 [mN / m]. If it is this range, since the nonuniformity at the time of drying is suppressed, it is preferable. More preferably, it is the range of 18 [mN / m]-36 [mN / m], and the range of 20 [mN / m]-33 [mN / m] is especially preferable. If it is this range, the upper limit speed | rate which can be apply | coated is not dropped, and it is preferable.

The surface energy of hard coat layer (γs ^v : unit, mJ / m ² ) is experimental on antiglare hard coat layer with reference to DKOwens: J.Appl.Polym.Sci., 13,1741 (1969) It is represented by the sum of pure water between H ₂ O and methylene iodide CH ₂ respective contact angle theta _{H2 O} of I _2, where theta following simultaneous equations from _CH2I2 (1) (2) from the obtained gamma] s ^d and gamma] s ^h obtained in This is an energy conversion value of the surface tension of the antiglare hard coat layer defined by the value γs ^v (= γs ^d + γs ^h ). (The mN / m unit is mJ / m ² unit.) Before the sample is measured, it is necessary to adjust the humidity for a certain period of time under a predetermined temperature and humidity condition. The temperature at this time is preferably in the range of 20 ° C. to 27 ° C., the humidity is preferably in the range of 50 RH% to 65 RH%, and the humidity conditioning time is preferably 2 hours or more.

(1) 1 + cos θH ₂ O = 2√γs ^d (√γH ₂ Od / γH ₂ Ov) + 2√γs ^h (√γH ₂ Oh / γH ₂ Ov)
_{(2) 1 + cosθCH 2 I} 2 = 2√γs d (√γCH 2 I 2 d / γCH 2 I 2 v) + 2√γs h (√γCH 2 I 2 h / γCH 2 I 2 v)
Here, γ _H2O ^d = 21.8 °, γ _H2O ^h = 51.0 °, γ _H2O ^v = 72.8 °, γ _CH2I2 ^d = 49.5 °, γ _CH2I2 ^h = 1.3 °, and γ _CH2I2 ^v = 50.8 °.

The surface energy of the hard coat layer is preferably 45 mJ / m ² or less, more preferably in the range of 20~45mJ / ^{m 2,} and most preferred range of 25~40mJ / m ^2.
By setting the surface energy of the hard coat layer to 45 mJ / m ² or less, an effect that uneven coating of the hard coat layer hardly occurs can be obtained.
However, since an upper layer such as a low refractive index layer is further coated on the hard coat layer, the leveling agent is preferably eluted into the upper layer. It is preferable that the surface energy of the hard coat layer is rather high, and it is preferable that the surface energy is 35 to 70 mJ / m ² .

Preferable examples of the silicone compound include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include polyether groups, alkyl groups, aryl groups, aryloxy groups, acryloyl groups, methacryloyl groups, vinyl groups, aryl groups, cinnamoyl groups, epoxy groups, oxetanyl groups, hydroxyl groups, fluoroalkyl groups, polyoxy groups. Examples include an alkylene group, a carboxyl group, an amino group and the like. Although there is no restriction | limiting in particular in molecular weight, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 1000-30000, It is most preferable that it is 1000-20000. Although there is no restriction | limiting in particular in silicone atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.8 mass%, and 30.0-37.0. Most preferably, it is mass%. Examples of preferable silicone-based compounds are X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-170DX, X-22-176D, X, manufactured by Shin-Etsu Chemical Co., Ltd. -22-1821 (named above), Chisso Corporation, FM-0725, FM-7725, FM-4421, FM-5521, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS- 083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121, FMS123, FMS131, FMS141, FMS221 (all trade names), manufactured by Toray Dow Corning, SH200, DC11PA, SH28PA, ST80PA, ST86PA, ST97PA, SH550, SH71 , L7604, FZ-2105, FZ2123, FZ2162, FZ-2191, FZ2203, FZ-2207, FZ-3704, FZ-3736, FZ-3501, FZ-3789 (above trade names), manufactured by GE Toshiba Silicone Co., Ltd., Examples thereof include, but are not limited to, TSF400, TSF401, TSF410, TSF433, TSF4450, TSF4460 (and above product names).

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

  It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the low refractive index layer film. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine-based compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited. Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine-based compounds include Daikin Chemical Industries, Ltd., R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink Co., Ltd., Megafac F-171. , F-172D, F-179A, F-470, F-475, R-08, Defender MCF-300 (trade name) and the like, but are not limited thereto.

  In the case of adding these leveling agents, it is preferably added in the range of 0.01 to 20% by mass of the total solid content of the hard coat layer, more preferably in the range of 0.05 to 10% by mass. Particularly preferably 0.1 to 5% by mass.

(Fluoroaliphatic group-containing monomer represented by the general formula (3))
The curable composition for forming the hard coat layer preferably contains a fluoroaliphatic group-containing monomer represented by the general formula (3).
In the general formula (3), R ⁰ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. L represents a divalent coupler, and a divalent coupler containing an oxygen atom, a sulfur atom, or a nitrogen atom is preferable. n represents an integer of 1 to 18, more preferably 4 to 12, and particularly preferably 6 to 8.

The monomer may form a copolymer with another type of copolymerizable monomer. Other types of such copolymerizable monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley lnterscience (1975) Chapter 2 Pages 1-483 can be used.
For example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. I can give you.

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

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

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

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

  In the copolymer, the amount of the polymerized units of the fluoroaliphatic group-containing monomer represented by the general formula (3) is preferably 90% by mass or less, based on all the polymerized units constituting the copolymer, 80% by mass. It is more preferable that it is the following in%, and it is still more preferable that it is 70 mass% or less.

A preferred mass average molecular weight of the polymer comprising the fluoroaliphatic group-containing monomer of the general formula (3) is preferably 1,000 to 100,000, more preferably 1,500 to 80,000, and 2,000 to 60,000. Is more preferable.
Here, the mass average molecular weight and the molecular weight are converted into polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both trade names manufactured by Tosoh Corporation) and solvent THF and differential refractometer detection. Is the molecular weight.

  The polymer comprising the fluoroaliphatic group-containing monomer of the general formula (3) can be produced by a known method. For example, the above-mentioned monomers such as (meth) acrylate having a fluoroaliphatic group and (meth) acrylate having a linear, branched or cyclic alkyl group are added to a general-purpose radical polymerization initiator in an organic solvent. Can be produced by polymerization. Alternatively, other addition-polymerizable unsaturated compounds can be added in some cases and produced in the same manner as described above. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition.

(Silane coupling agent)
For the silane coupling agent represented by the general formula (1), the hydrolyzate of the silane coupling agent, and the condensation reaction product of the hydrolyzate, the compound of the general formula (1) described in the curable composition, What was illustrated by the hydrolysis product and the condensation reaction product of the hydrolysis product can be used.

(Fine particles)
For the hard coat layer, fine particles of at least one of inorganic and organic may be used. By using the fine particles, the refractive index of the hard coat layer can be in the range described later.
The particle diameter of the fine particles is preferably 0.01 to 1 μm, more preferably 0.01 to 0.5 μm, and particularly preferably 0.01 to 0.3 μm. If it is the range of the said particle size, the transparency of a coating film is not impaired and it is preferable.

(Translucent beads)
Various light-transmitting bead particles can be used for the film of the present invention, particularly the antiglare layer and the hard coat layer, in order to impart antiglare property (surface scattering property) and internal scattering property.

  The translucent particles may be organic particles or inorganic beads. As the particle size is not varied, the scattering characteristics are less varied, and the design of the haze value is facilitated. As the translucent beads, plastic beads are suitable.

(Inorganic beads)
Examples of inorganic beads include silica beads (refractive index 1.44), cohesive silica beads (refractive index 1.48), alumina beads (refractive index 1.63), zirconia beads, titania beads, and hollows and pores. An inorganic bead is mentioned.
The inorganic beads are preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin. In the coating material containing inorganic beads, the amount of inorganic beads that settles with the passage of time increases. Therefore, when using the coating material, it is necessary to stir and disperse the precipitated inorganic beads. On the other hand, agglomerated silica is preferable because the primary particles are on the order of submicron, and sedimentation is unlikely to occur compared to other non-aggregable inorganic beads.

(Resin beads)
Resin beads having a refractive index of 1.40 to 1.60 can be used for the hard coat layer. By using resin beads, in addition to hard coat properties, antiglare properties can be imparted.
The reason why the refractive index of the resin beads is in such a range is that the refractive index of the resin used for the hard coat layer, particularly the acrylate or methacrylate resin is usually 1.45 to 1.55. This is because if resin beads having a refractive index as close as possible to the refractive index are selected, the transparency of the coating film is not impaired and antiglare properties can be imparted. Examples of resin beads having a refractive index close to the refractive index of the resin include, for example, crosslinked polymethyl methacrylate beads (1.49), polycarbonate beads (1.58), crosslinked polystyrene beads (1.61), and polyacrylstyrene. There are beads (1.57), polyvinyl chloride beads (1.54), etc., but those having the above refractive index range can be used.

  The particle diameter of these resin beads is preferably 3 to 8 μm, and is preferably 2 to 20 parts by mass, and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin. When resin beads such as paint are mixed, it is necessary to agitate and disperse the resin beads precipitated on the bottom of the container when using the paint. In order to eliminate such inconvenience, silica beads having a particle diameter of 0.5 μm or less, preferably 0.1 to 0.25 μm may be included in the coating material as an anti-settling agent for resin beads. Note that the more silica beads are added, the more effective the prevention of sedimentation of the organic filler is, but it adversely affects the transparency of the coating film. Therefore, the amount of less than 0.1 parts by mass, which is a range capable of preventing sedimentation, is preferable to the extent that the transparency of the coating film is not impaired with respect to 100 parts by mass of the resin.

(Other additives)
Additives such as thixotropic agents and antistatic agents can be used for the hard coat layer.

(Method for forming hard coat layer)
A hard-coat layer can be formed by the crosslinking reaction or polymerization reaction of the compound (For example, the above-mentioned polyfunctional monomer and polyfunctional oligomer) contained in a curable composition by irradiating a heat | fever or ionizing radiation.
This crosslinking reaction or polymerization reaction is preferably carried out in an atmosphere having an oxygen concentration of 3% by volume or less. By forming in an atmosphere having an oxygen concentration of 3% by volume or less, a hard coat layer excellent in physical strength and chemical resistance can be formed. Preferably, it is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 1% by volume or less. More preferably, the oxygen concentration is 0.5% by volume or less, and particularly preferably the oxygen concentration is 0.1% by volume or less.
As a method for reducing the oxygen concentration to 3% by volume or less, the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) is preferably replaced with another gas, and particularly preferably replaced with nitrogen ( Nitrogen purge).

  Moreover, it is preferable to irradiate heat or ionizing radiation for 0.3 second or more in an atmosphere with an oxygen concentration of 3% by volume or less. The irradiation time is more preferably from 0.3 second to 60 seconds, and further preferably from 0.5 second to 10 seconds from the start of irradiation. If it is less than 0.3 seconds, the curing reaction cannot be completed and sufficient curing cannot be performed.

  When the resin composition curable by at least one of heat and ionizing radiation forming the hard coat layer contains an unsaturated double bond, the non-reflection layer is formed when the antireflection layer is laminated on the surface of the hard coat layer. It is preferable that 10% or more of the saturated double bond amount remains before uncured. More preferably, it is 15% or more, particularly preferably 20% or more. Within the above range, the interfacial bond strength with the antireflection layer laminated on the surface of the hard coat layer is increased, and high scratch resistance is obtained.

  As another method for increasing the interfacial bonding force between the hard coat layer and the antireflection layer, there is a method of performing a surface treatment before coating the curable composition of the antireflection layer on the hard coat layer. Examples of the surface treatment of the hard coat layer include a high frequency discharge plasma method, an electron beam method, an ion beam method, a vapor deposition method, a sputtering method, an alkali treatment method, an acid treatment method, a corona treatment method, and an atmospheric pressure glow discharge plasma method. Can do. In particular, alkali treatment is effective. Examples of the alkaline aqueous solution used in the alkali treatment method include aqueous solutions such as sodium hydroxide and potassium hydroxide, and alkaline aqueous solutions obtained by adding various organic solvents such as alcohols to these. As the conditions for the alkali treatment, for example, when an aqueous sodium hydroxide solution is used, it is preferably used as an aqueous solution having a concentration of 0.1 to 10N, and more preferably a concentration of 1 to 2N. Moreover, the temperature of aqueous alkali solution is 0-100 degreeC, Preferably it is 20-80 degreeC. The alkali treatment time is 0.01 to 10 hours, preferably 0.1 to 1 hour.

