JP5046482B2 - Method for producing inorganic oxide fine particle dispersion, inorganic oxide fine particle dispersion, coating composition, optical film, antireflection film, polarizing plate, and liquid crystal display device - Google Patents

Description

  The present invention relates to an inorganic oxide fine particle dispersion in which inorganic oxide fine particles are stably dispersed, and a coating composition containing the same. Moreover, it is related with the optical film formed from this coating composition, especially an antireflection film. Furthermore, the present invention relates to a polarizing plate and a liquid crystal display device provided with the optical film, particularly an antireflection film.

It is being studied to improve the scratch resistance, strength of cured products, adhesion with other materials that come into contact with organic materials and inorganic materials in adhesives, exterior paints, hard coats, antireflection films, etc. Yes.
When blending an inorganic material and an organic material, it is necessary that the inorganic material does not cause unnecessary aggregation. One of the commonly performed methods is a method in which an inorganic material is dispersed in a solvent having an affinity for an organic material and then mixed with the organic material to form a film. In order to obtain stable performance, it is important that the inorganic material is stably dispersed in the solvent. Specifically, it is important to control hydrophilicity / hydrophobicity and steric hindrance on the surface of the inorganic material, and it is known that the inorganic oxide fine particles are subjected to a surface treatment using alkoxysilane. For example, “Pigment Dispersion Technology Surface Treatment, Usage of Dispersing Agents and Dispersibility Evaluation” (edited by the Technical Information Association, 1999) describes a method of dispersing inorganic particles in an organic solvent using a silane coupling agent. However, it was still insufficient in terms of the stability of the dispersion.

  In particular, in the combination of a polymerization-curing organic material and inorganic particles, alkoxysilanes containing a polymerization group and / or hydrolysis condensates thereof have attracted attention. For example, Patent Document 1 (Japanese Patent Laid-Open No. 9-169847) proposes the combined use of a specific polyalkoxypolysiloxane and a polymerizable silane coupling agent, but the polyalkoxypolysiloxane and the polymerizable silane coupling are proposed. Since the reaction with the agent is not sufficiently performed and the introduction rate of the polymerizable group is low, the scratch resistance and strength of the cured product are not sufficient. Patent Document 2 (Japanese Patent Laid-Open No. 9-40909) reports a partial co-hydrolysis condensate of an alkoxysilane containing an organic functional group and a tetraalkoxysilane. However, the storage stability of the liquid is not sufficient. There wasn't. As described above, the conventional techniques are insufficient in terms of the scratch resistance and strength of the film and the storage stability of the liquid, and further improvements have been demanded.

  On the other hand, optical films, particularly antireflection films, generally reflect external light in display devices such as cathode ray tube display (CRT), plasma display (PDP), electroluminescence display (ELD), and liquid crystal display (LCD). In order to prevent contrast reduction and image reflection due to the optical interference, it is arranged on the outermost surface of the display so as to reduce the reflectance by using the principle of optical interference.

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

  In order to lower the refractive index of the material, there are means of introducing fluorine atoms and lowering the density (introducing voids), but both are in the direction that the film strength and adhesion are impaired and the scratch resistance is lowered, and low Reconciling refractive index and high scratch resistance has been a difficult task.

  In Patent Document 3 (Japanese Patent Laid-Open No. 11-189621), Patent Document 4 (Japanese Patent Laid-Open No. 11-228631), and Patent Document 5 (Japanese Patent Laid-Open No. 2000-313709), a polysiloxane structure is contained in a fluorine-containing polymer. A means for reducing the coefficient of friction on the surface of the film and improving the scratch resistance by the introduction is described. Although this means is effective to some extent for improving scratch resistance, sufficient scratch resistance cannot be obtained only by this method for a film having an insufficient film strength and interfacial adhesion.

On the other hand, Patent Document 6 (Japanese Patent Application Laid-Open No. 2003-222704) describes that the scratch resistance is greatly improved by adding a silane coupling agent to a low refractive index layer material using a fluorine-containing polymer. Yes. However, the silane coupling agent having a low boiling point has a problem that it volatilizes in the coating and drying process, and requires an excessive amount of addition considering the volatilized content, and there is a problem that it is difficult to obtain stable performance.
JP-A-9-169847 Japanese Patent Laid-Open No. 9-40909 Japanese Patent Laid-Open No. 11-189621 Japanese Patent Laid-Open No. 11-228631 JP 2000-313709 A JP 2003-222704 A

An object of the present invention is to provide a stable inorganic oxide fine particle dispersion in which the dispersibility of the inorganic oxide fine particles is improved, and a coating composition containing the same.
A further object of the present invention is to provide an optical film, particularly an antireflection film, which has sufficient antireflection performance and improved scratch resistance.
Furthermore, the objective of this invention is providing the polarizing plate and liquid crystal display device which comprise the said optical film, especially an antireflection film.

（式中、Ｒ ¹ は水素原子、メチル基、メトキシ基、アルコキシカルボニル基、シアノ基、または塩素原子を表す。Ｙは単結合、−ＣＯＯ−、−ＣＯＮＨ−又は−Ｏ−を表し、Ｌは２価の連結基を表す。ｎは０または１を表す。Ｒ ¹⁰ は置換もしくは無置換のアルキル基、無置換のアリール基を表し、Ｘは水酸基または加水分解可能な基を表す。）
一般式［１］ （Ｒｆ−Ｌ ₁ ） _n −Ｓｉ（Ｒ ¹¹ ） _4-n
（式中、Ｒｆは炭素数１〜２０の直鎖、分岐、環状の含フッ素アルキル基、または炭素数６〜１４の含フッ素芳香族基を表す。Ｌ ₁ は炭素数１０以下の２価の連結基を表し、Ｒ ¹¹ は水酸基または加水分解可能な基を表す。ｎは１〜３の整数を表す。）
［２］
前記一般式［１］で表される含フッ素シランカップリング剤が下記一般式［２］で表されることを特徴とする上記［１］に記載の無機酸化物微粒子分散物の製造方法。
一般式[２] Ｃ_nＦ_2n+1−（ＣＨ₂）_m−Ｓｉ（Ｒ）₃
（式中、ｎは１〜１０の整数を表し、ｍは１〜５の整数を表す。Ｒは炭素数１〜５のアルコキシ基またはハロゲン原子を表す。） As a result of intensive studies, the inventor has obtained a method for producing an inorganic oxide fine particle dispersion having the following constitution, an inorganic oxide fine particle dispersion, a coating composition, an optical film, an antireflection film, a polarizing plate, and a liquid crystal display device. It has been found that the above object of the present invention is achieved.
[1] A method for producing an inorganic oxide fine particle dispersion in which inorganic oxide fine particles are dispersed in an organic solvent, the production method comprising:
(1) An organosilane represented by the following general formula (II) in the presence of at least one of an acid catalyst and the following metal chelate compound in an alcoholic organic solvent having a ketone solvent content of 30% by volume or less . A step of surface-treating inorganic oxide fine particles with at least one of a hydrolyzate and / or a partial condensate thereof and at least one fluorine-containing silane coupling agent represented by the following general formula [1] ; and
(2) A step of replacing the dispersion medium used in the surface treatment with a solvent so that the content of the ketone solvent in all the solvents is increased to 90% by volume or more ,
Including
The solvent substitution is a solvent substitution by distillation under reduced pressure while adding a ketone solvent so that the content of inorganic oxide particles is constant,
The method for producing an inorganic oxide fine particle dispersion, wherein the ketone solvent is a solvent selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
Metal chelate compounds (wherein, R ³ represents. An alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and / or the general formula R ⁴ COCH ₂ COR ⁵ (wherein represented by, R ⁴ is Zr, Ti, wherein the alkyl group has 1 to 10 carbon atoms, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. And at least one metal chelate compound having a metal selected from Al as a central metal.
Formula (II)

(In the formula, R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, or a chlorine atom. Y represents a single bond, —COO—, —CONH—, or —O—, and L represents Represents a divalent linking group, n represents 0 or 1. R ¹⁰ represents a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and X represents a hydroxyl group or a hydrolyzable group.
Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
(In the formula, Rf represents a linear, branched or cyclic fluorine-containing alkyl group having 1 to 20 carbon atoms or a fluorine-containing aromatic group having 6 to 14 carbon atoms. L ₁ is a divalent divalent having 10 or less carbon atoms. Represents a linking group, R ¹¹ represents a hydroxyl group or a hydrolyzable group, and n represents an integer of 1 to 3.)
[2]
The method for producing an inorganic oxide fine particle dispersion according to the above [1], wherein the fluorine-containing silane coupling agent represented by the general formula [1] is represented by the following general formula [2].
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
(In the formula, n represents an integer of 1 to 10, m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.)

[3]
The method for producing an inorganic oxide fine particle dispersion according to the above [1] or [2], wherein the inorganic oxide fine particles are silica fine particles.
[4]
The method for producing an inorganic oxide fine particle dispersion according to any one of [1] to [3] , wherein the inorganic oxide fine particles are hollow silica fine particles.
[5]
An inorganic oxide fine particle dispersion obtained by the production method according to any one of [1] to [4] above.
[6]
A coating composition comprising the inorganic oxide fine particle dispersion described in [5] above and a film-forming composition, wherein at least one component of the film-forming composition is a compound having an ethylenically unsaturated group A coating composition characterized by that.
[7]
A coating composition comprising the inorganic oxide fine particle dispersion according to the above [5] and a film-forming composition, wherein the main component of the film-forming composition is a compound having an ethylenically unsaturated group A coating composition.
[8]
An optical film comprising a layer formed using the coating composition according to the above [5] or [6] on a transparent support.
[9]
In the above [9], the inorganic oxide fine particles contained in the layer formed from the coating composition are hollow particles, and the refractive index of the layer is 1.20 or more and 1.46 or less. The optical film as described.
[10]
The inorganic oxide fine particles contained in the layer formed from the coating composition are hollow silica fine particles, and the refractive index of the hollow silica fine particles is 1.17 to 1.40. The optical film as described in [8] or [9] above.
[11]
The optical film according to any one of [8] to [10] above is an antireflection film having an antireflection layer on a transparent support, and a low refractive index layer is formed using the coating composition. An antireflection film characterized by being made.
[12]
The antireflection according to [11] , wherein the inorganic oxide fine particles contained in the coating composition are hollow silica fine particles having a thickness of 30% to 150% of the thickness of the low refractive index layer. the film.
[13]
The antireflection film as described in [11] or [12] above, wherein the low refractive index layer is formed from a coating solution containing a fluorine-containing polymer represented by the following general formula 1.

（式中、Ｌは炭素数１〜１０の連結基を表し、ｍは０または１を表す。Ｘは水素原子また
はメチル基を表す。Ａは任意のビニルモノマーの重合単位を表し、単一成分であっても複
数の成分で構成されていてもよい。ｘ、ｙ、ｚはそれぞれの構成成分のモル％を表し、３
０≦ｘ≦６０、５≦ｙ≦７０、０≦ｚ≦６５を満たす値を表す。）
［１４］
上記［８］〜［１３］のいずれか一項に記載のフィルムが、偏光板における偏光子の保
護フィルムに用いられていることを特徴とする偏光板。
［１５］
上記［８］〜［１３］のいずれかに記載のフィルム、または上記［１４］に記載の偏光
板が、ディスプレイの最表面に用いられていることを特徴とする画像表示装置。
本発明は、上記［１］〜［１５］に関するものであるが、その他の事項についても参考
のために記載した。

(Wherein L represents a linking group having 1 to 10 carbon atoms, m represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents a polymerized unit of any vinyl monomer, and a single component. Or x, y, z represents the mol% of each component, and 3
It represents a value satisfying 0 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. )
[14]
A polarizing plate, wherein the film according to any one of [8] to [13] is used as a protective film for a polarizer in a polarizing plate.
[15]
An image display device, wherein the film according to any one of [8] to [13] or the polarizing plate according to [14] is used on an outermost surface of a display.
The present invention relates to the above [1] to [15] , but other matters are also described for reference.

  The inorganic oxide fine particle dispersion of the present invention is excellent in dispersion stability. An optical film formed from the coating composition comprising the inorganic oxide fine particle dispersion and the film-forming composition of the present invention has low haze and excellent film scratch resistance. Furthermore, a display device provided with a polarizing plate using the optical film of the present invention, in particular, the antireflection film of the present invention, has very little visibility of external light and background reflection, and has extremely high visibility.

Hereinafter, the present invention will be described in 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”. .
The inorganic oxide fine particle dispersion of the present invention comprises an inorganic oxide fine particle surface-treated with a hydrolyzate and / or partial condensate of an organosilane compound represented by the following general formula (I) in an organic solvent. Dispersed. The surface treatment is performed in the presence of at least one of an acid catalyst and a metal chelate compound.
The surface treatment is performed by bringing an organosilane compound, inorganic oxide fine particles, and if necessary, water into contact in the presence of a catalyst having a hydrolysis function and / or a metal chelate compound having a condensation function. The organosilane compound may be partially hydrolyzed or partially condensed. The organosilane compound undergoes partial condensation subsequent to hydrolysis, which modifies the surface of the inorganic oxide fine particles, thereby improving dispersibility and obtaining a stable inorganic oxide fine particle dispersion.

Formula (I)
(R ¹⁰ ) _m -Si (X) _4-m
(In the formula, R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. X represents a hydroxyl group or a hydrolyzable group. M represents an integer of 1 to 3.)

