JP2000017099A - Thin film and antireflection film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a thin film having micro voids and an excellent antireflection property by preparing a film comprising a binder resin which contains a fluorine compound and an organic silicon compound as main components and a small particle. SOLUTION: As a fluorine compound, one having at least two polymerizing functional groups is preferable. An organic silicon compound, Si(R1)i(r2)j(r3)k(OR 4)4-(i+j+k) (wherein R1, R2 and R3 are each an organic group having at least one of H, O and F; R4 is an aliphatic, an alicyclic or an aromatic residue; (i), (j), (k) are each 0 or 1) is preferable. As a small particle, an inorganic oxide containing an element selected from Si, Al, Sn, Sb, Zn and Ti and an emulsion particle of magnesium fluoride, calcium fluoride or an organic compound can be used, but inorganic small particles are preferable. Usually 5-200 pts.wt. of a small particle is used against 100 pts.wt. of a binder resin. A thin film is obtained by dispersing or dissolving small particle and a binder and carrying out coating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-reflection film for various display devices such as an anti-reflection film for a CRT of a television or a liquid crystal display device, an anti-reflection filter for a CRT monitor, a case for exhibition, a show window, and a picture display. The present invention relates to a thin film suitably used for an antireflection film of a frame, a window glass, an optical lens, an eyeglass lens, and the like, and an antireflection film using the same. It can also be used as a semiconductor-related low dielectric.

[0002]

2. Description of the Related Art An antireflection article such as an antireflection filter used for a display device or the like has a low refractive index optical thin film provided on a substrate in a single layer, or a high refractive index and low refractive index optical thin film. In many cases, the anti-reflection layer is formed by alternately providing multiple layers.

A method for obtaining such an optical thin film is as follows.
In general, an inorganic substance is laminated on a substrate by vapor deposition, sputtering, or the like, and the antireflection film thus obtained has low reflection and excellent scratch resistance. However, in the method of performing antireflection treatment by vapor deposition or sputtering of an inorganic substance, although a high-performance antireflection layer can be obtained, productivity is poor because a large-scale apparatus requiring vacuum is used, and the production cost is high.
Further, in these methods, the substrate is heated to 80 ° C. or more during vapor deposition or sputtering, so that the usable substrates are limited in terms of heat resistance and the like.

Recently, there has been known a method of dissolving a low-refractive-index organic substance in a solvent, coating the substrate with a low-refractive-index organic substance to form a low-refractive-index organic thin film to form an antireflection film. It became so. Such a solution coating method is disclosed, for example, in JP-A-4-355401 and JP-A-6-355601.
No. -18705. The low refractive index substance used in these solution coating methods is a resin having a high fluorine content, and exhibits excellent antireflection characteristics. Further, since these form a thin film by solution coating, it is possible to form an antireflection film with high productivity, unlike the method of performing antireflection treatment by vapor deposition or sputtering of an inorganic oxide.

However, the organic thin film made of a fluorine-containing resin described in JP-A-4-355401 or JP-A-6-18705 has a high productivity because it can be solution-coated, and has an excellent reflection due to a low refractive index. Although they exhibit prevention properties, these cured fluorine-containing resins have low cross-linking densities and thus have low surface hardness and poor abrasion resistance.

As a fluorine-containing resin having a high surface hardness and a high crosslink density, a cured product of perfluorodivinyl ether disclosed in US Pat. No. 3,310,606 can be mentioned. An optical thin film cannot be obtained because it needs to be molded below.

On the other hand, an antireflection film described in Japanese Patent Application Laid-Open No. 4-121701 utilizing the principle of an inhomogeneous film in which bubbles having a wavelength smaller than the wavelength are formed inside the polymer and the refractive index continuously changes in the thickness direction. However, there is a problem that it is difficult to obtain a film whose refractive index changes continuously because a step of washing out a solvent-soluble component by solvent washing is included in the formation of the micro voids.

Japanese Patent Application Laid-Open No. 9-227713 discloses an antireflection film in which a low refractive index layer containing microvoids is formed in a thin film made of a resin by a reversed-phase emulsification method. The method is not always easy because of the necessity of a dispersion step of forming an emulsion in which water is dispersed to a particle size equal to or smaller than the wavelength of visible light.

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art, and a thin film which can be formed by a simple method and which has excellent surface hardness, and the use of the thin film. An object is to provide an antireflection film.

[0010]

In order to achieve the above object, the present invention has the following arrangement.

1. A thin film comprising a binder resin containing a fluorine compound and an organic silicon compound as main components, and fine particles, and having micro voids.

2. An antireflection film, wherein the thin film is formed on a film having a higher refractive index than the thin film.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thin film of the present invention is characterized by having micro voids. This thin film is used as a low-refractive-index film, and is preferably used in many cases by being provided on the outermost surface of a transparent base material to be provided with antireflection properties. Here, the micro void means either a micro void in the film or an air layer formed by unevenness on the film surface. Thus, the micro structure has a composite structure of a resin layer and voids, but the macro structure can be regarded as one layer, and a film having a lower refractive index than normally expected can be formed.