  The coating solvent is preferably a ketone solvent. By using the ketone solvent, the adhesion between the surface of the transparent support (particularly, triacetyl cellulose support) and the hard coat layer is further improved. Particularly preferred coating solvents are methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. The coating solvent may contain a solvent other than the ketone solvent. The coating solvent preferably contains a ketone solvent in an amount of 10% by mass or more of the total solvent contained in the coating composition. The content of the ketone solvent is more preferably 20% by mass or more, and further preferably 30% by mass or more.

  In addition, although a hard-coat layer may be provided directly on the surface of a transparent support body and may be provided through another layer between transparent supports, in order to provide physical strength to an antireflection film Is preferably provided directly on the surface of the transparent support.

(Physical properties of hard coat layer)
The hardness of the hard coat layer is preferably HB or higher, more preferably H or higher, in a pencil hardness test according to JIS K5400. Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.

  The refractive index of the hard coat layer of the present invention is preferably from 1.47 to 1.65. More preferred is 1.49 to 1.62.

[Antistatic layer]
The antireflection film of the present invention is preferably provided with an antistatic layer from the viewpoint of preventing static electricity on the film surface. The antistatic layer is formed by, for example, applying a coating solution of a conductive layer forming composition containing conductive fine particles and a reactive curable resin, or depositing or sputtering a metal or a metal oxide that forms a transparent film. It can be formed by a known method such as a method of forming a conductive thin film.

  The antistatic layer can be formed directly on the transparent support or via a primer layer that strengthens adhesion to the transparent support. Further, when the antistatic layer is used as a layer close to the outermost layer in the structure of the antireflection film, sufficient antistatic properties can be obtained even if the film is thin. The coating method is not particularly limited, and an optimum method may be selected from known methods such as roll coating, gravure coating, bar coating, extrusion coating, etc., depending on the characteristics and coating amount of the coating solution. . It is also preferable to adjust the refractive index of the antistatic layer so as to serve as a medium refractive index layer and a high refractive index layer.

  The thickness of the antistatic layer is preferably from 0.01 to 10 μm, more preferably from 0.03 to 7 μm, and even more preferably from 0.05 to 5 μm.

The surface resistance of the antistatic layer is preferably from 10 ⁵ to 10 is ¹² Omega / □, and further preferably 10 ⁵ to 10 ¹¹ Omega / □ is. By providing the antistatic layer, the surface resistance value logSR of the antireflection film is preferably 12 or less from the viewpoint of preventing dust adhesion to the surface of the antireflection film, and logSR is more preferably 11 or less. The surface resistance of the antistatic layer can be measured using a super insulation resistance / microammeter “TR8601” {manufactured by Advantest Co., Ltd.) at 25 ° C. and a humidity of 60% RH.

  The antistatic layer is preferably substantially transparent. Specifically, the haze of the antistatic layer is preferably 10% or less, more preferably 5% or less, further preferably 3% or less, and most preferably 1% or less. Further, the transmittance of light having a wavelength of 550 nm is preferably 50% or more, more preferably 60% or more, further preferably 65% or more, and most preferably 70% or more.

  The antistatic layer also preferably has a high hardness, and the specific antistatic layer has a pencil hardness of 1 kg (as defined in JIS K-5400), preferably H or higher, and preferably 2H or higher. Is more preferably 3H or more, and most preferably 4H or more.

(Conductive fine particles)
The antistatic layer preferably contains conductive fine particles. The conductive fine particles are preferably inorganic particles formed from a metal oxide or nitride. Examples of metal oxides or nitrides include tin oxide, indium oxide, zinc oxide, and titanium nitride. Tin oxide and indium oxide are particularly preferred.

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

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

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

  The conductive fine particles may be surface-treated. The surface treatment is performed using an inorganic compound or an organic compound. Examples of inorganic compounds used for the surface treatment include alumina and silica. Silica treatment is particularly preferred. Examples of the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Silane coupling agents are most preferred. Two or more types of surface treatments may be combined.

  The shape of the conductive fine particles is preferably a rice grain shape, a spherical shape, a cubic shape, a spindle shape or an indefinite shape. Two or more kinds of conductive fine particles may be used in combination in the antistatic layer.

  The proportion of the conductive fine particles in the antistatic layer is preferably 20 to 90% by mass, preferably 25 to 85% by mass, and more preferably 30 to 80% by mass.

The conductive fine particles are used for forming an antistatic layer in the form of a dispersion.
As the dispersion medium, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Examples of dispersion media include water, alcohols (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), esters (eg, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg hexane, cyclohexane), halogenated hydrocarbons (eg methylene chloride, chloroform, carbon tetrachloride), aromatic Hydrocarbon (eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran) Ether alcohols (e.g., 1-methoxy-2-propanol) are included. Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol are particularly preferred.

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

[Transparent support]
The light transmittance of the transparent support is preferably 80% or more, and more preferably 86% or more. The haze of the transparent support is preferably 2.0% or less, and more preferably 1.0% or less. The refractive index of the transparent support is preferably 1.4 to 1.7.

  The material for the transparent support is not particularly limited, but a plastic film is preferable to a glass plate. Examples of plastic film materials include cellulose esters (eg, cellulose triacetate, cellulose diacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene). Naphthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyether Imides include polymethyl methacrylate and polyether ketone, and the like. Cellulose ester, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

  In particular, when used in a liquid crystal display device, a cellulose acylate film which is a fatty acid ester of cellulose among the above cellulose esters is preferable. Cellulose acylate is produced by esterifying cellulose. The cellulose used is usually used after purifying linter, kenaf, pulp or the like.

As described above, the cellulose acylate in the present invention is a fatty acid ester of cellulose, and a lower fatty acid ester is particularly preferable.
Here, the lower fatty acid means a fatty acid having 6 or less carbon atoms. A cellulose acylate having 2 to 4 carbon atoms is preferable, and cellulose acetate is particularly preferable. It is also preferable to use mixed fatty acid esters such as cellulose acetate propionate and cellulose acetate butyrate.

  The viscosity average degree of polymerization (DP) of cellulose acylate is preferably 250 or more, and more preferably 290 or more. Cellulose acylate preferably has a narrow molecular weight distribution of Mw / Mn (Mw is a mass average molecular weight, Mn is a number average molecular weight) by gel permeation chromatography. A specific value of Mw / Mn is preferably 1.0 to 5.0. More preferably, it is 1.0-3.0, Most preferably, it is 1.0-2.0.

  As the transparent support, it is preferable to use cellulose acylate having an acetylation degree of 55.0 to 62.5%. The acetylation degree is more preferably 57.0 to 62.0%, and particularly preferably 59.0 to 61.5%. The degree of acetylation means the amount of bound acetic acid per unit mass of cellulose. The degree of acetylation is determined by measurement and calculation of the degree of acylation in ASTM: D-817-91 (testing method for cellulose acylate, etc.).

In cellulose acylate, the hydroxyl groups at the 2-position, 3-position and 6-position of cellulose are not evenly substituted, but the substitution degree at the 6-position tends to be small. In the cellulose acylate used in the present invention, it is preferable that the degree of substitution at the 6-position of cellulose is the same or greater than that at the 2- and 3-positions. The ratio of the substitution degree at the 6-position to the total substitution degree at the 2-position, the 3-position, and the 6-position is preferably 30 to 40%, more preferably 31 to 40%, and more preferably 32 to 40%. Most preferably it is.

  The cellulose acylate film is preferably a long film. Specifically, the cellulose acylate film has a thickness of about 100 m to 5000 m, and is usually in a form provided in a roll shape. Moreover, it is preferable that the width | variety of a resin film base material is 1.3-4 m from a viewpoint of providing an antireflection film with high productivity.

  The film thickness of the transparent support is preferably from 10 μm to 85 μm, more preferably from 10 μm to 70 μm, and most preferably from 20 μm to 60 μm. If the film thickness is thinner than this, failures such as film cutting and wrinkles are likely to occur during handling. If it is thicker than this, thinning is insufficient when pasted on a liquid crystal display.

Various additives are added to the transparent support to adjust the mechanical properties (film strength, curl, dimensional stability, slipperiness, etc.) and durability (wet heat resistance, weather resistance, etc.) of the film. Can be used. For example, plasticizers (phosphate esters, phthalate esters, esters of polyols and fatty acids, etc.), UV inhibitors (eg, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, cyanoacrylate compounds) Etc.), deterioration inhibitors (eg, antioxidants, peroxide decomposers, radical inhibitors, metal deactivators, acid scavengers, amines, etc.), fine particles (eg, SiO ₂ , Al ₂ O ₃ , TiO _2). , BaSO ₄ , CaCO ₃ , MgCO ₃ , talc, kaolin, etc.), release agents, antistatic agents, infrared absorbers, and the like.

  These details are disclosed in the Invention Association Public Technique No. 2001-1745 (issued March 15, 2001, Invention Association), p. Materials described in detail in 17-22 are preferably used. The amount of the additive used is preferably 0.01 to 20% by mass of the transparent support, and more preferably 0.05 to 10% by mass.

  In addition, by adding a small amount of matting agent, as a method that can sufficiently ensure good flatness, anti-tacking property, and transparency, it has a multilayer structure having at least a base layer and a surface layer, and the mat is formed only on the surface layer. There is a method of adding an agent.

  This surface layer may be laminated only on one side of the base layer, or may be laminated on both sides of the base layer. That is, as shown in FIG. 1 of Japanese Patent Application Laid-Open No. 2001-71418, a three-layer mode including a base layer 1 and a surface layer 2 laminated on both surfaces thereof may be used. As shown in FIG. A two-layer mode consisting of 1 and a surface layer 2 laminated on one surface thereof may be used. The surface layer is laminated at a position located on the surface, and another layer can be laminated between the base layer and the surface layer.

  In such a transparent support, a matting agent is added only to the surface layer, and no matting agent is added to the base layer. That is, by adding the matting agent only to the surface layer, the flatness of the surface of the transparent support and the anti-tacking property are ensured, and the base layer (including the intermediate layer when other layers are laminated in the middle) is also provided. By not adding a matting agent, the transparency of the entire transparent support is secured.

Examples of the matting agent include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc, and kaolin. In addition, examples of inorganic compounds include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide. Further, for example, synthetic silica obtained by wet method or gelation of silicic acid, etc. And titanium dioxide (rutile type or anatase type) produced by silicon dioxide or titanium slug and sulfuric acid. It can also be obtained by pulverizing from an inorganic substance having a relatively large particle diameter, for example, 20 μm or more, and then classifying (vibration filtration, air classification, etc.). A preferred inorganic compound matting agent includes conductive fine particles. Specifically, ZnO, TiO ₃ , SnO ₂ , Al ₂
There are fine particles of at least one crystalline metal oxide selected from O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, and MoO ₃ or a composite oxide thereof.

  Further, examples of the matting agent made of a polymer compound include polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch, and the like. . Further, a polymer compound synthesized by a suspension polymerization method, a polymer compound made spherical by a spray drying method or a dispersion method, or an inorganic compound can be used. Moreover, the polymer compound which is a polymer of one kind or two or more kinds of monomer compounds described below may be formed into particles by various means.

  For example, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are preferably used. Moreover, you may use the particle | grains which have a fluorine atom or a silicon atom as described in Unexamined-Japanese-Patent No. 62-14647, 62-17744, 62-177743. Among these, particle compositions preferably used are polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / methacrylic acid = 95/5) (molar ratio), poly (styrene / styrene sulfonic acid = 95/5). ) (Molar ratio), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10), silica and the like.