Metal chelate compound An alcohol represented by a general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and a general formula R ⁴ COCH ₂ COR ⁵ (wherein R ⁴ is the number of carbon atoms) Zr, Ti, and Al having a ligand of a compound represented by 1 to 10 alkyl groups, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. At least one metal chelate compound having a metal selected from

[Organosilane compound]
The organosilane compound of the present invention will be described in detail.
In the general formula (I), R ¹⁰ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl 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. Methyl, ethyl, propyl, isopropyl, hexyl, t-butyl, sec-butyl, hexyl Decyl, hexadecyl and the like. Examples of the aryl group include phenyl and naphthyl, and a phenyl group is preferable.

X represents a hydroxyl group or a hydrolyzable group. 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 (R ² is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples include CH ₃ COO, C ₂ H ₅ COO, etc.), preferably an alkoxy group, particularly preferably a methoxy group. Or it is an ethoxy group.
m represents an integer of 1 to 3. When R ¹⁰ or X there are a plurality, a plurality of R ¹⁰ or X groups may be different, even the same, respectively. m is preferably 1 or 2, particularly preferably 1.

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

In the general formula (II), 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. R ¹ is preferably a hydrogen atom, a methyl group, a methoxy group, a methoxycarbonyl group, a cyano group, a fluorine atom or a chlorine atom, more preferably a hydrogen atom, a methyl group, a methoxycarbonyl group, a fluorine atom or a chlorine atom, And methyl groups are particularly preferred.
Y represents a single bond, an ester group, an amide group, an ether group or a urea group. Single bonds, ester groups and amide groups are preferred, single bonds and ester groups are more preferred, and ester groups are particularly preferred.

  L is a divalent linking chain, specifically, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted group having a linking group (eg, ether, ester, amide) therein. A substituted alkylene group or a substituted or unsubstituted arylene group having a linking group therein, among which a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 carbon atoms, An arylene group, an alkylene group having 3 to 10 carbon atoms having a linking group inside is preferable, an unsubstituted alkylene group, an unsubstituted arylene group, an alkylene group having an ether or ester linking group inside is more preferable, A substituted alkylene group and an alkylene group having an ether or ester linking group therein are particularly preferred. Examples of the substituent include a halogen, a hydroxyl group, a mercapto group, a carboxyl group, an epoxy group, an alkyl group, and an aryl group, and these substituents may be further substituted.

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

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

Among these specific examples, (M-1), (M-2), (M-25) and the like are particularly preferable.
In the present invention, the amount of the organosilane compound represented by the general formula (I) or the general formula (II) is not particularly limited, but is preferably 1% by mass to 300% by mass with respect to the inorganic oxide fine particles. Preferably they are 2 mass%-100 mass%, Most preferably, they are 5 mass%-50 mass%. It is preferably 1 to 300 mol% per hydroxyl group on the surface of the inorganic oxide, more preferably 5 to 300 mol%, and most preferably 10 to 200 mol%. When the amount of the organosilane compound used is in the above range, a sufficient stabilizing effect of the dispersion can be obtained, and the film strength is also great when forming a coating film.

  In the present invention, the inorganic oxide fine particles are surface-modified with a compound having at least one fluorine-containing alkyl group or fluorine-containing aromatic group in addition to the hydrolyzate of the organosilane compound and / or the partial condensate thereof. It is preferable. It is preferable that a compound having a fluorine-containing alkyl group and / or a fluorine-containing aromatic group interacts with the inorganic oxide fine particles, and a chemical surface treatment is performed with a fluorine-based surfactant or a coupling agent. More preferably, surface treatment with a fluorine-based coupling agent is more preferable. As the coupling agent, an alkoxy metal compound (eg, titanium coupling agent, silane coupling agent) is preferably used. Of these, treatment with a silane coupling agent is effective, and a fluorine-containing silane coupling agent represented by the following general formula [1] is particularly effective. In the surface treatment with the fluorine-containing silane coupling agent, it is preferable that a partial condensate of the component derived from the fluorine-containing silane coupling agent and the inorganic oxide fine particles is formed. When a fluorine-based coupling agent is used, the stability of the inorganic oxide fine particles in the solution and the particle dispersibility in the coating film are improved. In particular, the combined use of a fluorine-containing silane coupling agent represented by the following general formula [1] and a compound represented by the general formula (II) is preferable because of excellent dispersibility of particles and scratch resistance in the coating film. The organosilane compound represented by the general formula (I) may be a fluorine-containing silane coupling agent represented by the following general formula [1], or a fluorine-containing silane coupling agent represented by the general formula [I] alone. Surface modification with is also effective.

(Fluorine-containing silane coupling agent)
A preferred fluorine-containing silane coupling agent in the present invention is represented by the following general formula [1].
General formula [1]
_{(Rf-L 1) n -Si} (R 11) n-4
In the above formula, 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, more preferably an alkylene group having 1 to 5 carbon atoms. The alkylene group is a linear or branched, substituted or unsubstituted alkylene group that 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.
R ¹¹ represents a hydroxyl group or a hydrolyzable group, preferably an alkoxy group having 1 to 5 carbon atoms or a halogen atom, more preferably a methoxy group, an ethoxy group, or a chlorine atom.
n represents an integer of 1 to 3.

Next, among the fluorine-containing silane coupling agents represented by the general formula [1], a fluorine-containing silane coupling agent represented by the following general formula [2] is preferable.
General formula [2]
_{C n F 2n + 1 - (} CH 2) m -Si (R) 3
In the above formula, n represents an integer of 1 to 10, and m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom. n is preferably 4 to 10, m is preferably 1 to 3, and R is preferably a methoxy group, an ethoxy group, or a chlorine atom.

  Specific examples of the fluorine-containing silane coupling agent represented by the general formula [1] or [2] are shown below, but are not limited thereto.

  These compounds can be synthesized, for example, by the method described in JP-A-11-189599.

The fluorine-containing silane coupling agent represented by the general formula [1] or [2] is preferably used in an amount of 1% by mass to 100% by mass with respect to the inorganic oxide fine particles, and more preferably 2% by mass to 80%. It is mass%, More preferably, it is 5 mass%-50 mass%.
Two or more kinds of fluorine-containing silane coupling agents may be used in combination, and the total amount of addition is preferably 1% to 100% by mass, more preferably 2% by mass to the inorganic oxide fine particles. 80% by mass, more preferably 5% by mass to 50% by mass.

  In the present invention, the ratio when the fluorine-containing silane coupling agent represented by the general formula [1] or [2] and the organosilane compound represented by the general formula (II) are used in combination is 99: 1 to 1. : 99 is preferable, 75:25 to 5:95 is more preferable, and 50:50 to 25:75 is most preferable.

  Moreover, when using multiple types of organosilane compounds (including a silane coupling agent) in the present invention, all of the organosilane compounds may be added simultaneously, or the reaction proceeds by adding one or more types. After the treatment, the remaining one kind or plural kinds may be added. It is also preferable to prepare a partial condensate with an organosilane compound in advance and then add it to the inorganic oxide fine particles.

  The organosilane compound is allowed to act on the surface of the inorganic oxide fine particles to improve the dispersibility of the inorganic oxide fine particles. Specifically, components derived from the silane coupling agent are bonded to the surface of the inorganic oxide fine particles by hydrolysis / condensation reaction of the organosilane compound.

[Surface treatment solvent]
The surface treatment of the inorganic oxide fine particles with the hydrolyzate and / or condensation reaction product of the organosilane compound can be carried out without a solvent or in a solvent. When a solvent is used, the concentration of the hydrolyzate of the organosilane compound and / or 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 is preferably a solvent that dissolves the hydrolyzate and / or condensation reaction product of the organosilane compound 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 and xylene, specific examples of ethers include tetrahydrofuran and dioxane, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These organic solvents can be used alone or in combination of two or more. Although the density | concentration of the organosilane compound with respect to the solvent in this process is not specifically limited, Usually, it is the range of 0.1 mass%-70 mass%, Preferably it is the range of 1 mass%-50 mass%.
In the present invention, it is preferable to disperse the inorganic oxide fine particles with an alcohol solvent and then perform a surface treatment, and subsequently replace the dispersion solvent with an aromatic hydrocarbon solvent or a ketone solvent. Substitution with a ketone solvent is preferable from the viewpoint of improving the affinity with the binder used at the time of coating and the stability of the dispersion itself. The organic solvent used for the dispersion medium of the inorganic oxide fine particles preferably has a low ketone solvent content, and preferably has a ketone solvent content of 30% by volume or less, more preferably 10%. It is not more than volume%, particularly preferably not more than 5 volume%. By substitution with a ketone solvent after the surface treatment, the content of the ketone solvent in the total solvent is preferably 50% by volume or more, more preferably 80% by volume or more, and particularly preferably 90% by volume or more. .

[Surface treatment catalyst]
The surface treatment of the inorganic oxide fine particles with the hydrolyzate and / or condensation reaction product of the organosilane compound is preferably 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, Organic bases such as pyridine; metal alkoxides such as triisopropoxyaluminum and tetrabutoxyzirconium, and the like. From the viewpoint of production stability and storage stability of the inorganic oxide fine particle dispersion, Catalysts (inorganic acids, organic acids) and / or metal chelate compounds are used. Among inorganic acids, hydrochloric acid, sulfuric acid, and organic acids preferably have an acid dissociation constant in water (pKa value (25 ° C.)) of 4.5 or less, and an acid dissociation constant in hydrochloric acid, sulfuric acid, or water of 3.0 or less. More preferred is an organic acid, hydrochloric acid, sulfuric acid, an organic acid having an acid dissociation constant of 2.5 or less in water is more preferred, an organic acid having an acid dissociation constant in water of 2.5 or less is more preferred, and methanesulfonic acid Further, oxalic acid, phthalic acid, and malonic acid are more preferable, and oxalic acid is particularly preferable.

  When the hydrolyzable group of the organosilane compound is an alkoxy group and the acid catalyst is an organic acid, the amount of water added can be reduced because the carboxyl group or sulfo group of the organic acid supplies protons. The amount of water added to 1 mol of the alkoxide group of the compound 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 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 of use 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 treatment is carried out by stirring at 15 to 100 ° C., but is preferably controlled by the reactivity of the organosilane compound.

[Metal chelate compounds]
The metal chelate compound is an alcohol represented by a general formula R ³ OH (wherein R ³ represents an alkyl group having 1 to 10 carbon atoms) and / or a general formula R ⁴ COCH ₂ COR ⁵ (where R 3 ⁴ represents an alkyl group having 1 to 10 carbon atoms, and R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.) As long as a metal selected from Ti or Al is used as a central metal, it can be suitably used without any particular limitation. Within this category, two or more metal chelate compounds may be used in combination. The metal chelate compound used in the present invention has the general formula Zr (OR ³ ) _p1 (R ⁴ COCHCOR ⁵ ) _p2 ,
Ti (OR ³ ) _q1 (R ⁴ COCHCOR ⁵ ) _q2 and Al (OR ³ ) _r1 (R ⁴ COCHCOR ⁵ ) _r2
Are preferably selected from the group of compounds represented by the formula (I), which serve to promote the condensation reaction of the organosilane compound.
R ³ and R ⁴ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, specifically, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, phenyl group and the like. R ⁵ represents an alkyl group having 1 to 10 carbon atoms as described above, or an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and n-butoxy. Group, sec-butoxy group, t-butoxy group and the like. In addition, p1, p2, q1, q2, r1, and r2 in the metal chelate compound represent integers determined so as to be tetradentate or hexadentate.

Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxy Cetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) 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 metal chelate compound of the present invention is preferably from 0.01 to 50% by mass, more preferably from 0.1 to 50% by mass, based on the organosilane compound, from the viewpoint of the speed of the condensation reaction and the film strength when it is used as a coating film. It is used in a proportion of 50% by mass, more preferably 0.5 to 10% by mass.

[Dispersion stabilization additive]
In addition to the organosilane compound and acid catalyst and / or chelate compound, the following component (c) is preferably added to the dispersion or coating composition of the present invention. Hereinafter, the component (c) will be further described. The component (c) used in the present invention is a β-diketone compound and / or β-ketoester compound represented by the general formula R ⁴ COCH ₂ COR ⁵ , and the stability of the dispersion or coating composition of the present invention It acts as an improver. That is, by coordinating to the metal atom in the metal chelate compound (zirconium, titanium and / or aluminum compound), the action of promoting the condensation reaction of the organosilane compound and the metal chelate component by these metal chelate compounds is suppressed. Therefore, it is considered that the resulting composition improves the storage stability. R ⁴ and R ⁵ constituting the component (c) is the same as R ⁴ and R ⁵ constituting the metal chelate compound.

  Specific examples of the (c) component β-diketone compound and / or β-ketoester compound include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate- n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl, 2,4-hexane-dione, 2,4-heptane-dione, 3,5-heptane-dione, 2,4-octane-dione, Examples include 2,4-nonane-dione, 5-methyl-hexane-dione, and the like. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketone compounds and / or β-ketoester compounds may be used alone or in combination of two or more. In the present invention, the β-diketone compound and / or β-ketoester compound as the component (c) is preferably used in an amount of 2 mol or more, more preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If it is less than 2 mol, the storage stability of the resulting composition may be inferior, which is not preferable.