In a normal case, a film composed of fine particles and a resin has a weighted average value of the refractive indices.
It is difficult to have a sufficiently low refractive index.

However, since the refractive index of air is 1, the refractive index of the thin film having micro voids of the present invention can be further reduced as compared with a film consisting of fine particles and resin. In other words, the low-refractive-index film having microvoids is between the refractive index of the air layer and the refractive index of the film made of resin and fine particles. Therefore, the refractive index of the thin film of the present invention can be made lower than the refractive index estimated from each material by the volume fraction of the micro void.

Such a layer having a low refractive index can be used not only as a single layer film but also as the uppermost layer of a multilayer film. Obtaining an effective antireflection film in a wider wavelength range by forming multiple layers is based on a known principle similar to that of the related art.

If the ratio of the micro voids in the film is too high, the physical strength of the film tends to be impaired, and the content of the micro voids is preferably 50% or less in volume fraction. Also,
The size of the micro voids is not particularly limited, but when physical strength of the film is required, it is preferably two thirds or less of the film thickness.

The fluorine compound used as the binder resin of the thin film of the present invention is usually not crosslinked at the time of coating, but is crosslinked after coating from the viewpoint of the ease of dispersibility of fine particles described below and the film strength. What can be used can be suitably used. Typically, a typical fluorine-containing compound used for such a purpose preferably has a polymerizable functional group in the molecule, and more preferably has two or more functional groups. Further, from the viewpoint of easy synthesis, the fluorine compound is represented by (meth) as a polymerizable functional group.
It is more preferred to have at least one selected from an acryloyloxy group, a vinyl group, an epoxy group and a vinyl ether group. This is because these functional groups can easily form a crosslinked structure by heat or light. The following is an example.

Examples of the fluorine-containing (meth) acrylate compound include aliphatic, alicyclic, and aromatic fluorine-containing mono (meth) acrylates such as 2,2,2-trifluoroethyl (meth) acrylate and 2,2,2-trifluoroethyl (meth) acrylate. 2,3,3,3-
Pentafluoropropyl (meth) acrylate, 2-
(Perfluorobutyl) ethyl (meth) acrylate,
3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 3-perfluorohexyl-
2-hydroxypropyl (meth) acrylate, 2-
(Perfluorooctyl) ethyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) acrylate, 2- (perfluorodecyl)
Ethyl (meth) acrylate, 2- (perfluoro-3)
-Methylbutyl) ethyl (meth) acrylate, 3-
(Perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 2- (perfluoro-
5-methylhexyl) ethyl (meth) acrylate, 2
-(Perfluoro-9-methyloctyl) ethyl (meth) acrylate, 2- (perfluoro-9-methyldecyl) ethyl (meth) acrylate, 2,2,3,3-
Tetrafluoropropyl (meth) acrylate, 1H,
1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoropentyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H, 1H, 11H
-Eicosafluoroundecyl (meth) acrylate,
2,2,2-trifluoro-1-trifluoromethylethyl (meth) acrylate, 2,2,3,4,4,4-
Hexafluorobutyl (meth) acrylate and the like can be mentioned.

In the present invention, polyfunctional fluorine-containing (meth) acrylates are particularly preferably used, and examples thereof include di (meth) acrylates represented by the following structural formula.

CH ₂ = CRCOO (CH ₂ ) f (CF ₂ ) g (CH ₂ ) hOCOCR = CH ₂ CH ₂ = CRCOOCH ₂ CH (OH) (CH ₂ ) f (CF ₂ ) g (CH ₂ ) hCH ( OH) CH ₂ OCOCR
= CH ₂ CH ₂ = CRCOOCH ₂ CH ₂ OCO (CF ₂ ) gCOOCH ₂ CH ₂ OCOCR = CH ₂ CH ₂ = CRCOOCH ₂ CH (OH) CH ₂ OCO (CF ₂ ) gCOOCH ₂ CH (OH) CH ₂ OCOCR
= CH ₂ CH ₂ = CRCONHCOO (CH ₂ ) f (CF ₂ ) g (CH ₂ ) hOCONHCOCR = CH ₂ CH ₂ = CRCOCH ₂ CH ₂ NHCOO (CH ₂ ) f (CF ₂ ) g (CH ₂ ) hOCONHCH ₂ CH ₂ OC
OCR = CH _{2 In} the above formula, R is H or CH ₃ , and f is 0 to
2, g represents an integer of 0 to 12, and h represents an integer of 0 to 2. further,
In order to reduce the refractive index and maintain a certain degree of hardness,
g is preferably 4 to 10. From the viewpoint of ease of synthesis and low refractive index, CH ₂ = CRCOO (CH ₂ ) f (CF ₂ ) g (CH ₂ ) hOC
OCR = CH ₂ is more preferably used.

In order to increase the crosslink density, monofunctional monomers such as ethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone, etc. Functional monomers such as triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,6-nonanediol diacrylate, dimethylol tricyclodecane diacrylate, 2-methacryloyloxyethyl acid phosphate, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, pentaerythritol tri (meth)
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane (meth) acrylate benzoic acid Esters, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, polytetramethylene glycol di (meth) acrylate,
When trimethylolpropane tetra (meth) acrylate, 1,3-butanediol di (meth) acrylate,
A compound containing no fluorine, such as 1,10-decanediol di (meth) acrylate, can also be mixed.