As the matting agent, various inorganic compounds and polymer compounds can be used as described above. However, inorganic compounds are preferable in a dispersion medium using methylene chloride, and silica (SiO ₂ ) is particularly inexpensive and easily available. preferable.

The addition amount of the matting agent is preferably ^{5~500mg / m 2, 10~100mg / m} 2 is more preferable. When the addition amount of the matting agent is less than 5 mg / m ² , it becomes difficult to ensure the slipperiness / tacking prevention property of the transparent support surface, and when it exceeds 500 mg / m ² , the transparency is deteriorated.

  The center line average roughness of the surface layer of the transparent support is preferably 0.01 μm to 5 μm, and the center line average roughness is more preferably 0.1 μm to 1 μm. When the center line average roughness of the surface layer is less than 0.01 μm, the film is squeaked and fine scratches are generated. On the other hand, when the center line average roughness exceeds 5 μm, the flatness deteriorates.

Surface treatment may be performed on the transparent support. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Specifically, for example, the contents described in pages 30 to 31 of the Japan Society of Invention and Innovation Technique No. 2001-1745 (issued on March 15, 2001), the contents described in Japanese Patent Application Laid-Open No. 2001-9973, and the like. It is done.
Preferably, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment, and more preferably glow discharge treatment and ultraviolet treatment.

[Other layers]
The antireflection film of the present invention may further be provided with a moisture proof layer, an antistatic layer (conductive layer), a primer layer, an undercoat layer or a protective layer, a shield layer, a sliding layer, and a gas barrier layer. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Characteristics of antireflection film]
(Photoelectron spectrum intensity ratio Si / C)
In the antireflection film, it is preferable that the photoelectron spectrum intensity ratio Si / C in the lowermost layer of the low refractive index layer (antireflection layer) and 80% lower layer from the outermost surface is twice or more larger than that in the lowermost layer. As for Si / C, it is more preferable that the outermost surface is 2.5 times or more larger than the lower layer of 80%, and it is more preferable that it is 3 times or more larger.

The photoelectron spectrum intensity ratio Si / C can be measured as follows. First, the top surface Si2p and C1s photoelectrons measured with an ESCA-3400 manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source; target Mg, voltage 12 kV, current 20 mA) for the antireflection film The spectrum intensity ratio Si2p / C1s (= Si (a)) was obtained, and the layer thickness of the low refractive index layer was reduced to 1/5 with an ion etching apparatus (ion gun, voltage 2 kV, current 20 mA) attached to ESCA-3400. The intensity ratio Si2p / C1s (= Si (b)) of the photoelectron spectrum measured in the 80% lower layer from the surface cut to (± 5%) is obtained. From these, changes in the respective intensity ratios before and after etching, Si (a) / Si (b), are obtained, and changes in the Si2p / C1s ratio before and after etching (intensity ratio of photoelectron spectrum at the top of the low refractive index layer / low) The degree of surface segregation can be determined by the intensity ratio of the photoelectron spectrum in the vicinity of the lower layer 80% deep from the surface of the refractive index layer.

In addition, C1s calculates the intensity at the peak position of each photoelectron spectrum, Si2p uses the intensity at the peak position derived from the Si atom of silicone (polydimethylsiloxane) (bonding energy is around 105 eV) for calculating the intensity ratio, and the inorganic silica It was distinguished from Si atoms derived from particles. Preliminary experiments are carried out in which the surface of the low refractive index layer is gradually scraped under various etching conditions in advance, and the conditions for a depth of 80% from the surface are obtained based on the etching conditions required to reach the lower hard coat layer. Then measure.
When controlling only the surface properties, the surface segregation compounds described in this specification can be used appropriately to selectively place only the necessary components on the surface. It can be controlled independently.

(Surface haze and gloss)
The haze (also referred to as surface haze) and the glossiness resulting from the surface scattering of the antireflection film are preferably any of the following (i) or (ii) depending on the application.
(I) Haze due to surface scattering is 3% or less, and 60 ° gloss is 60% to 120%.
(Ii) The haze resulting from surface scattering is 3.5% or more, and the 60 ° gloss is 20% to 80%.

The haze resulting from surface scattering (hereinafter referred to as surface haze) can be determined as follows. The total haze (H), internal haze (Hi), and surface haze (Hs) of the antireflection film are used.
(1) The total haze value (H) of the film obtained according to JIS-K7136 is measured.
(2) Add a few drops of silicone oil or liquid paraffin to the front and back surfaces of the resulting film on the low refractive index layer side, and add two 1 mm thick glass plates (micro slide glass product number S 9111, manufactured by MATSUNAMI) Using the two sides of the glass plate, the two glass plates and the resulting film were optically closely adhered, the haze was measured with the surface haze removed, and silicone oil was measured between the two separately measured glass plates. A value obtained by subtracting the haze measured by sandwiching only the film is calculated as the internal haze (Hi) of the film.
(3) A value obtained by subtracting the internal haze (Hi) calculated in (2) from the total haze (H) measured in (1) above is calculated as the surface haze (Hs) of the film.

(Limit load in swab rub test)
The antireflection film of the present invention preferably has a limit load of 400 g or more in a water swab rubbing test on the surface of the antireflection film after being exposed to 10 ppm of ozone for 192 hours. More preferably, it is 500 g or more, More preferably, it is 600 g or more.
The limit load in the water swab rubbing test can be determined as follows.
Each sample is processed into a polarizing plate, stored in an environment of ozone 10 ppm, 30 ° C., 60% RH for 192 hours (8 days) and then taken out into the atmosphere. A cotton swab (Health Refre (trade name) manufactured by Toyo Sanyo Co., Ltd.) is fixed to the rubbing tip of a rubbing tester. Is immersed in water at 25 ° C., a load is applied to a cotton swab, and a 20 reciprocating rubbing test is performed. Rubing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second After the water on the surface of the sample after rubbing is dried, whether the film is peeled off is visually observed. The test is performed 10 times on the same sample, and the test is performed by starting with an initial load of 100 g and increasing the load by 50 g until film peeling occurs 5 times or more. The load at which film peeling is less than 5 times in 10 tests is defined as the critical load. The film peeling is judged based on whether or not the reflection state of the surface is visually changed. When the section of the film in which the reflection state is changed is observed with an electron microscope, it is observed that the film thickness of the uppermost layer is 5% or more thinner, or the uppermost layer and other constituent layers are peeled off.

[Method for producing antireflection film]
Next, an embodiment of the method for producing an antireflection film of the present invention will be described.
The antireflection film of the present invention can be produced by the following method, but is not limited to this method.
(Preparation and application of composition)
First, the composition for forming each layer which comprises an antireflection film is prepared, and this is apply | coated on a support body. As the coating method, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method and a die coating method are preferable, and a gravure coating method, a wire bar coating method and a die coating method are more preferable. The die coating method is particularly preferable.

For application of each composition, it is preferable to use a die coater shown in FIG. The coater 10 shown in FIG. 1 forms a coating film 14b on the web 12 by applying the coating liquid 14 as a bead 14a from the slot die 13 to the web 12 supported continuously by the backup roll 11. To do.
A pocket 15 and a slot 16 are formed inside the slot die 13. The pocket 15 has a cross section constituted by a curve and a straight line, and may be, for example, a substantially circular shape as shown in FIG. 1 or a semicircular shape. The pocket 15 is a liquid storage space for the coating liquid extended in the width direction of the slot die 13 with its cross-sectional shape, and the length of the effective extension is generally equal to or slightly longer than the coating width.

  The supply of the coating liquid 14 to the pocket 15 is performed from the side surface of the slot die 13 or from the center of the surface opposite to the slot opening 16a. The pocket 15 is provided with a stopper that prevents the coating liquid 14 from leaking out.

The slot 16 is a flow path of the coating liquid 14 from the pocket 15 to the web 12, and has a cross-sectional shape in the width direction of the slot die 13 like the pocket 15, and the opening 16a located on the web side is generally Using a width regulating plate (not shown), the width is adjusted to be approximately the same as the coating width. The angle between the slot tip of the slot 16 and the tangent in the web traveling direction of the backup roll 11 is preferably 30 ° or more and 90 ° or less.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 18 called a land. In this land 18, the upstream side in the running direction of the web 12 with respect to the slot 16 is referred to as an upstream lip land 18 a and the downstream side is referred to as a downstream lip land 18 b.

  2A and 2B show the cross-sectional shape of the slot die 13 in comparison with the conventional one. FIG. 2A shows the slot die 13 shown in FIG. 1, and FIG. 2B shows the conventional slot die 30. Yes. In the conventional slot die 30, the distance between the upstream lip land 31a and the web 12 of the downstream lip land 31b is equal. In (B), reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13, the downstream lip land length ILO is shortened, so that application with a wet film thickness of 20 μm or less can be accurately performed.

  The land length IUP of the upstream lip land 18a is not particularly limited, but a range of 100 μm to 1 mm is preferably employed. The land length ILO of the downstream lip land 18b is 30 μm or more and 100 μm or less, preferably 30 μm or more and 80 μm or less, more preferably 30 μm or more and 60 μm or less.

  If the land length ILO of the downstream lip is shorter than 30 μm, the edge or land of the tip lip 17 is likely to be chipped, streaks are likely to occur in the coating film, and as a result, application becomes impossible. In addition, it becomes difficult to set the position of the wetting line on the downstream side, and there is a problem that the coating liquid tends to spread on the downstream side. It has been conventionally known that this spreading of the coating liquid on the downstream side means non-uniform wetting lines and leads to a problem of causing a defective shape such as a streak on the coating surface.

  On the other hand, when the land length ILO of the downstream lip is longer than 100 μm, the bead itself cannot be formed, so that it is impossible to perform thin layer coating.

  Further, the downstream lip land 18b has an overbite shape closer to the web 12 than the upstream lip land 18a. Therefore, the degree of decompression can be reduced, and a bead suitable for thin film coating can be formed. The difference in distance between the downstream lip land 18b and the web 12 of the upstream lip land 18a (hereinafter referred to as overbit length LO) is preferably 30 μm or more and 120 μm or less, more preferably 30 μm or more and 100 μm or less, and most preferably 30 μm. It is 80 μm or less.

  When the slot die 13 has an overbite shape, the gap GL between the tip lip 17 and the web 12 indicates a gap between the downstream lip land 18 b and the web 12.

  FIG. 3 is a perspective view showing the slot die 13 shown in FIG. 1 and its periphery. On the opposite side of the web 12 from the traveling direction, a decompression chamber 40 is installed at a position where it does not come into contact with the bead 14a so that sufficient decompression can be performed. The decompression chamber 40 includes a back plate 40a and a side plate 40b for maintaining its operating efficiency, and there are gaps GB and GS between the back plate 40a and the web 12, and between the side plate 40b and the web 12, respectively. Exists.

4 and 5 are cross-sectional views showing the decompression chamber 40 and the web 12 that are close to each other. The side plate 40b and the back plate 40a may be integrated with the chamber body as shown in FIG. 4, or are fastened to the chamber with screws 40c or the like so that the gap can be appropriately changed as shown in FIG. It may be a structure.

  Regardless of the structure, the portions actually opened between the back plate 40a and the web 12 and between the side plate 40b and the web 12 are defined as gaps GB and GS, respectively. The gap GB between the back plate 40a of the decompression chamber 40 and the web 12 is the distance GB from the uppermost end of the back plate 40a to the web 12 when the decompression chamber 40 is installed below the web 12 and the slot die 13 as shown in FIG. Indicates a gap.

  The gap GB between the back plate 40a and the web 12 is preferably set larger than the gap GL between the tip lip 17 of the slot die 13 and the web 12. Thereby, the pressure reduction degree change of the bead vicinity resulting from the eccentricity of the backup roll 11 can be suppressed.

  For example, when the gap GL between the tip lip 17 of the slot die 13 and the web 12 is not less than 30 μm and not more than 100 μm, the gap GB between the back plate 40 a and the web 12 is preferably not less than 100 μm and not more than 500 μm.