[Inorganic oxide fine particles]
Next, inorganic oxide fine particles that can be used in the present invention will be described.
The inorganic oxide fine particles are at least one selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Elemental oxide fine particles are preferred.

  Examples of these inorganic oxide fine particles include particles of silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, cerium oxide, and the like. be able to. Of these, particles of silica, alumina, zirconia and antimony oxide are preferred from the viewpoint of high hardness. These can be used alone or in combination of two or more. The inorganic oxide fine particle dispersion of the present invention is obtained by dispersing the above-mentioned inorganic oxide fine particles having a modified surface in an organic solvent. The surface of the inorganic oxide fine particles is preferably modified while being dispersed in a dispersion medium. From the viewpoint of compatibility with other components and dispersibility, the dispersion medium is preferably an organic solvent, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene, Aromatic hydrocarbons such as toluene and xylene; and amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  The number average particle diameter of the oxide fine particles is preferably 1 nm to 2000 nm, more preferably 3 nm to 200 nm, and particularly preferably 5 nm to 100 nm. When the number average particle diameter exceeds 2000 μm, the transparency when cured is reduced, and the surface state when the film is formed tends to be deteriorated. Various surfactants and amines may be added to improve the dispersibility of the particles.

  Examples of products that are commercially available as silicon oxide fine particle dispersions (for example, silica particles) include colloidal silica, methanol silica sol manufactured by Nissan Chemical Industries, Ltd., MA-ST-MS, IPA-ST, IPA- ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. ) Hollow silica CS60-IPA and the like. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Moreover, as an aqueous dispersion product of alumina, Nissan Chemical Industries, Ltd. alumina sol-100, -200, -520; As an alumina isopropanol dispersion product, Sumitomo Osaka Cement Co., Ltd. AS-150I; AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd .; HXU-110JC manufactured by Sumitomo Osaka Cement Co., Ltd. as a toluene dispersion of zirconia; ) Celnax; Alumina, Titanium oxide, Tin oxide, Indium oxide, Zinc oxide, etc. Powder and solvent dispersion products are nanotech made by CI Kasei Co., Ltd .; SN-100D, manufactured by Mitsubishi Materials Corporation, and ITO The aqueous dispersion, mention may be made of Taki Chemical Co., Ltd. Nidoraru like.

The shape of the oxide fine particles is spherical, hollow, porous, rod-like, plate-like, fibrous, or indefinite, and preferably spherical or hollow. The hollow silica particles will be described later. The specific surface area of the oxide fine particles (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These inorganic oxide fine particles can be obtained by dispersing a dry powder in an organic solvent. For example, a fine particle dispersion of oxide fine particles known in the art as a solvent dispersion sol of the above oxide is directly used. Can be used.

[Distribution method]
In order to prepare the inorganic oxide fine particles of the present invention by dispersing them from a powder in a solvent, a dispersant can also be used. In the present invention, it is preferable to use a dispersant having an anionic group.
As the anionic group, a group having an acidic proton such as a carboxyl group, a sulfonic acid group (sulfo), a phosphoric acid group (phosphono), a sulfonamide group, or a salt thereof is effective, and in particular, a carboxyl group, a sulfonic acid group, A phosphoric acid group or a salt thereof is preferable, and a carboxyl group and a phosphoric acid group are particularly preferable. A plurality of anionic groups may be contained for the purpose of further improving dispersibility. The average number is preferably 2 or more, more preferably 5 or more, and particularly preferably 10 or more. Moreover, the anionic group contained in a dispersing agent may contain multiple types in 1 molecule.
The dispersant may further contain a crosslinking or polymerizable functional group. Crosslinkable or polymerizable functional groups include ethylenically unsaturated groups (for example, (meth) acryloyl groups, allyl groups, styryl groups, vinyloxy groups, etc.) that can undergo addition reactions and polymerization reactions with radical species, and cationic polymerizable groups (epoxies). Groups, oxatanyl groups, vinyloxy groups, etc.), polycondensation reactive groups (hydrolyzable silyl groups, etc., N-methylol groups) and the like, and functional groups having an ethylenically unsaturated group are preferred.
In the present invention, a disperser can be used to grind the inorganic oxide fine particles. Examples of dispersers include sand grinder mills (eg, pinned bead mills), high speed impeller mills, pebble mills, roller mills, attritors and colloid mills. A sand grinder mill and a high-speed impeller mill are particularly preferred. Further, preliminary dispersion processing may be performed. Examples of the disperser used for the preliminary dispersion treatment include a ball mill, a three-roll mill, a kneader, and an extruder.

  The organic oxide dispersion of the inorganic oxide fine particles of the present invention described above is used as a fine particle component, which is combined with the film forming composition to form a coating composition, and each layer of the optical film can be formed from this composition. In particular, it is suitable for forming a low refractive index layer of an antireflection film.

[Layer structure of optical film]
The optical film of the present invention has at least one functional layer on a transparent substrate (hereinafter also referred to as a substrate film), and at least one of the functional layers is formed from the coating composition of the present invention. It is preferable that
Examples of the functional layer herein include an antistatic layer, a hard coat layer, an antireflection layer, an antiglare layer, an optical compensation layer, an alignment layer, and a liquid crystal layer. On the transparent substrate, if necessary, it has a hard coat layer which will be described later. It has a laminated antireflection layer.
The simplest structure of the antireflection film is obtained by coating an antireflection layer consisting of only a low refractive index layer on a substrate. In order to further reduce the reflectance, the antireflection layer is preferably constituted by combining a high refractive index layer having a higher refractive index than that of the base material and a low refractive index layer having a lower refractive index than that of the base material. Examples of configurations include two layers of a high refractive index layer / low refractive index layer from the base material side, and three layers having different refractive indices, a medium refractive index layer (having a higher refractive index than the base material or the hard coat layer , A layer having a refractive index lower than that of a high refractive index layer) / a layer having a high refractive index / a layer having a low refractive index, and the like. Among these, in view of durability, optical characteristics, cost, productivity, and the like, those laminated in the order of medium refractive index layer / high refractive index layer / low refractive index layer on a substrate having a hard coat layer are preferable. Further, the antireflection film of the present invention may have an antiglare layer, an antistatic layer or the like.

Examples of preferred layer configurations of the low reflection laminate of the present invention are shown below.
Base film / low refractive index layer,
Base film / antiglare layer / low refractive index layer,
Base film / hard coat layer / antiglare layer / low refractive index layer,
Base film / hard coat layer / high refractive index layer / low refractive index layer,
Base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / high refractive index layer / low refractive index layer,
Base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / hard coat layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Base film / antistatic layer / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / medium refractive index layer / high refractive index layer / low refractive index layer,
Antistatic layer / base film / antiglare layer / high refractive index layer / low refractive index layer / high refractive index layer / low refractive index layer,
As long as the reflectance can be reduced by optical interference, it is not limited to these layer configurations. The high refractive index layer may be a light diffusing layer having no antiglare property. The antistatic layer is preferably a layer containing conductive polymer particles or metal oxide fine particles (for example, SnO ₂ , ITO), and can be provided by coating or atmospheric pressure plasma treatment.

[Film-forming binder]
In the coating composition of the present invention, it is preferable that at least one component of the film-forming composition is a compound having an ethylenically unsaturated group. Particularly in the present invention, from the viewpoints of film strength, coating solution stability, coating film productivity, and the like, the main film-forming binder component of the film-forming composition is more preferably a compound having an ethylenically unsaturated group. . The main film-forming binder refers to one that accounts for 10% by mass or more of the film-forming components excluding inorganic particles. Preferably, they are 20 mass% or more and 100 mass% or less, More preferably, they are 30 mass% or more and 95% or less.
The film-forming binder is preferably a polymer having a saturated hydrocarbon chain or a polyether chain as a main chain, and more preferably a polymer having a saturated hydrocarbon chain as a main chain. As the binder polymer having a saturated hydrocarbon chain as the main chain and having a crosslinked structure, a (co) polymer of monomers having two or more ethylenically unsaturated groups is preferable.
In order to further increase the refractive index, the monomer structure preferably contains an aromatic ring or at least one atom selected from halogen atoms other than fluorine, sulfur atoms, phosphorus atoms, and nitrogen atoms.

  Examples of the monomer having two or more ethylenically unsaturated groups include esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra ( (Meth) acrylate), pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, polyester polymer Acrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, , Methylenebisacrylamide) and methacrylamide. Two or more of these monomers may be used in combination. In the present specification, “(meth) acrylate” represents “acrylate or methacrylate”.

  Specific examples of the high refractive index monomer include bis (4-methacryloylthiophenyl) sulfide, vinyl naphthalene, vinyl phenyl sulfide, 4-methacryloxyphenyl-4′-methoxyphenyl thioether, and the like. Two or more of these monomers may be used in combination.

  Polymerization of the monomer having an ethylenically unsaturated group can be performed by irradiation with ionizing radiation or heating in the presence of a photo radical initiator or a thermal radical initiator.

Photo radical polymerization initiators include 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-hydroxydimethylphenyl ketone, 1-hydroxycyclohexyl phenyl ketone, 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 the 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 Takashiro, 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, 907) manufactured by Nippon Ciba-Geigy Co., Ltd.
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. Ammonium sulfate, potassium persulfate, etc., 2-azo-bis-isobutyronitrile, 2-azo-bis-propionitrile, 2-azo-bis-cyclohexanedinitrile, etc. as diazo compounds, diazoaminobenzene, p -Nitrobenzenediazonium etc. can be mentioned.

  In the present invention, a polymer having a polyether as a main chain can also be used as a film-forming binder. The film-forming binder is preferably a ring-opening polymer of a polyfunctional epoxy compound. The ring-opening polymerization of the polyfunctional epoxy compound can be performed by irradiation with ionizing radiation or heating in the presence of a photoacid generator or a thermal acid generator.

Instead of or in addition to a monomer having two or more ethylenically unsaturated groups, a monomer having a crosslinkable functional group is used to introduce a crosslinkable functional group into the polymer, and by reaction of this crosslinkable functional group, A crosslinked structure may be introduced into the binder polymer.
Examples of the crosslinkable functional group include isocyanate group, epoxy group, aziridine group, oxazoline group, aldehyde group, carbonyl group, hydrazine group, carboxyl group, methylol group and active methylene group. Vinylsulfonic acid, acid anhydride, cyanoacrylate derivative, melamine, etherified methylol, ester and urethane, and metal alkoxide such as tetramethoxysilane can also be used as a monomer for introducing a crosslinked structure. A functional group that exhibits crosslinkability as a result of the decomposition reaction, such as a block isocyanate group, may be used. That is, in the present invention, the crosslinkable functional group may not react immediately but may exhibit reactivity as a result of decomposition.
These binder polymers having a crosslinkable functional group can form a crosslinked structure by heating after coating.

Hereinafter, the optical film of the present invention will be described using an antireflection film as an example.
[Material for low refractive index layer]
The low refractive index layer is preferably formed using the coating composition of the present invention.
The low refractive index layer is preferably formed by a cured film of a copolymer having a repeating unit derived from a fluorine-containing vinyl monomer and a repeating unit having a (meth) acryloyl group in the side chain as essential constituent components. The copolymer-derived component preferably occupies 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more. From the viewpoint of achieving both low refractive index and film hardness, a curing agent such as polyfunctional (meth) acrylate is also preferably used in an addition amount within a range that does not impair the compatibility.

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

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

  The copolymer of the present invention preferably has a repeating unit having a (meth) acryloyl group in the side chain as an essential component. If the composition ratio of these (meth) acryloyl group-containing repeating units is increased, the film strength is improved, but the refractive index is also increased. Generally, the (meth) acryloyl group-containing repeating unit preferably accounts for 5 to 90% by mass, more preferably 30 to 70% by mass, although it varies depending on the type of repeating unit derived from the fluorine-containing vinyl monomer. It is particularly preferred to account for ~ 60% by weight.

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

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

  A preferred form of the copolymer used in the present invention is that of the general formula 1.

In General Formula 1, L represents a linking group having 1 to 10 carbon atoms, more preferably a linking group having 1 to 6 carbon atoms, particularly preferably a linking group having 2 to 4 carbon atoms, It may have a branched structure, may have a ring structure, and may have a heteroatom selected from O, N, and S.
Preferred examples include *-(CH ₂ ) ₂ -O-**, *-(CH ₂ ) ₂ -NH-**, *-(CH ₂ ) ₄ -O-**, *-(CH ₂ ) ₆ -O-**, *-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-**, * -CONH- (CH ₂ ) ₃ -O-**, * -CH ₂ CH (OH ) CH ₂ -O-**, * -CH ₂ CH ₂ OCONH (CH ₂ ) ₃ -O-** (* represents the linking site on the polymer main chain side, ** represents the linking on the (meth) acryloyl group side) Represents a part). m represents 0 or 1;

  In general formula 1, X represents a hydrogen atom or a methyl group. From the viewpoint of curing reactivity, a hydrogen atom is more preferable.

  In the general formula 1, A represents a repeating unit derived from an arbitrary vinyl monomer, and is not particularly limited as long as it is a constituent component of a monomer copolymerizable with hexafluoropropylene. Tg (contributes to film hardness), solubility in solvents, transparency, slipperiness, dust / antifouling properties, etc., can be selected as appropriate, depending on the purpose, depending on the single or multiple vinyl monomers It may be configured.