  The longer the length of the tip lip 17 on the traveling direction side of the web 12 in the web traveling direction, the more disadvantageous it is for bead formation. If this length varies between arbitrary locations in the slot die width direction, the bead is caused by a slight disturbance. Becomes unstable. Therefore, it is preferable that the fluctuation width in the slot die width direction is within 20 μm.

  Further, when the material of the tip lip 17 of the slot die is made of a material such as stainless steel, the length of the slot die tip lip 17 in the web running direction is set to 30 as described above. Even in the range of ˜100 μm, the accuracy of the tip lip 17 cannot be satisfied.

  Therefore, in order to maintain high processing accuracy, it is important to use a cemented carbide material as described in Japanese Patent No. 2817053. Specifically, at least the tip lip 17 of the slot die is preferably made of a cemented carbide formed by bonding carbide crystals having an average particle size of 5 μm or less.

  Cemented carbides include carbide crystal particles such as tungsten carbide (hereinafter referred to as WC) bonded by a bonding metal such as cobalt, and other bonding metals include titanium, tantalum, niobium, and mixed metals thereof. Can also be used. The average particle size of the WC crystal is more preferably 3 μm or less.

  In order to achieve highly accurate coating, the length of the land on the web running direction side of the tip lip 17 and the variation in the slot die width direction of the gap with the web are also important factors. It is desirable to achieve a combination of the two factors, that is, straightness within a range in which the fluctuation range of the gap can be suppressed to some extent. Preferably, the straightness between the tip lip 17 and the backup roll 11 is set so that the fluctuation width of the gap in the slot die width direction is 5 μm or less.

(Curing treatment)
After applying the composition for forming each layer on the support as described above, a curing treatment is performed by at least one of heat and light irradiation. Thus, application | coating and a hardening process are repeated about each layer, and a hard-coat layer, a low refractive index layer, etc. are laminated | stacked on a support body. Moreover, you may harden all the layers which apply | coated the multilayer after simultaneous multilayer coating simultaneously.
In order to suppress coloring, decomposition, and deformation of the transparent support, it is preferably 150 ° C. or lower when heat-curing, and 1000 mJ / cm ² when irradiated with light. Furthermore, it is also preferable to carry out a photocuring treatment after the heat curing treatment, or heat treatment in the latter half of the photocuring treatment. In particular, in the low refractive index layer, it is preferable to carry out a photocuring treatment after the heat curing treatment or heat treatment in the latter half of the photocuring treatment.
Moreover, in order to improve the interlayer adhesion between the upper layer and the lower layer, it is preferable that the lower layer is half-cured within a range that does not affect the antireflection performance, and is fully cured after the upper layer is applied.

  The light source for light irradiation may be any one in the ultraviolet light region or near infrared light region, and as a light source for ultraviolet light, ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, metal halides. Lamp, xenon lamp, sunlight, and the like. Various available laser light sources having a wavelength of 350 to 420 nm may be irradiated as a multi-beam. Further, examples of the near-infrared light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp. Various available laser light sources having a wavelength of 750 to 1400 nm may be irradiated in a multi-beam form.

  When using a near-infrared light source, it may be used in combination with an ultraviolet light source, or may be irradiated from the substrate surface side opposite to the high refractive index layer coating side. As a result, film curing in the depth direction in the coating layer proceeds without delay with the vicinity of the surface, and a uniform low-refractive index layer is obtained.

In the case of radical photopolymerization by light irradiation, it can be carried out in air or in an inert gas, but in order to shorten the polymerization induction period of the radically polymerizable monomer or sufficiently increase the polymerization rate, etc. It is preferable that the atmosphere has a reduced oxygen concentration. Irradiation intensity of ultraviolet irradiation is preferably about 0.1~100mW / cm ^2, irradiation amount on the coating film surface is preferably 10~1000mJ / cm ^2. Further, the temperature distribution of the coating film in the light irradiation step is preferably as uniform as possible, preferably within ± 3 ° C., and more preferably controlled within ± 1.5 ° C. In this range, the polymerization reaction in the in-plane and in-layer depth directions of the coating film proceeds uniformly, which is preferable.
The above process may be performed every time each layer is formed, or a plurality of coating units-drying chambers-radiation curing units-thermosetting chambers may be provided to form each layer continuously. In view of the above, it is preferable to continuously form each layer.

  Curing by means of at least one of heat and light irradiation can be carried out by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a heat radical initiator.

  As radical photopolymerization initiators, acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds And fluoroamine compounds and aromatic sulfoniums. Examples of acetophenones include 2,2-diethoxyacetophenone, p-dimethylacetophenone, 1-hydroxydimethylphenylketone, 1-hydroxycyclohexylphenylketone, 2-methyl-4-methylthio-2-morpholinopropiophenone and 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone is included. Examples of benzoins include benzoin benzene sulfonate, benzoin toluene sulfonate, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether. Examples of benzophenones include benzophenone, 2,4-dichlorobenzophenone, 4,4-dichlorobenzophenone and p-chlorobenzophenone. Examples of phosphine oxides include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Various examples are described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasagi, publisher; Technical Information Association, Inc., published in 1991), which is useful for the present invention.
Preferable examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 819, OXE01) manufactured by Ciba Specialty Chemicals.
It is preferable to use a photoinitiator in the range of 0.1-15 mass parts with respect to 100 mass parts of polyfunctional monomers, More preferably, it is the range of 1-10 mass parts.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.

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

  In the present invention, the surface of the transparent support and / or hard coat layer may be subjected to discharge and / or radiation irradiation treatment for surface modification.

  Examples of the discharge or radiation irradiation treatment include corona discharge treatment, glow discharge treatment, arc discharge treatment, plasma treatment, ultraviolet irradiation treatment, and electron beam irradiation treatment. Of these, corona discharge treatment and ultraviolet irradiation treatment are preferred because they are simple and have high treatment effects. By performing these surface modification treatments on the hard coat layer, the adhesion between the hard coat layer and the low refractive index layer can be improved, and the durability of the antireflection film can be improved.

3. Polarizing plate The polarizing plate of the present invention has the antireflection film of the present invention on at least one of the polarizing film protective film (polarizing plate protective film). By using the antireflection film of the present invention as a protective film for a polarizing plate, a polarizing plate having an antireflection function excellent in physical strength and weather resistance can be produced, and drastic cost reduction and thinning of a display device can be realized. .

  Moreover, it is more preferable to use the antireflection film of the present invention for one of the protective films for a polarizing plate and use an optical compensation film having an optically anisotropic layer, which will be described later, for the other protective film for a polarizing plate. In such a polarizing plate, in addition to the above characteristics, the contrast in the bright room of the liquid crystal display device can be improved, and the viewing angle in the vertical and horizontal directions can be greatly widened.

(Protective film for polarizing plate)
When using the antireflection film of the present invention as a protective film for polarizing plate, the surface of the transparent support of the antireflection film (on the side opposite to the surface provided with the antireflection layer) is hydrophilized, and this hydrophilization treatment It is preferable to bond the processed surface to the deflection film. Similarly, it is preferable to perform a hydrophilic treatment on the bonding surface of the optical compensation film with the deflecting film.

The hydrophilic treatment of the surface of the transparent protective film can be performed by a known method. Examples thereof include a method for modifying the film surface by corona discharge treatment, glow discharge treatment, ultraviolet irradiation treatment, flame treatment, ozone treatment, acid treatment, alkali saponification treatment, and the like. These are described in detail in the aforementioned public technical number 2001-1745, pages 30-32.
Among these, it is particularly preferable to treat the surface of the cellulose acylate film with an alkali saponification treatment.

  Specific means for the alkali saponification treatment can be selected from the following four means (1) to (4). Among these, (1) is excellent in that it can be processed in the same process as a general-purpose cellulose acylate film, but since the saponification treatment is performed up to the surface of the antireflection layer, the surface is alkali-hydrolyzed and the film deteriorates. On the other hand, if the saponification solution remains, it may become a problem. On the other hand, the method (2) is preferable because it can improve the adhesion between the low refractive index layer and the lower layer in the antireflection film of the present invention.

(1) After forming the low refractive index layer of the antireflection layer on the transparent support, the surface and the back surface of the antireflection film are saponified by immersing in an alkaline solution at least once.
(2) Before the low refractive index layer is formed on the transparent support, the surface of the transparent support having a layer formed before forming the low refractive index layer by immersing in an alkaline solution at least once; Saponify the back side. In this method, the surface on which the low refractive index layer is provided is also subjected to alkali treatment.
(3) After forming up to the low refractive index layer of the antireflection layer on the transparent support, the surface on the low refractive index layer side is protected with a laminate, and immersed in an alkaline solution at least once, Saponify the back side.
(4) Before or after forming the layer constituting the antireflection layer on the transparent support, an alkaline liquid is applied to the surface of the transparent support opposite to the surface on which the antireflection layer is formed, and heated. Only the back surface of the antireflection film is saponified by washing with water and / or neutralizing.

  In addition, the protective film for polarizing plates has a contact angle with water on the surface of the transparent support opposite to the side having the antireflection layer, that is, the surface to be bonded to the polarizing film, in the range of 20 to 50 degrees. Preferably there is.

(Polarizing film)
The polarizing film is usually preferably a coating type polarizing film represented by Optiva Inc., or a polarizing film comprising a binder and iodine or a dichroic dye.
Iodine and dichroic dye in the polarizing film exhibit deflection performance by being oriented in the binder. It is preferable that the iodine and the dichroic dye are aligned along the binder molecule, or the dichroic dye is aligned in one direction by self-assembly such as liquid crystal.

At present, commercially available polarizers (polarizing films) are obtained by immersing a stretched polymer in a solution of iodine or dichroic dye in a bath and allowing iodine or dichroic dye to penetrate into the binder. It is common to make it.
Commercially available polarizers have iodine or dichroic dye distributed about 4 μm (about 8 μm on both sides) from the polymer surface, and a thickness of at least 10 μm is necessary to obtain sufficient polarization performance. The penetrability can be controlled by the solution concentration of iodine or dichroic dye, the temperature of the bath, and the immersion time.

  As described above, the lower limit of the binder thickness is preferably 10 μm. The upper limit of the thickness is preferably as thin as possible from the viewpoint of light leakage of the liquid crystal display device. It is preferably not more than a commercially available polarizing plate (about 30 μm), preferably 25 μm or less, and more preferably 20 μm or less. When the thickness is 20 μm or less, the light leakage phenomenon is not observed on a 17-inch liquid crystal display device.

As the binder for the polarizing film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used. Examples of the polymer include the same polymers as those described in the alignment film.
Most preferred are polyvinyl alcohol and modified polyvinyl alcohol.
The modified polyvinyl alcohol is described in JP-A-8-338913, JP-A-9-152509 and JP-A-9-316127.
Two or more kinds of polyvinyl alcohol and modified polyvinyl alcohol may be used in combination.

The binder of the polarizing film may be cross-linked. As the crosslinked binder, a polymer that can be crosslinked by itself can be used. A polarizing film can be formed by reacting a polymer having a functional group or a binder obtained by introducing a functional group into a polymer between the binders by light, heat, or pH change.
Moreover, you may introduce | transduce a crosslinked structure into a polymer with a crosslinking agent. Crosslinking is generally carried out by applying a coating liquid containing a polymer or a mixture of a polymer and a crosslinking agent on a transparent support and then heating. Since it is sufficient if durability can be ensured at the final product stage, the crosslinking treatment may be performed at any stage until the final polarizing plate is obtained.

The addition amount of the crosslinking agent in the binder is preferably 0.1 to 20% by mass with respect to the binder. The orientation of the polarizing element and the moisture and heat resistance of the polarizing film are improved.
The polarizing film contains a certain amount of a crosslinking agent that has not reacted even after the crosslinking reaction is completed.
However, the amount of the remaining crosslinking agent is preferably 1.0% by mass or less, more preferably 0.5% by mass or less in the polarizing film. In this way, even if the polarizing film is incorporated in a liquid crystal display device and used for a long time or left in a high temperature and high humidity atmosphere for a long time, the degree of polarization does not decrease.
About a crosslinking agent, the description of US reissue patent 23297 is mentioned. Boron compounds (eg, boric acid, borax) can also be used as a crosslinking agent.