  Preferred examples include methyl vinyl ether, ethyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, isopropyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, glycidyl vinyl ether, vinyl ethers such as allyl vinyl ether, vinyl acetate, vinyl propionate, butyric acid. (Meth) such as vinyl esters such as vinyl, methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl methacrylate, allyl (meth) acrylate, (meth) acryloyloxypropyltrimethoxysilane Acrylates, styrene, styrene derivatives such as p-hydroxymethylstyrene, crotonic acid, maleic acid, itaconic acid Can be mentioned unsaturated carboxylic acids and derivatives thereof, more preferably ether derivatives, vinyl ester derivatives, particularly preferably a vinyl ether derivative.

  x, y, and z represent mol% of each constituent component, and represent values satisfying 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Preferably, 35 ≦ x ≦ 55, 30 ≦ y ≦ 60, and 0 ≦ z ≦ 20, and particularly preferably 40 ≦ x ≦ 55, 40 ≦ y ≦ 55, and 0 ≦ z ≦ 10.

  A particularly preferred form of the copolymer used in the present invention is General Formula 2.

In general formula 2, X, x, and y have the same meaning as in general formula 1, and the preferred ranges are also the same.
n represents an integer of 2 ≦ n ≦ 10, preferably 2 ≦ n ≦ 6, and particularly preferably 2 ≦ n ≦ 4.
B represents a unit of a repeating unit derived from an arbitrary vinyl monomer, and may be composed of a single composition or a plurality of compositions. As an example, what was demonstrated as an example of A in the said General formula 1 is applicable.
z1 and z2 represent mol% of each repeating unit, and represent values satisfying 0 ≦ z1 ≦ 65 and 0 ≦ z2 ≦ 65. It is preferable that 0 ≦ z1 ≦ 30 and 0 ≦ z2 ≦ 10 respectively, and it is particularly preferable that 0 ≦ z1 ≦ 10 and 0 ≦ z2 ≦ 5.

  The copolymer represented by the general formula 1 or the general formula 2 can be synthesized, for example, by introducing a (meth) acryloyl group into a copolymer containing a hexafluoropropylene component and a hydroxyalkyl vinyl ether component. These copolymers can be synthesized by the method described in JP-A-2004-45462.

  Although the preferable example of the copolymer useful by this invention is shown below, this invention is not limited to these.

  The copolymer used in the present invention is synthesized by synthesizing a precursor such as a hydroxyl group-containing polymer by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, precipitation polymerization, bulk polymerization, and emulsion polymerization. It can be carried out by introducing a (meth) acryloyl group by a polymer reaction. The polymerization reaction can be performed by a known operation such as a batch system, a semi-continuous system, or a continuous system.

  The polymerization initiation method includes a method using a radical initiator, a method of irradiating light or radiation, and the like. These polymerization methods and polymerization initiation methods are, for example, the revised version of Tsuruta Junji “Polymer Synthesis Method” (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu, Masato Kinoshita, “Experimental Methods for Polymer Synthesis” It is described in pp. 47-154 published in 1972.

  Among the above polymerization methods, a solution polymerization method using a radical initiator is particularly preferable. Solvents used in the solution polymerization method include, for example, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, tetrahydrofuran, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, benzene, toluene, acetonitrile, A single organic solvent such as methylene chloride, chloroform, dichloroethane, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol, or a mixture of two or more thereof may be used, or a mixed solvent with water may be used.

  The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the type of initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but it is preferable to carry out the polymerization in the range of 50 to 100 ° C.

  The reaction pressure can be selected as appropriate, but usually 0.98 to 98 kPa, particularly about 0.98 to 30 kPa is desirable. The reaction time is about 5 to 30 hours.

  As the reprecipitation solvent for the obtained polymer, isopropanol, hexane, methanol and the like are preferable.

In the present invention, inorganic fine particles that can be preferably used for the low refractive index layer of the antireflection layer will be described.
The coating amount of the inorganic fine particles is preferably ^{1mg / m 2 ~100mg / m 2} , more preferably ^{5mg / m 2 ~80mg / m 2} , more preferably from ^{10mg / m 2 ~60mg / m 2} . If the amount is too small, the effect of improving the scratch resistance is reduced. If the amount is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. Since the inorganic fine particles are contained in the low refractive index layer, it is desirable that the inorganic fine particles have a low refractive index.
Specifically, surface-treated inorganic oxide fine particles or hollow inorganic oxide fine particles dispersed in the organic solvent dispersion described above and having a low refractive index are preferably used. For example, fine particles of silica or hollow silica can be mentioned. The average particle diameter of the silica fine particles is preferably 30% to 150% of the thickness of the low refractive index layer, more preferably 35% to 80%, and still more preferably 40% to 60%. That is, when the thickness of the low refractive index layer is 100 nm, the particle diameter of the silica fine particles is preferably 30 nm to 150 nm, more preferably 35 nm to 80 nm, and still more preferably 40 nm to 60 nm.
If the particle size of the silica fine particles is too small, the effect of improving the scratch resistance is reduced. If it is too large, fine irregularities are formed on the surface of the low refractive index layer, and the appearance such as black tightening and the integrated reflectance are deteriorated. The silica fine particles may be either crystalline or amorphous, and may be monodispersed particles or aggregated particles as long as a predetermined particle size is satisfied. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite. Here, the average particle diameter of the inorganic fine particles is measured by a Coulter counter.

In order to lower the refractive index of the low refractive index layer, it is preferable to use hollow silica fine particles. The hollow silica fine particles have a refractive index of 1.17 to 1.40, more preferably 1.17 to 1.35, and still more preferably 1.17 to 1.30. The refractive index here represents the refractive index of the whole particle, and does not represent the refractive index of only the outer shell silica forming the hollow silica fine particles. At this time, when the radius of the cavity in the particle is a and the radius of the particle outer shell is b, the porosity x is calculated by the following formula (VIII).
(Formula VIII)
^{x = (4πa 3/3)} / (4πb 3/3) × 100
The porosity x is preferably 10 to 60%, more preferably 20 to 60%, and most preferably 30 to 60%. If hollow silica fine particles are made to have a lower refractive index and a higher porosity, the thickness of the outer shell becomes thinner and the strength of the particles becomes weaker. Rate particles do not hold.
The refractive index of these hollow silica fine particles was measured with an Abbe refractometer (manufactured by Atago Co., Ltd.).

  Moreover, the refractive index of this layer can be reduced by including hollow particles in the low refractive index layer. When hollow particles are used, the refractive index of the layer is preferably 1.20 or more and 1.46 or less, more preferably 1.25 or more and 1.41 or less, and most preferably 1.30 or more and 1.39. It is as follows.

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

  In the present invention, from the viewpoint of improving the film strength, it is preferable to add a hydrolyzate of an organosilane compound and / or a partial condensate thereof together with the copolymer capable of forming the cured film. For the synthesis of the partial condensate (abbreviated as sol) of the organosilane compound, the acid catalyst or metal chelate compound used for the surface treatment (dispersion improving treatment) of the inorganic oxide fine particles of the present invention can be used. The preferable addition amount of sol is preferably 2 to 200% by mass of the inorganic oxide fine particles, more preferably 5 to 100% by mass, and most preferably 10 to 50% by mass.

(Other materials added to the low refractive index layer)
In the present invention, it is preferable to reduce the surface free energy on the surface of the antireflection film from the viewpoint of improving the antifouling property. Specifically, it is preferable to use a fluorine-containing compound or a compound having a polysiloxane structure for the low refractive index layer. Examples of the additive having a polysiloxane structure include reactive group-containing polysiloxanes (for example, KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (above trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), AK-5, AK-30, AK-32 (above trade name) , Manufactured by Toa Gosei Co., Ltd.), Silaplane FM0725, Silaplane FM0721 (trade name, manufactured by Chisso Corporation) and the like are also preferably added. In addition, silicone compounds described in Tables 2 and 3 of JP-A No. 2003-112383 can also be preferably used. These polysiloxanes are preferably added in the range of 0.1 to 10% by mass of the total solid content of the low refractive index layer, particularly preferably 1 to 5% by mass.

The low refractive index layer is irradiated with ionizing radiation (for example, light irradiation, electron beam irradiation) at the same time as coating, or after coating and drying a coating composition in which a fluorine-containing compound and other optional components optionally contained are dissolved or dispersed. It is preferably formed by curing by a crosslinking reaction by heating or a polymerization reaction.
In particular, when the low refractive index layer is formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, an outermost layer having excellent physical strength and chemical resistance can be obtained.
The oxygen concentration is preferably 6% by volume or less, more preferably 4% by volume or less, particularly preferably 2% by volume or less, and most preferably 1% by volume or less.

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

[Material for high refractive index layer]
The antireflection film in the present invention is preferably provided with a high refractive index layer. The high refractive index layer can be formed from a binder, mat particles for imparting antiglare properties, and an inorganic filler for increasing the refractive index, preventing crosslinking shrinkage, and increasing the strength.

For the purpose of imparting antiglare properties, the high refractive index layer has a matte particle having an average particle size of 0.1 to 5.0 μm, preferably 1.5 to 3.5 μm, for example, inorganic compound particles. Alternatively, resin particles can be contained. If the difference in refractive index between the matte particles and the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusion effect cannot be obtained, so 0.02 to 0.20 is preferable, and 0.04 to Particularly preferred is 0.10. Similarly to the refractive index, the addition amount of the matting particles with respect to the binder is too large, the film becomes cloudy, and if it is too small, a sufficient light diffusion effect cannot be obtained. A percentage is particularly preferred.
As specific examples of the mat particles, inorganic particles such as silica particles and TiO ₂ particles; resin particles such as acrylic particles, crosslinked acrylic particles, polystyrene particles, crosslinked styrene particles, melamine resin particles, and benzoguanamine resin particles are preferable. Can be mentioned. Of these, crosslinked styrene particles, crosslinked acrylic particles, and silica particles are preferred.
As the shape of the mat particle, either a true sphere or an indefinite shape can be used.

  Two or more different kinds of mat particles may be used in combination. When two or more kinds of mat particles are used, the difference in refractive index is preferably 0.02 or more and 0.10 or less in order to effectively exert the refractive index control by mixing the two, and 0.03 or more. Is particularly preferably 0.07 or less. Further, it is possible to impart an antiglare property with mat particles having a larger particle size and to impart another optical characteristic with mat particles having a smaller particle size. For example, when an optical film is attached to a high-definition display of 133 ppi or more, it is required that there is no problem in optical performance called glare. Glare originates from the fact that the pixels are enlarged or reduced due to unevenness existing on the film surface (contributing to anti-glare properties) and lose uniformity of brightness, but with a particle size smaller than that of mat particles that provide anti-glare properties. It can be greatly improved by using mat particles having a different refractive index from the binder.

  Furthermore, the particle size distribution of the mat particles is most preferably monodisperse, and the particle sizes of the particles are preferably closer to each other. For example, when particles having a particle size of 20% or more than the average particle size are defined as coarse particles, the proportion of coarse particles is preferably 1% or less of the total number of particles, more preferably 0.1%. Or less, more preferably 0.01% or less. Matt particles having such a particle size distribution are obtained by classification after a normal synthesis reaction, and a matting agent having a more preferable distribution can be obtained by increasing the number of classifications or increasing the degree of classification.

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

The high refractive index layer is selected from titanium, zirconium, aluminum, indium, zinc, tin, and antimony in addition to the above matte particles in order to increase the refractive index of the layer and to reduce cure shrinkage. It is preferable that an inorganic filler which contains an oxide of at least one metal and has an average particle size of 0.2 μm or less, preferably 0.1 μm or less, more preferably 0.06 μm or less.
In order to increase the difference in refractive index from the mat particles, it is also preferable to use a silicon oxide in order to keep the refractive index of the layer low in the high refractive index layer using the high refractive index mat particles. The preferred particle size is the same as that of the aforementioned inorganic filler.
Specific examples of the inorganic filler used for the high refractive index layer include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , In ₂ O ₃ , ZnO, SnO ₂ , Sb ₂ O ₃ , ITO and SiO ₂ . TiO ₂ and ZrO ₂ are particularly preferable from the viewpoint of increasing the refractive index. From the viewpoint of refractive index, titanium dioxide fine particles are most preferable. In the case of using a monomer and an initiator, a medium refractive index layer or a high refractive index layer having excellent scratch resistance and adhesion can be formed by curing the monomer by ionizing radiation or heat polymerization after coating. The average particle size of the inorganic fine particles in the film is 20 to 120 nm in view of haze, dispersion stability, adhesion to the upper layer due to moderate irregularities on the surface, and suppression of photoactivity when using titanium dioxide. It is preferable that there is, more preferably 30 to 100 nm, and further preferably 40 to 90 nm.

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

The particle diameter of the inorganic fine particles can be measured by a light scattering method or an electron micrograph. The specific surface area of the inorganic fine particles is preferably 10 to 400 m ² / g, more preferably from 20 to 200 m ² / g, and most preferably from 30 to 150 m ² / g.
The crystal structure of the inorganic fine particles containing titanium dioxide as a main component is preferably a rutile, rutile / anatase mixed crystal, anatase or amorphous structure, particularly preferably a rutile structure. The main component means a component having the largest content (mass%) among the components constituting the particles.

By containing at least one element selected from Co (cobalt), Al (aluminum) and Zr (zirconium) in the inorganic fine particles mainly composed of titanium dioxide, the photocatalytic activity of titanium dioxide can be suppressed, The weather resistance of the high refractive index layer and the middle refractive index layer of the present invention can be improved.
A particularly preferable element is Co (cobalt). It is also preferable to use two or more types in combination. The surface of the inorganic filler is preferably subjected to a silane coupling treatment or a titanium coupling treatment, and a surface treatment agent having a functional group capable of reacting with a binder species on the filler surface is preferably used.
The amount of these inorganic fillers added is preferably 10 to 90% of the total mass of the high refractive index layer, more preferably 20 to 80%, and particularly preferably 30 to 70%.
Such a filler does not scatter because the particle size is sufficiently smaller than the wavelength of light, and a dispersion in which the filler is dispersed in a binder polymer behaves as an optically uniform substance.

  The bulk refractive index of the mixture of the binder and the inorganic filler of the high refractive index layer of the present invention is preferably 1.48 to 2.00, more preferably 1.50 to 1.80. In order to make the refractive index within the above range, the kind and amount ratio of the binder and the inorganic filler may be appropriately selected. How to select can be easily known experimentally in advance.

The antireflection film of the present invention thus formed has a haze value of 3 to 70%, preferably 4 to 60%, and an average reflectance of 450 nm to 650 nm is preferably 3.0% or less, preferably Is 2.5% or less.
When the antireflection film of the present invention has a haze value and an average reflectance in the above range, good antiglare properties and antireflection properties can be obtained without causing deterioration of the transmitted image.

[Support]
A plastic film is preferably used as the transparent support of the optical film of the present invention. Examples of polymers forming the plastic film include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, typically TAC-TD80U, TD80UF, etc. manufactured by Fuji Photo Film), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene). Naphthalate), polystyrene, polyolefin, norbornene resin (Arton: trade name, manufactured by JSR), amorphous polyolefin (ZEONEX: trade name, manufactured by Nippon Zeon), and the like. Of these, triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate are preferable, and triacetyl cellulose is particularly preferable. In addition, the cellulose acylate film substantially free of halogenated hydrocarbons such as dichloromethane and the process for producing the same are disclosed in the JIII Journal of Technical Disclosure (Publication No. 2001-1745, published on March 15, 2001; The cellulose acylate described here can also be preferably used in the present invention.

[Saponification]
When the optical film of the present invention is used in a liquid crystal display device, it is disposed on the outermost surface of the display by providing an adhesive layer on one side. When the transparent support is triacetyl cellulose, since triacetyl cellulose is usually used as a protective film for protecting the polarizing layer of the polarizing plate, it is costly to use the optical film of the present invention as it is for the protective film. preferable.

The optical film of the present invention, for example, the antireflection film of the present invention is sufficiently bonded when it is disposed on the outermost surface of a display by providing an adhesive layer on one side or used as a protective film for a polarizing plate as it is. For this purpose, it is preferable to carry out a saponification treatment after forming an outermost layer mainly composed of a fluoropolymer on a transparent support. The saponification treatment is performed by a known method, for example, by immersing the film in an alkali solution for an appropriate time. After being immersed in the alkaline solution, it is preferable to sufficiently wash with water or neutralize the alkaline component by dipping in a dilute acid so that the alkaline component does not remain in the film.
By saponification treatment, the surface of the transparent support opposite to the side having the outermost layer is hydrophilized.
The hydrophilized surface is particularly effective for improving the adhesion with a polarizing film containing polyvinyl alcohol as a main component. In addition, the hydrophilic surface makes it difficult for dust in the air to adhere to it, making it difficult for dust to enter between the polarizing film and the optical film when bonded to the polarizing film, and is effective in preventing point defects caused by dust. It is.
The saponification treatment is preferably carried out so that the contact angle of water on the surface of the transparent support opposite to the side having the outermost layer is 40 ° or less. More preferably, it is 30 ° or less, particularly preferably 20 ° or less.

Specific means for the alkali saponification treatment can be selected from the following two means (1) and (2). (1) is superior in that it can be processed in the same process as a general-purpose triacetylcellulose film, but since the saponification is performed up to the outermost layer surface, the surface is alkali-hydrolyzed and the membrane is deteriorated. If it remains, it becomes a problem that it becomes dirty. In that case, although it becomes a special process, (2) is excellent.
(1) After forming a functional layer on a transparent support, the back surface of the film is saponified by immersing it in an alkaline solution at least once.
(2) Before or after the functional layer is formed on the transparent support, the alkaline liquid is applied to the surface of the optical film opposite to the surface on which the optical film is formed, and is heated, washed and / or neutralized. Then, only the back surface of the film is saponified.

[Coating method]
The optical film of the present invention can be formed by the following method, but is not limited to this method. Hereinafter, the method for producing an optical film of the present invention will be described in detail by taking the method for forming an antireflection film as an example.
First, a coating solution containing components for forming each layer is prepared. The coating solution is applied on a transparent support by dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating or extrusion coating (see US Pat. No. 2,681,294). Heat and dry. Of these coating methods, a gravure coating method is preferable because a coating solution with a small coating amount such as each layer of the antireflection film can be applied with high film thickness uniformity. Among the gravure coating methods, the micro gravure method has a high film thickness uniformity and is more preferable.
In addition, a coating solution with a small coating amount can be applied with high film thickness uniformity even by using the die coating method. Furthermore, since the die coating method is a pre-weighing method, the film thickness can be controlled relatively easily, and the solvent in the coating part can be controlled. Is preferred because of less transpiration. Two or more layers may be applied simultaneously. The methods for simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

It is a production cost that at least two of the plurality of layers of the antireflection film of the present invention are formed by the steps of feeding the support film once, forming each optical thin film, and winding the film. From the viewpoint of the above, when the antireflection layer has a three-layer structure, it is more preferable to form the three layers in one step. In such a manufacturing method, a plurality of coating stations and drying / curing zone sets, preferably the same number or more as the number of optical thin films, are cascaded between feeding and winding of the support film of the coating machine. This is achieved by providing.
FIG. 1 shows an example of the device configuration. During one step from roll film delivery (101) to winding (112), the first coating station (102), the first drying zone (103), the first UV irradiator (104), the second Coating station (105), second drying zone (106), second UV irradiator (107), third coating station (108), third drying zone (109), third UV irradiator (110) is an example including a post-heating zone (111), for example, three layers of a medium refractive index layer, a high refractive index layer, and a low refractive index layer, a hard coat layer, a high refractive index layer, and a low refractive index layer. Functional layers up to three layers can be formed in one step, such as three layers, a hard coat layer, an antiglare layer, and a low refractive index layer. If necessary, the number of coating stations is reduced to two, and only two layers, the middle refractive index layer and the high refractive index layer, are formed in one step, and the results of checking the surface shape, film thickness, etc. are fed back. To improve the yield, to produce an antiglare antireflection film consisting of two layers, an antiglare layer and a low refractive index layer, at low cost, or as a device configuration increased to four, a hard coat layer, Another preferred embodiment is a manufacturing method in which the refractive index layer, the high refractive index layer, and the low refractive index layer are formed in one step to significantly reduce the coating cost. In addition, it is desirable from the viewpoint of cost and installation location that the layer is formed only with the UV curable resin and the post-heating zone is omitted.

[Polarizer]
The polarizing plate is mainly composed of two protective films that sandwich the polarizing film from both sides. The optical film of the present invention, particularly the antireflection film, is preferably used for at least one of the two protective films sandwiching the polarizing film from both sides. Since the antireflection film of the present invention also serves as a protective film, the production cost of the polarizing plate can be reduced. Further, by using the antireflection film of the present invention as the outermost layer, reflection of external light and the like can be prevented, and a polarizing plate having excellent scratch resistance, antifouling property and the like can be obtained.

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

  The method for stretching the polymer film is described in detail in paragraphs 0020 to 0030 of JP-A-2002-86554.

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

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).
For a VA mode liquid crystal cell, a polarizing plate prepared by combining a triacetyl cellulose film stretched biaxially with the optical film of the present invention is preferably used. As for the method for producing a biaxially stretched triacetyl cellulose film, for example, the methods described in JP-A Nos. 2001-249223 and 2003-170492 are preferably used.

  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. Among them, by using it on the surface opposite to the antireflection film of the present invention, a polarizing plate having an antireflection effect and a viewing angle widening effect can be obtained with the thickness of one polarizing plate, which is particularly preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these. Unless otherwise specified, “part” and “%” are based on mass. In addition, hereinafter, the dispersion Nos. 1 to 9 and Example 10 were used. c-5, c-6, c-7, c-8, c-9, 2c-1, 2c-4, 2c-5, antireflection film No. 10 of Example 11. 303 and 306 shall be read as “reference example”.

<Example 1>
[Stabilization of inorganic oxide fine particles]
(Preparation of dispersion A-1)
Silica fine particle sol (isopropyl alcohol silica sol, IPA-ST-L manufactured by Nissan Chemical Industries, Ltd., average particle size 45 nm, silica concentration 30%), 333 parts, acryloyloxypropyltrimethoxysilane 30 parts, and diisopropoxyaluminum ethyl After adding 1.5 parts of acetate and mixing, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid A-1 was obtained.

(Preparation of Dispersion B-1)
To 333 parts of silica fine particle sol (manufactured by Nissan Chemical Industries, Ltd., methanol silica sol, average particle size 12 nm, silica concentration 30%), 30 parts of acryloyloxypropyltrimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate are added and mixed. After that, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid B-1 was obtained.

(Preparation of dispersion C-1)
Hollow silica fine particle sol (isopropyl alcohol silica sol, CS60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica particle refractive index 1.31) in 500 parts, acryloyloxypropyl After 30 parts of trimethoxysilane and 1.5 parts of diisopropoxyaluminum ethyl acetate were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid C-1 was obtained.

(Preparation of dispersion D-1)
Zirconium oxide fine particle sol (methyl ethyl ketone zirconium sol, manufactured by Sumitomo Osaka Cement Co., Ltd., average particle size 10 nm, zirconium oxide concentration 30%), 333 parts, acryloyloxypropyltrimethoxysilane 30 parts, and diisopropoxyaluminum ethyl acetate 1 After adding 5 parts and mixing, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 8 hours, the mixture was cooled to room temperature, and 1.8 parts of acetylacetone was added to obtain dispersion D-1.

  In the above dispersion, (A-2) to (A-9), (B-) were changed in exactly the same manner except that the compound of general formula (I), acid catalyst or metal chelate compound was changed as shown in Table 1. Dispersions of (2) to (B-6), (C-2) to (C-5) and (D-2) to (D-4) were prepared. The obtained dispersion liquid was subjected to the following evaluation immediately after preparation and after storage at 40 ° C. for 2 weeks.

Evaluation 1: Evaluation of foreign matter in dispersion 10 cc of the dispersion was collected in a test tube having a diameter of 10 mm, and the foreign matter was visually observed. The degree of occurrence of foreign matters that can be visually observed was divided into the following four ranks and evaluated.
○: Foreign matter is not recognized.
Δ: Foreign matter of about 50 μm is slightly observed.
X: Foreign matter of 500 μm or more is clearly recognized.
XX: In addition to foreign matters of 500 μm or more, clear aggregated sediment is observed.
Evaluation 2: Viscosity of dispersion liquid The viscosity of the dispersion liquid was measured at 25 ° C. using a vibration viscometer.
Table 1 shows the results of evaluation for each dispersion immediately after preparation and after standing at 40 ° C. for 2 weeks.
Table 1

From Table 1, the following is clear.
According to the present invention, a dispersion obtained by treating inorganic oxide fine particles using a compound represented by the general formula (I) and at least one of an acid catalyst and a metal chelate compound can be used immediately after preparation and after storage at high temperature. There is little generation of foreign matter in the dispersion, and there is little increase in viscosity and it is stable. In particular, a dispersion prepared using a compound represented by a metal chelate compound has little change in viscosity with time and is excellent in stability.
In addition, a dispersion using di-n-butoxybis (ethyl acetate) zirconium instead of diisopropoxyaluminum acetoacetate at the time of preparing the dispersion (C-1), and a diisotropy at the time of preparing the dispersion (D-4). A dispersion using diisopropoxybis (ethyl acetate) titanium instead of propoxyaluminum acetoacetate was prepared and evaluated in the same manner as described above. The dispersion prepared using the metal chelate compound of the present invention had a viscosity of There was little change with time, and there was a tendency to be excellent in stability.

<Example 2>
[Preparation of dispersion subjected to solvent substitution treatment A2-1]
While adding methyl isobutyl ketone to 500 g of the dispersion liquid (A-1) of Example 1 so that the silica content was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 150 torr. When the residual amount of isopropyl alcohol in the obtained dispersion was analyzed by gas chromatography, it was 1.0% or less. There was no generation of foreign matter in the dispersion, and the viscosity when the solid concentration was adjusted to 30% with methyl isobutyl ketone was 3 mPa · s at 25 ° C.
[Preparation of solvent-dispersed dispersion B2-2]
While adding methyl ethyl ketone to 500 g of the dispersion liquid (B-2) of Example 1 so that the silica content was substantially constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 150 torr. When the residual amount of methanol in the obtained dispersion was analyzed by gas chromatography, it was 1.0% or less. There was no generation of foreign matter in the dispersion, and the viscosity was 3 mPa · s at 25 ° C. when the solid content was adjusted to 30% with methyl ethyl ketone.
[Preparation of dispersion subjected to solvent substitution C2-1]
While adding methyl isobutyl ketone to 500 g of the dispersion (C-1) of Example 1 so that the content of silica was almost constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 150 torr. When the residual amount of isopropyl alcohol in the obtained dispersion was analyzed by gas chromatography, it was 1.0% or less. No foreign matter was generated in the dispersion, and the viscosity when the solid concentration was adjusted to 20% with methyl isobutyl ketone was 2 mPa · s at 25 ° C.