As the dichroic dye, an azo dye, stilbene dye, pyrazolone dye, triphenylmethane dye, quinoline dye, oxazine dye, thiazine dye or anthraquinone dye is used. The dichroic dye is preferably water-soluble. The dichroic dye preferably has a hydrophilic substituent (eg, sulfo, amino, hydroxyl).
As an example of the dichroic dye, for example, as a specific example of such a dichroic dye, for example, “Application of Polarizing Film” (published on February 10, 1986, published by CMC) or “COLOR INDEX” , Third Edition, Volume 2 ”(published by The Society of Dyers and Colorists, The American Association of Textile Chemists and Colrists, published in 1971).

(Optical compensation film)
The optical compensation film is generally used in a liquid crystal display device and refers to an optical material that compensates for a phase difference, and is synonymous with a phase difference plate, an optical compensation sheet, and the like. The optical compensation sheet has a birefringence provided with an optically anisotropic layer, and is used for the purpose of removing the coloring of the display screen of the liquid crystal display device or improving the viewing angle characteristics.
The optically anisotropic layer may be formed from a composition containing a liquid crystalline compound or may be formed from a polymer film having birefringence. As the liquid crystal compound, a discotic liquid crystal compound or a rod-like liquid crystal compound is preferable.

  Examples of rod-like liquid crystalline molecules include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. These low-molecular liquid crystalline molecules preferably have a polymerizable group in the molecule (for example, described in paragraph No. [0016] of JP-A No. 2000-304932). In addition to the above low-molecular liquid crystalline molecules, high-molecular liquid crystalline molecules can also be used. The high-molecular liquid crystalline molecule is a polymer having a side chain corresponding to the above low-molecular liquid crystalline molecule. Examples of the optical compensation sheet using polymer liquid crystalline molecules include compounds described in JP-A-5-53016.

  As the discotic liquid crystalline molecule, various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by the Chemical Society of Japan, quarterly chemistry review, No. 22). , Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J. Am. Chem. Soc., Vol. 116, page 2655 (1994)). Regarding the polymerization of discotic liquid crystalline molecules, the description of JP-A-8-27284 can be mentioned.

In order to fix the discotic liquid crystalline molecules by polymerization, it is necessary to bond a polymerizable group as a substituent to the discotic core of the discotic liquid crystalline molecules. A compound in which the discotic core and the polymerizable group are bonded via a linking group is preferable, whereby the alignment state can be maintained even in the polymerization reaction. Examples thereof include compounds described in paragraph numbers [0151] to [0168] of JP-A No. 2000-155216.
In order to optically compensate a liquid crystal cell in which rod-like liquid crystalline molecules such as STN mode are twisted, it is preferable that the discotic liquid crystalline molecules are also twisted.
When an asymmetric carbon atom is introduced into the linking group, the discotic liquid crystal molecules can be twisted and aligned in a spiral shape. Further, even when an optically active compound containing an asymmetric carbon atom (chiral agent) is added to the optically anisotropic layer, the discotic liquid crystalline molecules can be twisted and aligned in a helical manner.

Two or more kinds of discotic liquid crystal molecules may be used in combination. For example, a polymerizable discotic liquid crystalline molecule and a non-polymerizable discotic liquid crystalline molecule as described above can be used in combination.
The non-polymerizable discotic liquid crystalline molecule is preferably a compound obtained by changing the polymerizable group of the polymerizable discotic liquid crystalline molecule described above to a hydrogen atom or an alkyl group. That is, examples of the non-polymerizable discotic liquid crystalline molecules include compounds described in Japanese Patent No. 2640083.

  When the optical compensation film is used as a protective film for the polarizing film, the surface on the side to be bonded to the polarizing film is preferably saponified, and is preferably performed according to the saponifying process.

(adhesive)
The polarizing film and the polarizing plate protective film can be bonded together with an adhesive. As the adhesive, a polyvinyl alcohol resin (including a modified polyvinyl alcohol by an acetoacetyl group, a sulfonic acid group, a carboxyl group, or an oxyalkylene group) or an aqueous boron compound solution can be used. A polyvinyl alcohol resin is preferred. The thickness of the adhesive layer is preferably in the range of 0.01 to 10 μm after drying, and particularly preferably in the range of 0.05 to 5 μm.

(Transmittance)
In order to increase the contrast ratio of the liquid crystal display device, the transmittance of the polarizing plate is preferably higher and the degree of polarization is preferably higher. The transmittance of the polarizing plate is preferably in the range of 30 to 50%, more preferably in the range of 35 to 50%, and most preferably in the range of 40 to 50% with respect to light having a wavelength of 550 nm. . The degree of polarization is preferably in the range of 90 to 100%, more preferably in the range of 95 to 100%, and most preferably in the range of 99 to 100% in light having a wavelength of 550 nm.

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

Moreover, the polarizing plate using the antireflection film of the present invention can be used as a polarizing plate on the image display surface side among two polarizing plates sandwiching the liquid crystal cell of the liquid crystal display device.
In this case, twisted nematic (TN), super twisted nematic (STN), vertical alignment (VA), in-plane switching (IPS), optically compensated bend cell (OCB), electrically controlled birefringence (ECB), etc. The present invention is preferably applied to a mode transmissive, reflective, or transflective liquid crystal display device.

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

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

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

  In particular, for TN mode and IPS mode liquid crystal display devices, as described in JP-A-2001-100043, an optical compensation film having an effect of widening a viewing angle is used as a protective film having two polarizing films on both sides. Of these, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate by using it on the surface opposite to the antireflection film of the present invention.

In addition, when the polarizing plate using the antireflection film of the present invention is used for a transmissive or transflective liquid crystal display device, a commercially available brightness enhancement film (a polarized light separation film having a polarization selective layer, for example, Sumitomo 3M Co., Ltd.) ) Manufactured D-BEF, etc.), a display device with higher visibility can be obtained.
Further, by combining with a λ / 4 plate, it can be used to reduce reflected light from the surface and the inside as a polarizing plate for reflective liquid crystal or a surface protective plate for organic EL display.

The present invention will be described in more detail based on examples, but the present invention is not limited thereto.
(1) Preparation of a solution (sol solutions a to d) containing at least one of hydrolyzate and condensation reaction product of organosilane (A) (preparation of sol solution a (concentration 15.7%))
In a 2,000 ml reaction vessel equipped with a thermometer, nitrogen introduction tube, and dropping funnel, 116 parts by mass of dimethyldimethoxysilane (KBM22, manufactured by Shin-Etsu Chemical Co., Ltd.), 600 parts by mass of i-propanol and diisopropoxyaluminum ethyl 3 parts by mass of acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) was charged, and 20.0 parts by mass of ion-exchanged water was slowly added dropwise at room temperature with stirring. After completion of the dropping, the mixture was stirred at room temperature for 3 hours, reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain a sol solution a. As a result of GPC measurement of the substance thus obtained, Mw = 2,500.

(Preparation of sol solution b (concentration 15.7%))
In a 2,000 ml reaction vessel equipped with a thermometer, nitrogen introduction tube, and dropping funnel, 116 parts by mass of dimethyldimethoxysilane (KBM22, manufactured by Shin-Etsu Chemical Co., Ltd.), 600 parts by mass of i-propanol and diisopropoxyaluminum ethyl 3 parts by mass of acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) was charged, and 20.0 parts by mass of ion-exchanged water was slowly added dropwise at room temperature with stirring. After completion of the dropping, the mixture was stirred at room temperature for 3 hours, reacted at 60 ° C. for 6 hours, and then cooled to room temperature to obtain a sol solution b. As a result of GPC measurement of the substance thus obtained, Mw = 6,000.

(Preparation of sol solution c (concentration: 15.4%))
In a 2,000 ml reaction vessel equipped with a thermometer, nitrogen introduction tube, and dropping funnel, 116 parts by mass of tetramethoxysilane (KBM04, manufactured by Shin-Etsu Chemical Co., Ltd.), 600 parts by mass of i-propanol, and 15 parts by mass of acetylacetone 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) was charged, and 20.0 parts by mass of ion-exchanged water was slowly added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, reacted at 60 ° C. for 1 hour, and then cooled to room temperature to obtain a sol solution c. As a result of GPC measurement of the substance thus obtained, Mw = 1,200.

(Preparation of sol solution d (concentration: 15.4%))
In a 2,000 ml reaction vessel equipped with a thermometer, nitrogen introduction tube, and dropping funnel, 116 parts by mass of tetramethoxysilane (KBM04, manufactured by Shin-Etsu Chemical Co., Ltd.), 600 parts by mass of i-propanol, and 15 parts by mass of acetylacetone 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) was charged, and 20.0 parts by mass of ion-exchanged water was slowly added dropwise at room temperature with stirring. After completion of the dropping, the mixture was stirred at room temperature for 3 hours, reacted at 40 ° C. for 1 hour, and then cooled to room temperature to obtain a sol solution d. As a result of GPC measurement of the substance thus obtained, Mw = 250.

(2) Preparation of fluororesin solution (B) (sol solution e (concentration: 7.9%)) In a 2,000 ml reaction vessel equipped with a thermometer, nitrogen introduction tube, and dropping funnel, Si (OC ₂ H ₅ ) ₄ 5.5 parts by mass, 4 ₃ parts by mass of CF ₃ (CF ₃ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ and 600 parts by mass of i-propanol were charged, and 0.1 mol / L hydrochloric acid at room temperature with stirring. 14.5 parts by mass were slowly added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours, reacted at 60 ° C. for 8 hours, and then cooled to room temperature to obtain sol solution e. As a result of GPC measurement of the substance thus obtained, Mw = 8,800.

(3) Preparation of a solution (sol solution f and g) containing at least one of the hydrolyzate of the silane coupling agent and the condensation reaction product of the hydrolyzate (sol solution f and g) (sol solution f (concentration 10%)) Preparation In a 2,000 ml reaction vessel equipped with a thermometer, a nitrogen inlet tube, and a dropping funnel, 100 parts by mass of 3-acryloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 800 parts by mass of methyl ethyl ketone And 3 parts by mass of diisopropoxyaluminum ethyl acetoacetate (Kelope EP-12, manufactured by Hope Pharmaceutical Co., Ltd.) were added, and 20.0 parts by mass of ion-exchanged water was slowly added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, reacted at 60 ° C. for 3 hours, and then cooled to room temperature to obtain a sol solution f. As a result of GPC measurement of the substance thus obtained, Mw = 2,000.

Preparation of (sol liquid g) In a 1,000 ml reaction vessel equipped with a thermometer, a nitrogen inlet tube, and a dropping funnel, 187 g (0.80 mol) of acryloxyoxypropyltrimethoxysilane and 27.2 g of methyltrimethoxysilane (0. 20 mol), 320 g (10 mol) of methanol and 0.06 g (0.001 mol) of KF were charged, and 15.1 g (0.86 mol) of water was slowly added dropwise at room temperature with stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and then heated and stirred for 2 hours under methanol reflux. Thereafter, low-boiling components were distilled off under reduced pressure, and further filtered to obtain 120 g of sol liquid a-2. As a result of GPC measurement of the substance thus obtained, the mass average molecular weight was 1500, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 30%.

  Moreover, from the measurement result of 1H-NMR, the structure of the obtained substance was the following structure.

  From the gas chromatography analysis, the raw material acryloxypropyltrimethoxysilane had a residual rate of 5% or less.