<Example 3>
The multilayer antireflection film shown below was produced.
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by mass of trimethylolpropane triacrylate (TMPTA: Biscote # 295, manufactured by Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500.0 parts by mass of cyclohexanone and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, Nippon Ciba Geigy Co., Ltd.) were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5 mass ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 70 nm.

Dispersant

(Preparation of coating solution for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.6 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by mass, 279.6 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer)
To 469.8 parts by mass of the above titanium dioxide dispersion, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Geigy Co., Ltd.), 1.1 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and 459.6 parts by mass of cyclohexanone. Parts were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of coating solution A for low refractive index layer)
74.4 parts by mass of the following perfluoroolefin copolymer (1), 3 parts by mass of terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.), 200 parts by mass of methyl isobutyl ketone Radical generator Irgacure 907 (trade name) 3 parts by mass, photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, 18.6 parts by mass of Nippon Kayaku Co., Ltd.) was added and dissolved. A coating solution A was prepared by diluting with methyl ethyl ketone so that the solid content concentration of the entire coating solution was 7% by mass.

Perfluoroolefin copolymer (1)

(Synthesis of perfluoroolefin copolymer (1))
Into a stainless steel autoclave with a stirrer of 100 ml, 40 ml of ethyl acetate, 14.7 g of hydroxyethyl vinyl ether and 0.55 g of dilauroyl peroxide were charged, and the inside of the system was deaerated and replaced with nitrogen gas. Furthermore, 25 g of hexafluoropropylene (HFP) was introduced into the autoclave and the temperature was raised to 65 ° C. The pressure when the temperature in the autoclave reached 65 ° C. was 5.4 kg / cm ² . The reaction was continued for 8 hours while maintaining the temperature, and when the pressure reached 3.2 kg / cm ² , the heating was stopped and the mixture was allowed to cool. When the internal temperature dropped to room temperature, unreacted monomers were driven out, the autoclave was opened, and the reaction solution was taken out. The obtained reaction solution was poured into a large excess of hexane, and the polymer was precipitated by removing the solvent by decantation. Further, this polymer was dissolved in a small amount of ethyl acetate and reprecipitated twice from hexane to completely remove the residual monomer. After drying, 28 g of polymer was obtained. Next, 20 g of the polymer was dissolved in 100 ml of N, N-dimethylacetamide, and 11.4 g of acrylic acid chloride was added dropwise under ice cooling, followed by stirring at room temperature for 10 hours. Ethyl acetate was added to the reaction solution, washed with water, the organic layer was extracted and concentrated, and the resulting polymer was reprecipitated with hexane to obtain 19 g of perfluoroolefin copolymer (1). The resulting polymer had a refractive index of 1.421.

(Preparation of antireflection film 301)
A hard coat layer coating solution was applied onto a triacetyl cellulose film (TD-80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^2. Irradiation with an irradiation amount of 300 mJ / cm ² was applied to cure the coating layer to form a hard coat layer having a thickness of 8 μm.
On the hard coat layer, an intermediate refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution A were successively applied using a gravure coater having three coating stations.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 400 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

The low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.458 and a film thickness of 85 nm.

(Preparation of antireflection film 302)
A sample 302 was prepared by changing the low refractive index layer in the sample 301 as follows. Samples 301 and 302 are synonymous with antireflection films 301 and 302. The same applies hereinafter.
(Preparation of sol solution a)
A stirrer, a reactor equipped with a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed. Thereafter, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of coating solution B for low refractive index layer)
Fluoropolymer 51 parts by mass and terminal methacrylate group-containing silicone resin X-22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass with respect to 200 parts by mass of methyl isobutyl ketone Parts, photoradical generator Irgacure 907 (trade name) 3 parts by mass, photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) 1 part by mass, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) 13 parts by mass were added and dissolved, and then the sol solution a was prepared in 22.5 parts by mass (9 parts by mass as the solid content after solvent volatilization) and Example 1. 111 parts by mass (20 parts by mass as silica solid content) of dispersion A-1 was added. The coating solution B was completed by diluting with methyl ethyl ketone so that the solid content concentration of the entire coating solution was 7% by mass.
The low refractive index layer coating liquid B thus obtained was applied according to Sample 301, and the low refractive index layer thickness was adjusted to 85 nm to prepare Sample 302.

(Preparation of antireflection film 312)
A sample 312 was produced in the same manner as the sample 302 except that the dispersion C-1 prepared in Example 1 was used. The low refractive index layer after curing had a refractive index of 1.44 and a film thickness of 85 nm.

(Preparation of antireflection film 318)
A sample 318 in which the low refractive index layer of the sample 301 was changed as follows was produced.

(Preparation of coating solution C for low refractive index layer)
For 200 parts by mass of methyl isobutyl ketone, 44 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), terminal methacrylate group-containing silicone resin X-22-164C ( 3 parts by weight of Shin-Etsu Chemical Co., Ltd., 2.5 parts by weight of photoradical generator Irgacure 907 (trade name), 0.5 parts by weight of photosensitizer (Kayacure-DETX, Nippon Kayaku Co., Ltd.) After addition and dissolution, 45 parts by mass of the sol liquid a (18 parts by mass as a solid content after solvent evaporation) and 222 parts by mass of the dispersion C-1 prepared in Example 1 (40 parts by mass as a silica solid content) ) Was added. The coating liquid C was completed by diluting with methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 7% by mass.

  The low refractive index layer coating liquid C thus obtained was applied according to the sample 301 and adjusted so that the thickness of the low refractive index layer was 85 nm to prepare a sample 318. The low refractive index layer after curing had a refractive index of 1.44 and a film thickness of 85 nm.

(Preparation of antireflection film 324)
A sample 324 in which the low refractive index layer in the sample 301 was changed as follows was produced.
(Preparation of coating solution D for low refractive index layer)
3 parts by weight of cyclohexanone is added to 100 parts by weight of OPSTAR JTA113 (thermally crosslinkable fluorine-containing polymer composition (solid content 6%), solvent methyl ethyl ketone: manufactured by JSR Corporation) to prepare a coating solution D for a low refractive index layer. did.
The low refractive index layer coating liquid D thus obtained was applied according to Sample 301, and the low refractive index layer thickness was adjusted to 85 nm to prepare Sample 324. The low refractive index layer was dried at 120 ° C. for 12 minutes, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less. ), And the irradiation amount was 120 mW / cm ² and the irradiation amount was 120 mJ / cm ² .

(Preparation of antireflection film 325)
A sample 325 in which the low refractive index layer in the sample 324 was changed as follows was produced.
(Preparation of coating liquid E for low refractive index layer)
70 parts by mass of OPSTAR JTA113 (thermally crosslinkable fluorine-containing polymer composition (solid content: 6%): manufactured by JSR Corporation) and 9.9 parts by mass of dispersion C-1 of Example 1 (1. 8 parts by mass) and 2.0 parts by mass of sol liquid a (0.81 parts by mass as a solid content) were added with 2.4 parts by mass of cyclohexanone to prepare a coating solution E for low refractive index layer.
Using the coating solution E for the low refractive index layer thus obtained, coating and curing were performed according to the sample 324. A sample 325 was prepared by adjusting the thickness of the low refractive index layer to 85 nm.

(Evaluation of antireflection film)
About the obtained film, the following items were evaluated.
(1) Haze of coating film sample Haze meter MODEL 1001DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.) was used for measurement. In the evaluation, both the sample coated within 3 hours after the preparation of the low refractive index layer coating solution and the sample coated after storing the low refractive index layer coating solution at 40 ° C. for 48 hours were compared and evaluated.
(2) Steel Wool Scratch Resistance (SW Strength) Evaluation Using a rubbing tester, a rubbing test was performed under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
○: Even when viewed very carefully, no scratches are visible.
○ △: Slightly weak scratches are visible when viewed very carefully.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.
XX: Single-sided film is damaged.

[Preparation of Antireflection Films 303 to 317, 319 to 323, 326 to 330]
Samples 302 to 317, 319 to 323, and 326 were the same except that the main binder composition of the low refractive index layer formulation of Samples 302, 318, and 325 was left unchanged, and the inorganic fine particle dispersion was changed as shown in Table 1. ~ 330 were made. The details of the sample 312 have already been described.
The evaluation results are shown in Table 2.
Table 2

From the results shown in Table 2, the following is clear.
It can be seen that the coating film using the inorganic oxide fine particles treated with the dispersion of the present invention has no increase in haze and the film strength is improved. In particular, it can be seen that samples mainly using a photo-curing binder have excellent film strength (samples 302 to 304, 307 to 312, 315 to 318, 321 to 323, and 328 to 330).
Moreover, it can be seen that the sample using the dispersion liquid in which the solvent was replaced according to Example 2 had less haze after the coating liquid preparation time-lapse and was excellent in coating liquid stability. (Samples 311, 317, 323, 330)

<Example 4>
In Example 3, a sample in which the polymerizable group of the fluorine-containing polymer of the low refractive index layer coating liquids A and B was changed from acrylate to methacrylate was prepared, and the evaluation according to Example 3 was performed. The same effect was obtained except that the wool scratch resistance deteriorated.

<Example 5>
Example 3 A triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm, which was immersed in an aqueous 1.5 mol / L, 55 ° C. NaOH solution for 2 minutes, then neutralized and washed with water. A polarizing plate was produced by adhering and protecting both sides of a polarizer prepared by adsorbing iodine to polyvinyl alcohol on the backside saponified triacetylcellulose film of the sample according to the present invention. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the D-BEF made by the manufacturing method was replaced with the polarizing plate on the viewing side (having between the backlight and the liquid crystal cell), there was very little reflection of the background, and a display device with very high display quality was obtained. In particular, samples (samples 312, 315, and 316) using hollow silica particles having a refractive index of 1.31 of the inorganic oxide fine particles were able to obtain a display device with particularly low reflection and high visibility.

<Example 6>
The multilayer antireflection film shown below was produced.

(Preparation of coating liquid A for hard coat layer)
PETA 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.5g
Cross-linked acrylic-styrene particles (30%) 13.9g
FP-132 0.75g
KBM-5103 10.0g
Toluene 38.5g
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution.

The compounds used are shown below.
PETA: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (manufactured by Nippon Kayaku Co., Ltd.)
Irgacure 184: Polymerization initiator (Ciba Specialty Chemicals 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 in a Polytron disperser for 20 minutes).
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser).

FP-132: Fluorine surface modifier

  KBM-5103: acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Coating of hard coat layer)
An 80 μm-thick triacetyl cellulose film (TAC-TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form and directly coated with the above coating liquid A for hard coat layer 180 lines / inch, depth 40 μm. Using a micro gravure roll with a diameter of 50 mm and a doctor blade having a gravure pattern, the coating was applied under the conditions of a gravure roll rotational speed of 30 rpm and a conveying speed of 30 m / min, dried at 60 ° C. for 150 seconds, and further oxygen concentration under nitrogen purge Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 0.1% and 160 W / cm, the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² A 6 μm thick layer was formed and wound up. The surface roughness of the coating film 601 obtained in this manner was Ra = 0.18 μm, Rz = 1.40 μm, and haze 35%.

  As a result of coating the low refractive index layers of Examples 3 and 4 on the coating film 601 and performing the evaluation according to Example 3, the obtained antireflection film according to the present invention had high steel wool scuff resistance. .

<Example 7>
In Examples 3 and 6, samples in which the coating method was changed from a gravure coater to a die coater were prepared, and evaluations according to Examples 3 and 6 were performed. As a result, the antireflection film according to the present invention was excellent in the surface of the coating film, had a low reflectance, and was excellent in the scratch resistance of the film.

<Example 8>
When the samples according to the present invention of Examples 3 and 6 were bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained. It was.

<Example 9>
[Stabilization of inorganic oxide fine particles]
(Preparation of dispersion a-1)
30 parts of tridecafluorooctyltrimethoxysilane (A-1) to 333 parts of silica fine particle sol (isopropyl alcohol silica sol, IPA-ST-L manufactured by Nissan Chemical Industries, Ltd., average particle diameter 45 nm, silica concentration 30% by mass) And 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, and then 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, added 1.8 parts of acetylacetone, and obtained dispersion liquid a-1.

(Preparation of dispersion b-1)
Silica fine particle sol (methanol silica sol (trade name), average particle size 12 nm, silica concentration 30%, manufactured by Nissan Chemical Industries, Ltd.) 333 parts, heptadecafluorodecyltrimethoxysilane (A-3) (TSL-8233, 30 parts of GE Toshiba Silicone Co., Ltd.) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, and then 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid b-1 was obtained.

(Preparation of dispersion c-1)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) After 30 parts of fluorooctyltrimethoxysilane (A-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid c-1 was obtained.

(Preparation of dispersion d-1)
Zirconium oxide fine particle sol (Methyl ethyl ketone zirconium oxide sol, Sumitomo Osaka Cement Co., Ltd. average particle size 10 nm, zirconium oxide concentration 30%), 333 parts, heptadecafluorodecyltrimethoxysilane (A-3) 30 parts, and diiso After adding 1.5 parts of propoxyaluminum ethyl acetoacetate and mixing, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid d-1 was obtained.

  In the preparation of the dispersions a-1, b-1, c-1, and d-1, the compounds represented by the general formula [1] or [2] and the compounds represented by the general formula (II) are shown in Table 3. Except for changing to, dispersions a-2 to a-4, b-2 to b-4, c-2 to c-4, d-2 to d-4 were prepared in the same manner. The obtained dispersion liquid was subjected to the following evaluation immediately after preparation and after storage at 40 ° C. for 2 weeks.

Evaluation 1: Evaluation of foreign matter in dispersion 10 cc of the dispersion was collected in a test tube having a diameter of 10 mm, and the foreign matter was visually observed. The degree of occurrence of foreign matters that can be visually observed was evaluated in the following four ranks.
○: Foreign matter is not recognized.
Δ: Slightly foreign matter of about 50 μm is observed.
X: Foreign matter of 500 μm or more is clearly recognized.
XX: Aggregate precipitate is clearly observed in addition to foreign matters of 500 μm or more.

Evaluation 2: Viscosity of Dispersion Viscosity of the dispersion was measured at 25 ° C. with a vibration viscometer (CJV5000 manufactured by A & D Co., Ltd.). Table 3 shows the evaluation results for each dispersion immediately after preparation and after standing at 40 ° C. for 2 weeks.
Table 3

From Table 3, the following is clear.
In accordance with the present invention, inorganic oxide fine particles were treated with a compound represented by general formula [1] or [2] and / or a compound represented by general formula (II) in the presence of a metal chelate compound. The dispersion produces little foreign matter in the dispersion immediately after preparation and after storage at a high temperature. Further, the viscosity is stable with little increase in viscosity after standing at 40 ° C. for 2 weeks.

<Example 10>
[Preparation of solvent-dispersed dispersion]
(Preparation of sol solution a)
A reactor equipped with a stirrer and a reflux condenser, 120 parts of methyl ethyl ketone, 100 parts of acryloyloxypropyltrimethoxysilane (M-1) (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), diisopropoxyaluminum ethyl acetoacetate 3 After adding parts and mixing, 30 parts of ion-exchanged water was added and reacted at 60 ° C. for 4 hours, and then cooled to room temperature to obtain sol solution a. The mass average molecular weight was 1600, and among the components higher than the oligomer component, the component having a molecular weight of 1000 to 20000 was 100%. Further, from the gas chromatography analysis, the raw material acryloyloxypropyltrimethoxysilane did not remain at all.

(Preparation of sol solution b)
In the preparation of the sol solution a, a sol solution b which differs only in that the reaction time was changed to 2 hours was prepared.
(Preparation of sol solution c)
In the preparation of the sol solution b, instead of 100 parts of acryloyloxypropyltrimethoxysilane (M-1), tridecafluorooctyltrimethoxysilane (A-1) (TSL-8257, manufactured by GE Toshiba Silicone Co., Ltd.) 40 Sol solutions c differing only in the addition of 60 parts of acryloyloxypropyltrimethoxysilane (M-1).
(Preparation of dispersion c-5)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) in 500 parts, acryloyloxy After 30 parts of propyltrimethoxysilane (M-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and the dispersion liquid c-5 was obtained.

(Preparation of dispersion c-6)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) After 10 parts of fluorooctyltrimethoxysilane (A-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 4 hours, 30 parts of acryloyloxypropyltrimethoxysilane (M-1) was further added and reacted for 4 hours. After cooling to room temperature, 1.8 parts of acetylacetone was added to obtain dispersion c-6.

(Preparation of dispersion c-7)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) in 500 parts, acryloyloxy After 15 parts of propyltrimethoxysilane (M-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 4 hours, 63 parts of the sol solution c was further added and reacted for 4 hours. After cooling to room temperature, 1.8 parts of acetylacetone was added to obtain dispersion c-7.

(Preparation of dispersion c-8)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) After 10 parts of fluorooctyltrimethoxysilane (A-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. After reacting at 60 ° C. for 4 hours, 75 parts of the sol solution b was further added and reacted for 4 hours. After cooling to room temperature, 1.8 parts of acetylacetone was added to obtain dispersion c-8.

(Preparation of dispersion c-9)
Hollow silica fine particle sol (Isopropyl alcohol hollow silica sol, CS-60-IPA manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) After 10 parts of fluorooctyltrimethoxysilane (A-1), 30 parts of acryloyloxypropyltrimethoxysilane (M-1) and 1.5 parts of diisopropoxyaluminum ethyl acetoacetate were added and mixed, 9 parts of ion-exchanged water was added. added. After making it react at 60 degreeC for 8 hours, it cooled to room temperature, 1.8 parts of acetylacetone was added, and dispersion liquid c-9 was obtained.

(Preparation of solvent-dispersed dispersion: 2 blank)
Approximately 500 g of an untreated hollow silica fine particle sol (isopropyl alcohol silica sol, CS-60-IPA, manufactured by Catalytic Chemical Industry Co., Ltd., average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20%, silica refractive index 1.31) While adding cyclohexanone so that the content of silica was constant, solvent substitution was performed by distillation under reduced pressure at a pressure of 39 hPa. No foreign matter was generated in the dispersion, and the viscosity when the solid content concentration was adjusted to 20% with cyclohexanone was 30 mPa · s at 25 ° C. The residual amount of isopropyl alcohol in the obtained dispersion was analyzed by gas chromatography and found to be 0.5% or less.

(Preparation of solvent-dispersed dispersion: 2c-1)
The same operation as 2blank was performed with 500 g of the dispersion c-1 of Example 9 to obtain 2c-1. The viscosity was 12 mPa · s at 25 ° C.
(Preparation of solvent-dispersed dispersion: 2c-2)
2c-2 was obtained by carrying out the same operation as 2blank with 500 g of the dispersion c-2 of Example 9. The viscosity was 13 mPa · s at 25 ° C.
(Preparation of solvent-dispersed dispersion: 2c-3)
2c-3 was obtained by performing the same operation as 2 blank with 500 g of the dispersion liquid (c-3) of Example 9. The viscosity was 13 mPa · s at 25 ° C.
(Preparation of solvent-dispersed dispersion: 2c-5)
The same operation as 2blank was performed with 500 g of the dispersion (c-5) to obtain 2c-5. The viscosity was 15 mPa · s at 25 ° C.
(Preparation of solvent-dispersed dispersion: 2c-6 to 2c-8)
Dispersions c-6, c-7, c-8 and c-9 were also subjected to the same operation as 2blank to obtain 2c-6, 2c-7, 2c-8 and 2c-9, respectively.

<Example 11>
The multilayer antireflection film shown below was produced.
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.
750.0 parts by mass of trimethylolpropane triacrylate (Biscoat # 295, manufactured by Nippon Kayaku Co., Ltd.), 270.0 parts by mass of poly (glycidyl methacrylate) having a mass average molecular weight of 15000, 730.0 parts by mass of methyl ethyl ketone, 500 cyclohexanone 0.0 part by mass and 50.0 parts by mass of a photopolymerization initiator (Irgacure 184, manufactured by Ciba Geigy Japan, Inc.) were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a hard coat layer.

(Preparation of titanium dioxide fine particle dispersion)
As the titanium dioxide fine particles, titanium dioxide fine particles (MPT-129C, manufactured by Ishihara Sangyo Co., Ltd., TiO ₂ : Co ₃ O ₄ : containing cobalt and subjected to surface treatment using aluminum hydroxide and zirconium hydroxide: Al ₂ O ₃ : ZrO ₂ = 90.5: 3.0: 4.0: 0.5 mass ratio) was used.
The following dispersant (41.1 parts by mass) and cyclohexanone (701.8 parts by mass) were added to 257.1 parts by mass of the particles and dispersed by dynomill to prepare a titanium dioxide dispersion having a mass average diameter of 70 nm.
Dispersant

(Preparation of coating solution for medium refractive index layer)
In 99.1 parts by mass of the above titanium dioxide dispersion, 68.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA), 3.6 parts by mass of a photopolymerization initiator (Irgacure 907), light A sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1.2 parts by mass, 279.6 parts by mass of methyl ethyl ketone and 1049.0 parts by mass of cyclohexanone were added and stirred. After sufficiently stirring, the solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a medium refractive index layer.

(Preparation of coating solution for high refractive index layer)
To 469.8 parts by mass of the above titanium dioxide dispersion, 40.0 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907) 3.3 parts by mass, manufactured by Ciba Geigy Co., Ltd.), 1.1 parts by mass of photosensitizer (Kayacure-DETX, manufactured by Nippon Kayaku Co., Ltd.), 526.2 parts by mass of methyl ethyl ketone, and 459.6 parts by mass of cyclohexanone. Parts were added and stirred. The solution was filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a coating solution for a high refractive index layer.

(Preparation of coating solution A for low refractive index layer)
2-butanone 200 parts by weight, cyclohexanone 150 parts by weight, fluorine-containing polymer (P-3) 75.2 parts by weight, methacrylate group-containing silicone resin RMS-033 (manufactured by Gelest Co., Ltd.) 3 parts by weight, photoradical generation 3 parts by mass of the agent Irgacure 907 (trade name) and 18.8 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (DPHA, Nippon Kayaku Co., Ltd.) were added and dissolved. A low refractive index layer coating solution A was prepared by diluting with methyl ethyl ketone so that the solid content concentration of the entire coating solution was 7% by mass.

(Preparation of antireflection film 301)
A hard coat layer coating solution was applied on a triacetyl cellulose film (TD80UF, manufactured by Fuji Photo Film Co., Ltd.) having a thickness of 80 μm using a gravure coater. After drying at 100 ° C., an irradiance of 400 mW / cm using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of 160 W / cm while purging with nitrogen so that the oxygen concentration becomes 1.0 vol% or less. ^2. Irradiation with an irradiation amount of 300 mJ / cm ² was applied to cure the coating layer to form a hard coat layer having a thickness of 8 μm.
On the hard coat layer, an intermediate refractive index layer coating solution, a high refractive index layer coating solution, and a low refractive index layer coating solution A were successively applied using a gravure coater having three coating stations.

The medium refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 180 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 1.0% by volume or less. ), And the irradiation dose was 400 mW / cm ² and the irradiation dose was 400 mJ / cm ² .
The medium refractive index layer after curing had a refractive index of 1.630 and a film thickness of 67 nm.

The drying condition of the high refractive index layer is 90 ° C. for 30 seconds, and the ultraviolet curing condition is a 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0 vol. ), And the irradiation dose was 600 mW / cm ² and the irradiation dose was 400 mJ / cm ² . The cured high refractive index layer had a refractive index of 1.905 and a film thickness of 107 nm.

The low refractive index layer was dried at 90 ° C. for 30 seconds, and the ultraviolet curing condition was 240 W / cm air-cooled metal halide lamp (eye graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.05% by volume or less. ), And the irradiation amount was 600 mW / cm ² and the irradiation amount was 600 mJ / cm ² .
The low refractive index layer after curing had a refractive index of 1.458 and a film thickness of 85 nm.

(Preparation of antireflection film 302)
A sample 302 was prepared by changing the low refractive index layer in the sample 301 as follows. Samples 301 and 302 are synonymous with antireflection films 301 and 302. The same applies hereinafter.

(Preparation of coating solution B for low refractive index layer)
2 parts by mass of 2-butanone and 150 parts by mass of cyclohexanone, 30 parts by mass of the fluorine-containing polymer used in the coating solution A for low refractive index layer, 3 parts by mass of methacrylate group-containing silicone resin RMS-033 (manufactured by Gelest Co., Ltd.) Parts, photoradical generator Irgacure 907 (trade name) 3 parts by mass, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (DPHA, Nippon Kayaku Co., Ltd.) 7 parts by mass, 45 parts by mass of the sol liquid a (27 parts by mass as the solid content after solvent evaporation) and 150 parts by mass of the dispersion 2 blank prepared in Example 10 (30 parts by mass as the silica solid content) were added. The coating liquid B for low refractive index layer was completed by diluting with methyl ethyl ketone so that the solid content concentration of the entire coating liquid was 7% by mass.
The low refractive index layer coating liquid B thus obtained was applied according to Sample 301, and the low refractive index layer thickness was adjusted to 85 nm to prepare Sample 302. The refractive index of the low refractive index layer of Sample 302 was 1.435.

(Evaluation of antireflection film)
About the obtained film, the following items were evaluated.
(1) Planar shape of coating film sample Oily black ink was applied to the back surface of the coated sample, and the angle was changed at about 10 cm under a 500 W three-wavelength fluorescent lamp and visually evaluated.
The unevenness in which reflected light is diffused and appears white and dull is evaluated according to the following criteria.
A: Even if you look very carefully, you can not see any haze.
○: Slightly diffused when viewed very carefully.
Δ: A haze-like white portion is observed.
X: One surface has a white haze.