(4) Preparation of hard coat layer coating solution (Preparation of hard coat layer coating solution (HCL-1))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass F-470 1.5 parts by mass KBM-5103 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-2))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure OXE01 51 parts by mass F-470 1.5 parts by mass KBM-403 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of hard coat layer coating solution (HCL-3))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 651 51 parts by mass F-470 1.5 parts by mass KBM-603 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-4))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass F-470 1.5 parts by mass Sol solution f 800 parts by mass MEK (methyl ethyl ketone) 28 parts by mass Cyclohexanone 503 parts by mass

(Preparation of hard coat layer coating solution (HCL-5))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass F-476 1.5 parts by mass KBM-5103 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of hard coat layer coating solution (HCL-6))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass P-1 1.5 parts by mass KBM-5103 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-7))
PET-30 854 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass F-470 1.5 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-8))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass KBM-5103 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of hard coat layer coating solution (HCL-9))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass F-476 0.10 parts by mass KBM-5103 10.0 parts by weight MEK (methyl ethyl ketone) 11.5 parts by weight MIBK (methyl isobutyl ketone) 27.0 parts by weight

(Preparation of anti-glare hard coat layer coating solution (HCL-10))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass F-476 0.10 parts by mass KBM-5103 10.0 parts by mass Toluene 38.5 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-11))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass F-470 0.10 parts by mass KBM-403 10.0 parts by mass Toluene 38.5 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-12))
PETA 60.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Cross-linked acrylic-styrene particles (30%) 13.3 parts by mass F-470 0.10 parts by mass Toluene 38. 5 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-13))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass KBM-5103 10.0 parts by mass Toluene 38. 5 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-14))
Desolite Z7404 100 parts by mass DPHA 31 parts by mass KBM-5103 10 parts by mass Methyl isobutyl ketone (MIBK) 45 parts by mass

(Preparation of coating liquid for hard coat layer (HCL-15))
Desolite Z7401 100 parts by mass DPHA 20 parts by mass KBM-5103 8 parts by mass Irgacure 184 4 parts by mass KE-P150 7.5 parts by mass Methyl ethyl ketone (MEK) 15 parts by mass Cyclohexanone 10 parts by mass

(Preparation of coating solution for hard coat layer (HCL-16))
PET-30 742 parts by mass Poly (glycidyl methacrylate) 277 parts by mass Irgacure 184 51 parts by mass F-470 1.5 parts by mass KBM-5103 112 parts by mass MEK (methyl ethyl ketone) 728 parts by mass Cyclohexanone 503 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-17))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass F-476 0.10 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10.0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-18))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass SH28PA 0.02 parts by mass Sol solution g 10. 0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10.0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-19))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass Aggregated silica particles (30%) 12.0 parts by mass F-476 0.10 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10. 0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-20))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass Aggregated silica particles (30%) 12.0 parts by mass SH28PA 0.02 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10.0 parts by mass Part

(Preparation of anti-glare hard coat layer coating solution (HCL-21))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Crosslinked acrylic-styrene particles (30%) 13.3 parts by mass FZ-2191 0.02 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10.0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-22))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass Aggregated silica particles (30%) 12.0 parts by mass FZ-2191 0.02 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10. 0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-23))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass SX-350 (30%) 1.7 parts by mass Cross-linked acrylic-styrene particles (30%) 13.3 parts by mass TSF4460 0.05 parts by mass Sol solution g 10. 0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10.0 parts by mass

(Preparation of anti-glare hard coat layer coating solution (HCL-24))
PETA 50.0 parts by mass Irgacure 184 2.0 parts by mass Aggregated silica particles (30%) 12.0 parts by mass FZ-3704 0.05 parts by mass Sol solution g 10.0 parts by mass Toluene 28.5 parts by mass Cyclohexanone 10. 0 parts by mass

Each of the above components is as follows.
“PET-30”: Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd.).
“PETA”: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.).
“Poly (glycidyl methacrylate)”: weight average molecular weight 15,000.
“Irgacure 184/651 / OXE01”: photopolymerization initiator (manufactured by Ciba Specialty Chemicals).
“KBM-5103 / 403/603”: a silane coupling agent represented by the general formula (1) (manufactured by Shin-Etsu Chemical Co., Ltd.).
“SX-350”: average particle size 3.5 μm crosslinked polystyrene particles (refractive index 1.60, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser).
“Crosslinked acrylic-styrene particles”: average particle size 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion).
“P-1”: F-470 was purified to have a molecular weight distribution (Mw / Mn) of 1.2 “F-470 / 476”: a fluorine-based surface modifier. (Dainippon Ink Co., Ltd.)
“Desolite Z7404”: hard coat composition containing zirconia fine particles: solid content concentration of 60% by mass, zirconia fine particle content of 70% by mass, solid content, average particle size of about 20 nm, solvent composition MIBK: MEK = 9: 1, JSR Corporation Made)
“Desolite Z7401”: hard coat composition containing zirconia fine particles: solid content concentration 48% by mass, zirconia fine particle content 70% by mass, solid content, average particle size of about 20 nm, solvent composition cyclohexanone: MEK = 5: 5, JSR Corporation “DPHA”: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
“KE-P150”: silica particles having an average particle diameter of 1.5 μm, manufactured by Nippon Shokubai Co., Ltd., 30% cyclohexanone dispersion. (Used after dispersion for 20 minutes at 10,000rpm in a Polytron disperser)
“SH28PA / FZ-2191 / FZ-3704”: a silicone-based surface modifier. (Toray Dow Corning Co., Ltd.)
“TSF4460”: silicone-based surface modifier. (GE Toshiba Silicone Co., Ltd.)
“Aggregated silica particles (30%)”: secondary average particle size of 1.5 μm (refractive index: 1.48, 30% toluene dispersion, used after dispersion for 20 minutes at 10,000 rpm in a polytron disperser)

(5) Preparation of coating solution for low refractive index layer Each component shown below was put into a mixing tank, stirred, and then filtered through a polypropylene filter having a pore size of 0.4 μm.
(Preparation of coating solution for low refractive index layer (LL-1))
Sol liquid c 15.9 parts by weight Sol liquid e 12.7 parts by weight Sol liquid f 8.0 parts by weight Cymel 303 0.1 parts by weight p-toluenesulfonic acid 0.03 parts by weight i-propanol 36.0 parts by weight MEK (Methyl ethyl ketone) 30.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-2))
Sol liquid c 13.7 parts by mass Sol liquid e 11.0 parts by mass Sol liquid f 7.0 parts by mass IPA-ST-L 2.3 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass Parts i-propanol 36.0 parts by weight MEK (methyl ethyl ketone) 30.0 parts by weight butanol 4.8 parts by weight

(Preparation of coating solution for low refractive index layer (LL-3))
Sol liquid c 12.7 parts by mass Sol liquid e 11.0 parts by mass Sol liquid f 7.0 parts by mass Hollow silica fine particle sol 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 30.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-4))
Sol liquid c 12.7 parts by mass Sol liquid e 11.0 parts by mass KBM-5103 0.7 parts by mass Hollow silica fine particle sol 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 36.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-5))
Sol liquid c 12.7 parts by mass Sol liquid e 11.0 parts by mass KBM-403 0.7 parts by mass Hollow silica fine particle sol 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 36.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-6))
Sol liquid c 12.7 parts by mass Sol liquid e 11.0 parts by mass KBM-603 0.7 parts by mass IPA-ST-L 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass Parts i-propanol 36.0 parts by weight MEK (methyl ethyl ketone) 36.0 parts by weight butanol 4.8 parts by weight

(Preparation of coating solution for low refractive index layer (LL-7))
Sol liquid a 12.7 parts by mass Sol liquid e 11.0 parts by mass KBM-5103 0.7 parts by mass Hollow silica fine particle sol 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 36.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-8))
Sol liquid b 12.7 parts by mass Sol liquid e 11.0 parts by mass KBM-5103 0.7 parts by mass Hollow silica fine particle sol 4.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 36.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-9))
Sol liquid d 15.9 parts by mass Sol liquid e 12.7 parts by mass Sol liquid f 8.0 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (Methyl ethyl ketone) 30.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-10))
Sol liquid c 8.8 parts by mass Sol liquid e 30.0 parts by mass Sol liquid f 1.0 parts by mass Cymel 303 0.3 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 19.0 parts by mass MEK (Methyl ethyl ketone) 36.8 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-11))
Sol liquid c 17.2 parts by mass Sol liquid e 3.8 parts by mass Sol liquid f 1.0 parts by mass IPA-ST-L 2.3 parts by mass Cymel 303 0.02 parts by mass p-toluenesulfonic acid 0.01 parts by mass Parts i-propanol 36.2 parts by weight MEK (methyl ethyl ketone) 36.0 parts by weight butanol 4.8 parts by weight

(Preparation of coating solution for low refractive index layer (LL-12))
Sol liquid c 13.7 parts by mass Sol liquid e 11.0 parts by mass KBM-503 0.7 parts by mass Hollow silica fine particle sol 2.3 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 36.0 parts by mass Butanol 4.8 parts by mass

(Preparation of coating solution for low refractive index layer (LL-13))
Sol liquid c 18.1 parts by mass Sol liquid e 14.6 parts by mass Cymel 303 0.1 parts by mass p-toluenesulfonic acid 0.03 parts by mass i-propanol 36.0 parts by mass MEK (methyl ethyl ketone) 30.0 parts by mass 4.8 parts by mass of butanol

(Preparation of coating solution for low refractive index layer (LL-14))
Colcoat N103 (2%) 245 parts by mass Opstar JTA105 (5%) 100 parts by mass Opster JTA105A (5%) 1 part by mass IPA-ST-L 23 parts by mass Sol solution f 15 parts by mass Butyl acetate 365 parts by mass

(Preparation of coating solution for low refractive index layer (LL-15))
Colcoat N103 (2%) 245 parts by mass Opstar JTA105 (5%) 100 parts by mass Opstar JTA105A (5%) 1 part by mass Hollow silica fine particle sol 23 parts by mass Sol solution f 15 parts by mass Butyl acetate 365 parts by mass

(Preparation of coating solution for low refractive index layer (LL-16))
Sol liquid c 15.9 parts by weight Sol liquid e 12.7 parts by weight Sol liquid f 8.0 parts by weight Cymel 303 0.1 parts by weight Salt of p-toluenesulfonic acid and 4-methylmorpholine 0.05 parts by weight i- Propanol 36.0 parts by mass MEK (methyl ethyl ketone) 30.0 parts by mass Butanol 4.8 parts by mass

“IPA-ST-L”: colloidal silica dispersion (average particle size 45 nm, solid content concentration 30%, manufactured by Nissan Chemical Co., Ltd.)
“Hollow silica fine particle sol”: particle size of about 40 to 50 nm, shell thickness of 6 to 8 nm, refractive index of 1.31, solid content concentration of 20%, main solvent isopropyl alcohol, according to Preparation Example 4 of JP-A-2002-79616 By changing the particle size)
“Cymel 303”: Methoxylated methylmelamine (Mitsui Cytec Co., Ltd.)
“KBM-5103 / 403/603/503”: a silane coupling agent represented by the general formula (1) (manufactured by Shin-Etsu Chemical Co., Ltd.).
"Colcoat N103": Organosiloxane oligomer (mass average molecular weight 950, manufactured by Colcoat)
“OPSTAR JTA105”: Fluorine compound (polyethylene glycol, hexamethylol melamine, containing acid generator, manufactured by JSR, mass average molecular weight 10,000 to 30,000)
"OPSTAR JTA105A": Curing agent (manufactured by JSR)

(6) Preparation of antistatic layer-forming composition coating solution (AS-1) 100 g of ATO-dispersed hard coat agent “Pertron C-4456-S7” (solid content 45%) manufactured by Nippon Pernox Co., Ltd., 30 g of cyclohexanone , 10 g of methyl ethyl ketone, silane coupling agent “KBM-5103” {3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.} 1.5 g are added, and after stirring, filtered through a polypropylene filter having a pore size of 10 μm. Then, an antistatic layer forming composition coating solution (AS-1) was prepared.

[Example 1]
(Preparation of antireflection film)
Using the above coating liquid for hard coat layer (HCL-1) and low refractive index layer (LL-1), coating was performed according to the coating and drying methods described below. A hard coat layer coating solution (HCL-1) is applied to a triacetylcellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd., refractive index: 1.48) with a thickness of 80 μm under the condition of a conveyance speed of 20 m / min. Apply using a gravure coater, after drying at 30 ° C. for 30 seconds in the first (first) drying zone, and further at 110 ° C. for 2 minutes in the subsequent second drying zone, the oxygen concentration is 0 Using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under a nitrogen purge of 1% or less, the coating layer was irradiated by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 300 mJ / cm ^2. Cured and wound up. The maximum wind speed in the first drying zone was 0.2 m / s, and it was confirmed that the coating film was set in the drying zone. This hard coat layer had a refractive index of 1.51 and a layer thickness of 7 μm.

Subsequently, the above-described coating solution for low refractive index layer (LL-1) is applied using a gravure coater under the condition of a conveyance speed of 20 m / min, and dried at 25 ° C. for 30 seconds in the first (first) drying zone. After that, it was dried at 90 ° C. for 2 minutes, heat-cured at 140 ° C. for 5 minutes, and purged with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less, and a 240 W / cm air-cooled metal halide lamp (
The low refractive index layer (refractive index: 1.43, layer thickness: 86 nm) was provided by irradiating with ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² . . In this way, an antireflection film (AF-1) was produced.

Furthermore, antireflection films (AF-2) to (AF-24) and (AF-51) to (AF-60) were produced in the same manner as AF-1 using the coating solutions shown in Tables 1 and 2. . In AF-2, 6, 14, 19, 23, 53, 54, an antistatic layer provided between a support and a hard coat layer was prepared. The thickness of the antistatic layer was set to 100 nm. In AF-53, 54, 56, and 58, the thickness of the hard coat layer was set to 2.5 μm.
In AF-59, a corona discharge treatment was performed on the hard coat layer under the conditions of 2.0 kW and a line speed of 12 m / min before coating the coating solution for the low refractive index layer.
However, the coating solution LL-9 for low refractive index layer used for AF-25 gradually thickened after the preparation, and finally gelled and could not be applied.
Further, the low refractive index layer coating solution LL-16 used in AF-60 was superior in stability over time to other low refractive index layer coating solutions.

(Evaluation of antireflection film (AF))
About the film sample obtained above, the following items were evaluated.
(1) Specular reflectance The spectrophotometer "V-550" {manufactured by JASCO Corporation} is equipped with an adapter "ARV-474", and the incident angle of each antireflection film sample in the wavelength range of 380 to 780 nm. The specular reflectance at an outgoing angle of -5 ° at 5 ° was measured, the average reflectance in the region of 450 to 650 nm was calculated, and the antireflection property was evaluated.

(2) Steel Wool Scratch Resistance Evaluation A rubbing test of each antireflection film sample surface was performed using a rubbing tester under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool “Grade No. 0000” (manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ²
Tip contact area: 1 cm × 1 cm, number of rubs: 10 reciprocations The oily black ink was applied to the back of the rubbed sample and visually observed with reflected light, and scratches on the rubbed part were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully.
○ △: Weak scratches are visible.
Δ: Moderate scratches are visible.
Δ: There are scratches that can be seen at first glance.

(3) Fingerprint wiping property A finger is pressed against the surface of each antireflective film sample having the low refractive index layer to attach a fingerprint, and wiped with a cellulose nonwoven fabric “Bencot M-3” {manufactured by Asahi Kasei Corporation}. The ease of removal was evaluated according to the following three levels.
○: Wipe cleanly in 3 round trips.
Δ: Wipe off with 10 reciprocations.
X: The fingerprint remains unwiped even after 10 round trips.

(4) Evaluation of antifouling property An oil-based pen “Mackey Care” {manufactured by Zebra} attached to the surface of each antireflective film sample having a low refractive index layer is made of cellulose nonwoven fabric “Bencot M-3” {Asahi Kasei ( The product was wiped off and the ease of removal was evaluated by the following two steps.
○: The oil pen can be completely wiped off.
X: A trace of wiping off the oil pen remains.

(5) Antifouling durability evaluation The above antifouling evaluation was repeated at the same location, and the following three-stage evaluation was performed by the number of remaining wiping traces.
○: Can be wiped 6 times or more in total.
Δ: Wipe off 2 to 5 times in total.
×: Can be wiped off only once.

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

(7) Color unevenness evaluation Oily black ink is applied to the back side of the sample, and visually observed with reflected light of “National Parrook 3 wavelength type daylight white (FL 15EX-N 15W)” in the dark room. Evaluated by criteria.
A: Little concern.
○: It looks faint but I don't mind.
Δ: A little worrisome
X: I am quite worried.

(8) Evaluation of surface segregation degree of silicone (Si atom) and fluoroalkyl (F atom) Measured for each antireflection film with ESCA-3400 manufactured by Shimadzu Corporation (vacuum degree 1 × 10 ⁻⁵ Pa, X-ray source The intensity ratio Si2p / C1s (= Si (a)) of the photoelectron spectrum of the outermost surface Si2p, C1s, which is the target Mg, voltage 12 kV, current 20 mA) and the ion etching apparatus attached to ESCA-3400 (ion gun, voltage 2 kV, From the intensity ratio Si2p / C1s (= Si (b)) of the photoelectron spectrum measured from the surface obtained by cutting the low refractive index layer at a current of 20 mA until the layer thickness is reduced to 1/5 (± 5%). , Changes in the respective strength ratios before and after etching, Si (a) / Si (b), and changes in Si2p / C1s ratio before and after (Intensity ratio of photoelectron spectrum at the top of the low refractive index layer / change in intensity ratio of photoelectron spectrum in the vicinity of the lower layer 80% deep from the surface of the low refractive index layer) was evaluated in the following three stages. The above measurement was performed at three locations at least 2 cm apart from each other on the same film surface.
A: Strength ratio after etching is 2 times or more.
○: Strength ratio after etching is less than 2 times, 1.5 times or more.
Δ: Intensity ratio after etching is less than 1.5 times Note that C1s is the intensity at the peak position of each photoelectron spectrum, and Si2p is the peak position derived from silicone (Si atom of polydimethylsiloxane) having a binding energy of around 105 eV. The strength of was used for the above-described strength ratio calculation, and was distinguished from Si atoms derived from inorganic silica particles. Preliminary experiment in which the surface of the low-refractive index layer is gradually scraped under various etching conditions, and measurement is performed after obtaining the condition that the depth from the surface is 80% from the etching conditions required to reach the lower hard coat layer. did.

(9) Surface haze By the following measurements, the total haze (H), internal haze (Hi), and surface haze (Hs) of the obtained film were measured.
(A) The total haze value (H) of the film obtained according to JIS-K7136 is measured.
(B) A few drops of silicone oil were added to the front and back surfaces of the obtained film on the low refractive index layer side, and two glass plates having a thickness of 1 mm (micro slide glass product number S 9111, manufactured by MATSANAMI) were used from the front and back. The two glass plates and the obtained film are optically closely attached, and the haze is measured with the surface haze removed, and only silicone oil is sandwiched between two separately measured glass plates. The value obtained by subtracting the haze measured in step 1 was calculated as the internal haze (Hi) of the film.
(C) A value obtained by subtracting the internal haze (Hi) calculated in (b) from the total haze (H) measured in (a) above was calculated as the surface haze (Hs) of the film.

(10) 60 ° Glossiness The 60 ° glossiness was measured according to JIS-Z8741 using a gloss meter (GM-26PRO / Auto, manufactured by Murakami Color Research Laboratory Co., Ltd.).

(11) Measurement of log SR (Surface Resistance) After adjusting the humidity at 25 ° C. and 60% RH for 2 hours, the surface resistance value (SR) was measured by the circular electrode method. The log SR was calculated by taking the common logarithm of SR.

(12) Limit load by rubbing swab after ozone exposure Each sample was processed into a polarizing plate (processing to the polarizing plate was performed in the same manner as in Example 3), and then in an environment of ozone 10 ppm, 30 ° C., 60% RH. And stored for 192 hours (8 days). A cotton swab (Health Refre (trade name) manufactured by Toyo Sanyo Co., Ltd.) is fixed to the rubbing tip of a rubbing tester, and the sample is fixed with clips on the top and bottom of a smooth dish. Was immersed in water at 25 ° C., a load was applied to a cotton swab, and a 20 reciprocating rubbing test was conducted.
Rubbing distance (one way): 1 cm, rubbing speed: about 2 reciprocations / second After drying the water on the surface of the sample after rubbing, it was visually observed whether the film was peeled off. The test was performed 10 times on the same sample, and the test was performed starting from an initial load of 100 g and increasing the load by 50 g until film peeling occurred 5 times or more. The load at which film peeling was less than 5 times during 10 tests was defined as the critical load. The film peeling was judged based on whether the reflection state of the surface was visually changed. A larger limit load corresponds to better scratch resistance.

  The above results are shown in Tables 3 and 4 below.

  As shown in Tables 3 and 4 above, it was found that AF-15 and 20 as comparative examples were inferior in scratch resistance. It can be seen that AF-7 is inferior in fingerprint wiping and dusting.

[Example 2]
(Preparation of antireflection film)
With an ultrasonic dust remover, the surface of the application side of a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) with a film thickness of 80 μm is subjected to charge removal treatment, and then the hard coat layer coating liquid (HCL-1) is applied. The die coater 10 shown in FIG. 1 was applied at a coating rate of 30 m / min and a coating amount of 17.5 cc / m ² . The degree of vacuum in the vacuum chamber was 0.5 kPa. In the application of HCL-1, the application was performed with the gap GL between the downstream lip land 18b and the web 12 set to 100 μm. The coated web was then dried at 80 ° C., and then a 160 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. Then, the coating layer was cured by irradiating with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 500 mJ / cm ² , and a hard coat layer having a refractive index of 1.51 and a thickness of 7 μm was formed.

On the hard coat layer, a low refractive index layer coating solution (LL-1) was applied at a coating speed of 30 m / min and a coating amount of 5.0 cc / m ² using the die coater. The degree of vacuum in the vacuum chamber was 0.55 kPa. The coated web is then dried at 25 ° C. for 30 seconds, then dried at 90 ° C. for 2 minutes, heated and cured at 140 ° C. for 5 minutes, and purged with nitrogen so that the atmosphere has an oxygen concentration of 0.1% by volume or less. However, a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) was used to irradiate ultraviolet rays having an illuminance of 600 mW / cm ² and an irradiation amount of 400 mJ / cm ² , and a low refractive index layer (refractive index of 1.43). , A film thickness of 83 nm) was formed. In this way, an antireflection film (AF-26) was produced.

Further, antireflection films (AF-27) to (AF-49) and (AF-61) to (AF-70) were produced in the same manner as AF-26 using the coating solutions shown in Table 5 and Table 6 below. did. In AF-27, 31, 39, 44, 48, 63, 64, the thickness of the antistatic layer was adjusted to 100 nm. In AF-63, 64, 66, and 67, the thickness of the hard coat layer was set to 2.5 μm. In AF-69, a corona discharge treatment was performed on the hard coat layer under the conditions of 2.0 kW and a line speed of 12 m / min before coating the coating solution for the low refractive index layer. However, the coating solution LL-9 for low refractive index layer used for AF-50 was gradually thickened after preparation, and finally gelled and could not be applied.
Further, the low refractive index layer coating solution LL-16 used for AF-70 was superior in stability over time to other low refractive index layer coating solutions.

(Evaluation of antireflection film (AF))
About the film sample obtained above, evaluation similar to Example 1 was performed and the film sample produced using the same coating liquid obtained the same result.

[Example 3]
(Preparation of protective film for polarizing plate)
In the antireflection films (AF-1) to (AF-24), (AF-26) to (AF-49), and (AF-51) to (AF-70) produced in Examples 1 and 2, reflection was performed. An alkali solution composed of 57 parts by mass of potassium hydroxide, 120 parts by mass of propylene glycol, 535 parts by mass of isopropyl alcohol, and 288 parts by mass of water is kept at 40 ° C. on the surface of the transparent support opposite to the side having the prevention layer. The surface of the transparent support was saponified.
The alkaline solution on the surface of the saponified transparent support was thoroughly washed with water and then sufficiently dried at 100 ° C. Thus, the protective film for polarizing plates was produced.