(2) Steel Wool Scratch Resistance (SW Strength) Evaluation Using a rubbing tester, a rubbing test was performed under the following conditions.
Evaluation environmental conditions: 25 ° C., 60% RH
Rub material: Steel wool (No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was wound around the rubbing tip (1 cm × 1 cm) of a tester in contact with the sample, and the band was fixed so as not to move.
Moving distance (one way): 13 cm, rubbing speed: 13 cm / sec, load: 500 g / cm ² , tip contact area: 1 cm × 1 cm, rubbing frequency: 10 reciprocations.
An oil-based black ink was applied to the back side of the rubbed sample and visually observed with reflected light, and scratches on the rubbed portion were evaluated according to the following criteria.
A: Even when viewed very carefully, no scratches are visible.
○: Slightly weak scratches are visible when viewed very carefully, but there is no practical problem.
Δ: A weak scratch is visible.
Δ ×: moderate scratches are visible.
X: There are scratches that can be seen at first glance.
XX: Single-sided film is damaged.

(Preparation of antireflection films 303 to 307)
Samples 303 to 306 were prepared in the same manner except that the main binder composition of the low refractive index layer formulation of sample 302 was left unchanged and the addition amount of the inorganic fine particle dispersion and sol liquid a was changed as shown in Table 4. . The refractive indexes of Samples 303 to 306 were all around 1.435. Sample 307 was produced in the same manner as sample 305, except that the fluoropolymer (P-3) was replaced with DPHA. The refractive index of Sample 307 was 1.44.
Table 4

From the results shown in Table 4, the following is clear.
It was found that the coating film using the hollow silica fine particles treated with the dispersion of the present invention showed good values for both the surface shape and the SW strength.

Samples 308 to 311 were prepared in the same manner except that the sol solution a was removed by changing the inorganic fine particle dispersion as shown in Table 5 while keeping the main binder composition of the low refractive index layer formulation of the sample 302. did.
Table 5

From the results shown in Table 5, the following is clear.
When the dispersion of the present invention was compared with the same amount of the partial condensate with the silane coupling agents (A-1) and (M-1), (M-1) was added from the middle of the reaction (sample 308). In addition, it was found that the SW strength and the surface shape tend to be improved by adding the sol liquid b which is the sol of (M-1) (sample 310).
Further, it was found that the surface shape and the SW intensity tend to be improved by adding sol c (sample 309) which is the sol of (A-1) and (M-1).

<Example 12>
In Example 11, a sample in which the polymerizable group of the fluorine-containing polymer in the low refractive index layer coating liquids A and B was changed from acrylate to methacrylate was prepared, and the evaluation according to Example 11 was performed. A similar effect was obtained except that the scratch resistance deteriorated.

<Example 13>
80 μm-thick triacetylcellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.), neutralized and washed with a 1.5 mol / L, 55 ° C. NaOH aqueous solution for 2 minutes, and the book of Example 11 A polarizing plate was prepared by adhering and protecting both sides of a polarizer prepared by adsorbing iodine to polyvinyl alcohol on a back-saponified triacetyl cellulose film of the sample according to the invention and stretching. A liquid crystal display device of a notebook personal computer equipped with a transmissive TN liquid crystal display device (Sumitomo 3M Co., Ltd., which is a polarization separation film having a polarization selection layer) so that the anti-reflection film side is the outermost surface. When the D-BEF made by the manufacturing method was replaced with the polarizing plate on the viewing side (having between the backlight and the liquid crystal cell), there was very little reflection of the background, and a display device with very high display quality was obtained. In particular, a sample using hollow silica particles having a refractive index of 1.31 of the inorganic oxide fine particles was able to obtain a display device with particularly low reflection and high visibility.

<Example 14>
The multilayer antireflection film shown below was produced.

(Preparation of coating liquid A for hard coat layer)
PETA 50.0g
Irgacure 184 2.0g
SX-350 (30%) 1.5g
Cross-linked acrylic-styrene particles (30%) 13.9g
FP-132 0.75g
KBM-5103 10.0g
Toluene 38.5g
The mixed solution was filtered through a polypropylene filter having a pore size of 30 μm to prepare a hard coat layer coating solution.

The compounds used are shown below.
PETA: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (KAYARAD PET-30 (trade name), manufactured by Nippon Kayaku Co., Ltd.)
Irgacure 184: Polymerization initiator (Ciba Specialty Chemicals 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 in a Polytron disperser for 20 minutes).
Cross-linked acrylic-styrene particles: average particle size 3.5 μm (refractive index 1.55, manufactured by Soken Chemical Co., Ltd., 30% toluene dispersion, used after dispersion at 10,000 rpm for 20 minutes in a Polytron disperser).
FP-132: Fluorine surface modifier

  KBM-5103: acryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).

(Coating of hard coat layer)
An 80 μm-thick triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) is unwound in a roll form and directly coated with the coating liquid A for hard coat layer 180 lines / inch and a depth of 40 μm. Using a micro gravure roll having a diameter of 50 mm and a doctor blade having a pattern, coating was performed under the conditions of a gravure roll rotation speed of 30 rpm and a conveyance speed of 30 m / min, drying at 60 ° C. for 150 seconds, and then an oxygen concentration of 0. Using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) at 1%, the coating layer is cured by irradiating ultraviolet rays with an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² , and a thickness of 6 μm The layer was formed and wound up. The surface roughness of the coating film 601 obtained in this manner was Ra = 0.18 μm, Rz = 1.40 μm, and haze 35%.

  As a result of coating the low refractive index layers of Examples 11 and 12 on the above hard coat layer and performing an evaluation according to Example 11, the obtained antireflection film according to the present invention has an excellent surface shape and is steel. Wool scuff resistance was strong.

<Example 15>
(Preparation of coating solution for hard coat layer)
The following composition was put into a mixing tank and stirred to obtain a hard coat layer coating solution.

(Coating solution composition for hard coat layer)
Desolite Z7404
(Zirconia fine particle-containing hard coat composition solution: manufactured by JSR Corporation) 100 parts by mass DPHA (UV curable resin: manufactured by Nippon Kayaku Co., Ltd.) 31 parts by mass KBM-5103 (silane coupling agent: Shin-Etsu Chemical Co., Ltd.) )) 10 parts by mass KE-P150 (1.5 μm silica particles: manufactured by Nippon Shokubai Co., Ltd.) 8.9 parts by mass MXS-300 (3 μm cross-linked PMMA particles: manufactured by Soken Chemical Co., Ltd.) 3.4 parts by mass MEK 29 parts by weight MIBK 13 parts by weight

(Preparation of antireflection film)
A triacetyl cellulose film (TD80U, manufactured by Fuji Photo Film Co., Ltd.) as a support is unrolled in a roll form, and the above coating liquid for hard coat layer has a diameter of 135 lines / inch and a gravure pattern with a depth of 60 μm. Using a 50 mm micro gravure roll and a doctor blade, the coating was carried out under conditions of a conveyance speed of 10 m / min, dried at 60 ° C. for 150 seconds, and further under a nitrogen purge, an air-cooled metal halide lamp (Igraphics Corporation) )), The coating layer was cured by being irradiated with ultraviolet rays having an illuminance of 400 mW / cm ² and an irradiation amount of 250 mJ / cm ² . The rotational speed of the gravure roll was adjusted so that the thickness of the hard coat layer after curing was 3.6 μm. When the surface roughness of the hard coat layer was measured with a scanning probe microscope system (manufactured by Seiko Instruments Inc., SPI model 3800), the center line average roughness Ra = 0.04 μm and the root mean square roughness RMS = 0.06 μm. The ten-point average roughness Rz = 0.27 μm. As a result of coating the low refractive index layer of Example 11 on the above hard coat layer and performing the evaluation according to Example 11, the obtained antireflection film according to the present invention was excellent in surface shape and was made of steel wool. Scratch resistance was strong.

<Example 16>
In Examples 11 and 15, samples in which the coating method was changed from the gravure coater to the die coater were produced, and evaluation according to Examples 11 and 15 was performed. As a result, the antireflection film according to the present invention was excellent in the surface of the coating film, had a low reflectance, and was excellent in the scratch resistance of the film.

<Example 17>
When the samples according to the present invention of Examples 11 and 15 were bonded to the glass plate on the surface of the organic EL display device via an adhesive, reflection on the glass surface was suppressed, and a display device with high visibility was obtained. It was.

It is a schematic diagram which shows an example of a structure of the apparatus for manufacturing the antireflection film of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Roll film delivery 102 1st coating station 103 1st drying zone 104 1st UV irradiation machine 105 2nd coating station 106 2nd drying zone 107 2nd UV irradiation machine 108 3rd coating station 109 Third drying zone 110 Third UV irradiator 111 Post-drying zone 112 Roll film winding

Claims (15)

A method for producing an inorganic oxide fine particle dispersion in which inorganic oxide fine particles are dispersed in an organic solvent, the production method comprising:
(1) An organosilane represented by the following general formula (II) in the presence of at least one of an acid catalyst and the following metal chelate compound in an alcoholic organic solvent having a ketone solvent content of 30% by volume or less . A step of surface-treating inorganic oxide fine particles with at least one of a hydrolyzate and / or a partial condensate thereof and at least one fluorine-containing silane coupling agent represented by the following general formula [1] ; and
(2) A step of replacing the dispersion medium used in the surface treatment with a solvent so that the content of the ketone solvent in all the solvents is increased to 90% by volume or more ,
Including
The solvent substitution is a solvent substitution by distillation under reduced pressure while adding a ketone solvent so that the content of inorganic oxide particles is constant,
The method for producing an inorganic oxide fine particle dispersion, wherein the ketone solvent is a solvent selected from acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone.
Metal chelate compounds (wherein, R ³ represents. An alkyl group having 1 to 10 carbon atoms) Formula R ³ OH alcohol and / or the general formula R ⁴ COCH ₂ COR ⁵ (wherein represented by, R ⁴ is Zr, Ti, wherein the alkyl group has 1 to 10 carbon atoms, R ⁵ represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. And at least one metal chelate compound having a metal selected from Al as a central metal.
Formula (II)

(In the formula, R ¹ represents a hydrogen atom, a methyl group, a methoxy group, an alkoxycarbonyl group, a cyano group, or a chlorine atom. Y represents a single bond, —COO—, —CONH—, or —O—, and L represents Represents a divalent linking group, n represents 0 or 1. R ¹⁰ represents a substituted or unsubstituted alkyl group or an unsubstituted aryl group, and X represents a hydroxyl group or a hydrolyzable group.
Formula _{[1] (Rf-L 1} ) n -Si (R 11) 4-n
(In the formula, Rf represents a linear, branched or cyclic fluorine-containing alkyl group having 1 to 20 carbon atoms or a fluorine-containing aromatic group having 6 to 14 carbon atoms. L ₁ is a divalent divalent having 10 or less carbon atoms. Represents a linking group, R ¹¹ represents a hydroxyl group or a hydrolyzable group, and n represents an integer of 1 to 3.) The method for producing an inorganic oxide fine particle dispersion according to claim 1, wherein the fluorine-containing silane coupling agent represented by the general formula [1] is represented by the following general formula [2].
Formula _{[2] C n F 2n +} 1 - (CH 2) m -Si (R) 3
(In the formula, n represents an integer of 1 to 10, m represents an integer of 1 to 5. R represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom.) Method of producing an inorganic oxide fine particle dispersion according to claim 1 or 2, wherein the inorganic oxide fine particles are silica fine particles. The method for producing an inorganic oxide fine particle dispersion according to any one of claims 1 to 3 , wherein the inorganic oxide fine particles are hollow silica fine particles. An inorganic oxide fine particle dispersion obtained by the production method according to any one of claims 1 to 4 . A coating composition comprising the inorganic oxide fine particle dispersion according to claim 5 and a film-forming composition, wherein at least one component of the film-forming composition is a compound having an ethylenically unsaturated group. A coating composition characterized by A coating composition comprising the inorganic oxide fine particle dispersion according to claim 5 and a film-forming composition, wherein the main component of the film-forming composition is a compound having an ethylenically unsaturated group. Coating composition. An optical film having a layer formed using the coating composition according to claim 6 on a transparent support. Wherein an inorganic oxide fine particles hollow particles contained in the layer formed from the coating composition, according to claim 8, characterized in that the layer of a refractive index of 1.20 or more 1.46 or less Optical film. The inorganic oxide fine particles contained in the layer formed from the coating composition are hollow silica fine particles, and the refractive index of the hollow silica fine particles is 1.17 to 1.40. The optical film according to claim 8 or 9 . The optical film as described in any one of Claims 8-10 is an antireflection film which has an antireflection layer on a transparent support body, Comprising: The low refractive index layer is formed using the said coating composition. An antireflection film characterized by that. The antireflection film according to claim 11 , wherein the inorganic oxide fine particles contained in the coating composition are hollow silica fine particles having a thickness of 30% to 150% of the thickness of the low refractive index layer. . The antireflective film according to claim 11 or 12 , wherein the low refractive index layer is formed from a coating solution containing a fluorine-containing polymer represented by the following general formula 1.

(Wherein L represents a linking group having 1 to 10 carbon atoms, m represents 0 or 1, X represents a hydrogen atom or a methyl group, A represents a polymerized unit of any vinyl monomer, and a single component. Or x, y, z represents the mol% of each component, and satisfies 30 ≦ x ≦ 60, 5 ≦ y ≦ 70, and 0 ≦ z ≦ 65. Represents the value.) The film as described in any one of Claims 8-13 is used for the protective film of the polarizer in a polarizing plate, The polarizing plate characterized by the above-mentioned. An image display device, wherein the film according to any one of claims 8 to 13 or the polarizing plate according to claim 14 is used on an outermost surface of a display.

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