(Preparation of polarizing plate)
A polyvinyl alcohol film {made by Kuraray Co., Ltd.} having a layer thickness of 75 μm was immersed in an aqueous solution composed of 1000 g of water, 7 g of iodine, and 10.5 g of potassium iodide to adsorb iodine. Subsequently, this film was uniaxially stretched 4.4 times in the longitudinal direction in a 4% by mass boric acid aqueous solution, and then dried in a tension state to produce a polarizing film.

  Next, a saponified triacetyl cellulose surface of each antireflection film of the present invention (protective film for polarizing plate) was bonded to one surface of the polarizing film using a polyvinyl alcohol adhesive as an adhesive. . Further, a cellulose acylate film “TD80UF” (manufactured by Fuji Photo Film Co., Ltd.) saponified in the same manner as described above was bonded to the other surface of the polarizing film using the same polyvinyl alcohol-based adhesive.

(Evaluation of image display device)
Each polarizing plate of the present invention thus produced is mounted on a TN, STN, IPS, VA, OCB, and ECB mode transmissive, reflective, or transflective liquid crystal display device and evaluated. As a result, all of these liquid crystal display devices were excellent in antireflection performance and extremely excellent in visibility.

[Example 4]
(Preparation of polarizing plate)
The surface of the optical compensation film “Wide View Film A 12B” {manufactured by Fuji Photo Film Co., Ltd.) opposite to the side having the optical compensation layer was saponified under the same conditions as in Example 3.

  Next, the antireflection film (protective film for polarizing plate) prepared in Example 3 was formed on one surface of the polarizing film by using a polyvinyl alcohol adhesive as an adhesive for the polarizing film prepared in Example 3. The saponified triacetyl cellulose surfaces were bonded together. Further, the triacetyl cellulose surface of the saponified optical compensation film was bonded to the other surface of the polarizing film using the same polyvinyl alcohol adhesive.

(Evaluation of image display device)
Each polarizing plate of the present invention thus manufactured is mounted on a TN, STN, IPS, VA, OCB, and ECB mode transmission type, reflection type, or semi-transmission type liquid crystal display device and evaluated. As a result, these liquid crystal display devices do not use an optical compensation film and are superior in contrast in a bright room than the liquid crystal display device equipped with the polarizing plate described above, and have very high vertical and horizontal viewing angles. It was wide and excellent in antireflection performance, and was extremely excellent in visibility and display quality.

[Example 5]
A polarizing plate was prepared using the following support.
Support 1: A triacetylcellulose film produced according to Example 1 of JP-A-2001-249223.
Support 2: A triacetylcellulose film produced according to Example 2 of JP-A-2001-249223.
Support 3: A triacetylcellulose film produced according to Example 2 of JP-A-2003-170492.
Support 4: Triacetyl cellulose film “Fujitac TD-80U” having a thickness of 80 μm {manufactured by Fuji Photo Film Co., Ltd.}.

Each retardation value is shown below.
Support 1: Re = 40 nm, Rth = 130 nm.
Support 2: Re = 50 nm, Rth = 240 nm.
Support 3: Re = 64 nm, Rth = 120 nm.
Support 4: Re = 4 nm, Rth = 45 nm.

[Preparation of Polarizing Plate (P-1)]
Iodine was adsorbed on the stretched polyvinyl alcohol film to produce a polarizing film (PF-1). First, a commercially available triacetyl cellulose (support 4) was saponified and attached to one side of the polarizing film (PF-1) using a polyvinyl alcohol-based adhesive. Next, the support 1 was subjected to saponification treatment and attached to the opposite side of the polarizing film (PF-1) using a polyvinyl alcohol-based adhesive. At that time, the transmission axis of the polarizing film (PF-1) and the slow axis of the support 1 are arranged in parallel, and the transmission axis of the polarizing film (PF-1) and a commercially available triacetyl cellulose film ( A polarizing plate was produced by placing the support 4) so as to be orthogonal to the slow axis of the support 4). The polarizing plate thus obtained was designated as P-1.

[Preparation of Polarizing Plate (P-2)]
A polarizing plate (P-2) was produced in the same manner as in the polarizing plate (P-1) except that the support 1 was used instead of the support 4.

[Preparation of Polarizing Plate (P-3)]
A polarizing plate (P-3) was produced in the same manner as in the polarizing plate (P-1) except that the support 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-4)]
A polarizing plate (P-4) was produced in the same manner as in the polarizing plate (P-1) except that the support 3 was used instead of the support 4.

[Preparation of Polarizing Plate (P-1A)]
A polarizing plate (P-1A) was produced in the same manner as in the polarizing plate (P-1) except that the antireflection film sample AF-3 of Example 1 was used instead of the support 4.

[Preparation of Polarizing Plate (P-2A)]
A polarizing plate (P-2A) was produced in exactly the same manner as in the polarizing plate (P-2) except that the antireflection film sample AF-18 of Example 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-3A)]
A polarizing plate (P-3A) was produced in the same manner as in the polarizing plate (P-3) except that the antireflection film sample AF-23 of Example 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-1B)]
A polarizing plate (P-1B) was produced in the same manner as in the polarizing plate (P-1) except that the antireflection film sample AF-54 of Example 1 was used instead of the support 4.

[Preparation of Polarizing Plate (P-2B)]
A polarizing plate (P-2B) was produced in the same manner as in the polarizing plate (P-2) except that the antireflection film sample AF-64 of Example 2 was used instead of the support 4.

[Preparation of Polarizing Plate (P-3B)]
A polarizing plate (P-3B) was produced in the same manner as in the polarizing plate (P-3) except that the antireflection film sample AF-65 of Example 2 was used instead of the support 4.

[Example 6]
A pair of polarizing plates and a pair of optical compensation sheets provided in a liquid crystal display device “VL-1530S” {manufactured by Fujitsu Ltd.} using a vertical alignment type liquid crystal cell were peeled off, and produced in Example 5 instead. One polarizing plate was attached to each of the observer side and the backlight side via an adhesive. The crossed nicols were arranged so that the transmission axis of the polarizing plate on the observer side was in the vertical direction and the transmission axis of the polarizing plate on the backlight side was in the horizontal direction. Images of the manufactured liquid crystal display device were displayed, and sensory evaluation of external light, reflection of background, and glare was performed.

  As a result, the devices having the polarizing plates (P-1A to 3A, P-1B to 3B) of the present invention have lower reflectivity than the devices having the polarizing plates (P-1 to 4), so that the external light and background are reduced. It was found that there was little reflection of the image and the visibility was extremely high with no glare.

It is a cross-sectional schematic diagram which shows an example of the die-coater used suitably for manufacture of the antireflection film of this invention. It is a figure which shows the cross-sectional shape of the slot die 13 shown in FIG. FIG. 2 is a perspective view showing a slot die 13 shown in FIG. 1. FIG. 3 is a cross-sectional view showing a decompression chamber 40 and a web 12. FIG. 3 is a cross-sectional view showing a decompression chamber 40 and a web 12.

Explanation of symbols

GB gap GS gap 10 coater 11 backup roll 12 web 13 slot die 14 coating solution 14a bead 14b A coating film is formed.
15 Pocket 16 Slot 16a Opening 17 Tip lip 18 Land (flat part)
18a upstream lip land 18b downstream lip land 30 conventional slot die 31a upstream lip land 31b downstream lip land 32 pocket 33 slot 40 decompression chamber 40a back plate 40b side plate rate 40c screw

Claims (22)

At least one of hydrolyzate of organosilane having a weight average molecular weight in terms of ethylene glycol of 500 to 10,000 and a condensation reaction product of the hydrolyzate (A), and having a weight average molecular weight in terms of polystyrene of 5000 or more, Fluorine-containing resin (B) having an alkyl structure and a polysiloxane structure, and at least a silane coupling agent represented by the general formula (1) or a hydrolyzate of the silane coupling agent and a condensation reaction product of the hydrolyzate A curable composition containing any one of (C).
Formula _{^{(1) :( R a) m}} -Si (X a) 4-m
(However, X ^a is a hydroxyl group or a hydrolyzable group. R ^a is a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkenyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, A substituent having at least one of a carbamoyl group and an acylamino group, m is an integer represented by 1 ≦ m ≦ 3. The organosilane in the hydrolyzate of the organosilane and the condensation reaction product of the hydrolyzate (A) is a compound represented by the general formula (2). Curable composition.
General formula (2): ( ^Rb ) _m- Si ( ^Xb ) _4-m
(However, ^Xb is a hydroxyl group or a hydrolyzable group. ^Rb represents an unsubstituted alkyl group or an unsubstituted aryl group. M is an integer represented by 0 ≦ m ≦ 3.) The curable composition according to claim 1 or 2, wherein R ^a is a substituent having at least one of an epoxy group, an acyloxy group, and an acylamino group. The curable composition according to claim 1, wherein R ^a is a substituent having an acryloyloxy group.   The curable composition according to any one of claims 1 to 4, comprising inorganic fine particles (D) having an average particle diameter of 5 nm to 100 nm.   The curable composition according to claim 5, wherein the inorganic fine particles (D) have pores having an average pore diameter of 0.01 nm to 90 nm in at least one of the inside and the surface.   The curable composition according to any one of claims 1 to 6, wherein a fluorine atom content in the curable composition is 5 to 60% by mass.   The curable composition according to claim 1, further comprising a crosslinkable compound and an acid generator.   A cured film obtained by curing the curable composition according to claim 1 by at least one of heat and ionizing radiation. An antireflection film in which a hard coat layer is provided directly or via another layer on a transparent support, and an antireflection layer is further laminated on the hard coat layer,
The hard coat layer comprises a resin composition curable by at least one of heat and ionizing radiation, a silane coupling agent represented by the general formula (1), a hydrolyzate of the silane coupling agent, and its hydrolysis Formed by a cured film comprising a curable composition containing at least one of the condensation reaction products of decomposition products,
And the said antireflection layer is formed with the cured film of Claim 9, The antireflection film characterized by the above-mentioned.
Formula _{^{(1) :( R a) m}} -Si (X a) 4-m
(However, ^Xa is a hydroxyl group or a hydrolyzable group, and ^Ra is a halogen atom, hydroxyl group, mercapto group, carboxyl group, epoxy group, alkenyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group. A substituent having at least one acylamino group, m is an integer represented by 1 ≦ m ≦ 3.)   The antireflective film according to claim 10, wherein the cured composition forming the hard coat layer contains a leveling agent.   The anti-reflection film according to claim 11, wherein the leveling agent is a fluorine-based compound and / or a silicone-based compound. The curable composition for forming the hard coat layer contains a compound composed of a fluoroaliphatic group-containing monomer represented by the following general formula (3). Antireflection film.
General formula (3)

(In General Formula (3), R ⁰ represents a hydrogen atom, a halogen atom or a methyl group, L represents a divalent linking group, and n represents an integer of 1 to 18.)   14. The photoelectron spectrum intensity ratio Si / C in an 80% lower layer from the outermost surface and the outermost surface of the antireflection layer is at least twice as large as the 80% lower layer in the outermost surface. The antireflection film as described.   The antireflection film according to any one of claims 10 to 14, wherein the haze caused by surface scattering is 3% or less, and the 60 ° gloss is 60% to 120%.   The haze caused by surface scattering is 3.5% or more, and the 60 ° glossiness is 20% to 80%.   The antireflection film according to claim 10, further comprising a transparent antistatic layer having a conductive material, wherein the antireflection film has a surface resistance value logSR of 12 or less.   The antireflection film according to any one of claims 10 to 17, wherein a limit load in a water swab rubbing test on the surface of the antireflection film after exposure to 10 ppm of ozone for 192 hours is 400 g or more.   A polarizing plate comprising the antireflection film according to claim 10 as at least one of a protective film for a polarizing film.   The antireflection film according to any one of claims 10 to 18 is used for one of the protective films of the polarizing film, and an optical compensation film having optical anisotropy is used for the other of the protective films of the polarizing film. Polarizer.   An image display device, wherein the antireflection film according to claim 10 or the polarizing plate according to claim 19 or 20 is disposed on an image display surface.   The image according to claim 21, wherein the image display device is a transmissive, reflective, or transflective liquid crystal display device in any one of TN, STN, IPS, VA, OCB, and ECB modes. Display device.

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