These compounds are used alone or as a mixture.

These (meth) acrylate compounds are:
Azo-based, peroxide-based radical polymerization initiators are preferably used for thermal polymerization under conditions of low oxygen concentration, or acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethyl Thiuram monosulfide, thioxanthones, and as a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, ketals,
A photo-radical polymerization initiator such as anthraquinones is used.

The heat treatment must be performed at a temperature lower than the deformation temperature of the substrate. Further, in the case of performing the active ray energy irradiation treatment, an electron beam or an ultraviolet ray is usually used. In particular, in the case of ultraviolet curing, an apparatus using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon arc, a carbon arc, and a metal halide lamp is used. In some cases, the reaction is performed by replacing oxygen in the system with an inert gas such as nitrogen.

Examples of the fluorine-containing epoxy compound include aliphatic, alicyclic, and aromatic fluorine-containing monofunctional epoxy compounds such as hexafluoroepoxypropane, 3-perfluorobutyl-1,2-epoxypropane, and 3-perfluoropropane. Fluorohexyl-1,2-epoxypropane, 3-
Perfluorooctyl-1,2-epoxypropane, 3
-Perfluorodecyl-1,2-epoxypropane, 3
-(Perfluoro-3-methylbutyl) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1,1, 2-epoxypropane,
3- (perfluoro-9-methyldecyl) -1,2-epoxypropane, 3- (2,2,3,3-tetrafluoropropoxy) -1,2-epoxypropane, 3- (1
H, 1H, 5H-octafluoropentyloxy)-
1,2-epoxypropane, 3- (1H, 1H, 7H-
Dodecafluoroheptyloxy) -1,2-epoxypropane, 3- (1H, 1H, 9H-hexadecafluorononyloxy) -1,2-epoxypropane and the like.

Particularly preferably used in the present invention are polyfunctional fluorine-containing epoxy compounds, examples of which include epoxy compounds represented by the following structural formula.

Ep-CH _2- (O) _a- (CH ₂ ) _b- (CF ₂ ) _c- (CH ₂ ) _d- (O) _e -CH ₂ -Ep where Ep is an epoxy group, a = 0 -1, b = 0-2, c
= 2 to 12, d = 0 to 2, and e = 0 to 1.

In the above formula, c is preferably an integer of 2 or more and 12 or less, and c is preferably 4 or more and 10 or less in order to reduce the refractive index and maintain hardness and low refractive index. preferable.

In order to increase the crosslink density, aliphatic,
Alicyclic, aromatic monofunctional epoxy compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, hexahydrobisphenol A type diglycidyl ether, (hydrogenated) bisphenol A-type diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether,
Polyfunctional epoxy compounds such as phthalic acid diglycidyl ester, dimer acid diglycidyl ester, triglycidyl isocyanurate, tetraglycidylaminodiphenylmethane, cresol novolac polyglycidyl ether, and epoxy group-containing silane compounds can also be added.

In the case of epoxy compounds, examples of the polymerization initiator include acid anhydrides, amines, amides, phenols, (poly) mercapto compounds, imidazoles, aromatic diazonium salts, and cation-providing systems. Can be
Examples of the photolytic cation imparting system include protonic acids, acidic metal halides, organometallic compounds, and stable carbonium ion salts. Among them, compounds having a photolytic cation-imparting system are suitable for curing due to the long pot life and the high curing speed, and diallyliodonium salts, triallylsulfonium salts, triallylselenonium salts, triallylpyrylium salts, and benzylpyridinium Thiocyanate,
A dialkylphenacylsulfonium salt, a dialkylhydroxyphenylsulfonium salt, a dialkylhydroxyphenylphosphonium salt, an iron allene complex or the like is used alone or as a mixture.

As the fluorine-containing vinyl ether compound,
In addition to monofunctional compounds, polyfunctional compounds having the following structures can be given.

CH ₂ = CH-O-CH ₂ -O- (CF ₂ ) kO-CH ₂ -O-CH = CH ₂ CH ₂ = CH-O-CH ₂ -O-CH _2- (CF ₂ ) k -CH ₂ -O-CH ₂ -O-CH = CH ₂ CH ₂ = CH-O-CH ₂ -O- (CH ₂ ) _2- (CF ₂ ) k- (CH ₂ ) ₂ -O-CH _2- O-CH = CH ₂ CH ₂ = CH-O-CH ₂ -O- (CH ₂ ) _3- (CF ₂ ) k- (CH ₂ ) ₃ -O-CH ₂ -O-CH = CH ₂ CH ₂ = CH-O- (CH ₂ ) ₂ -O- (CF ₂ ) _k -O- (CH ₂ ) ₂ -O-CH = CH ₂ CH ₂ = CH-O- (CH ₂ ) ₂ -O-CH _2- (CF ₂ ) _k -CH ₂ -O- (CH ₂ ) ₂ -O-CH = CH ₂ CH ₂ = CH-O- (CH ₂ ) ₂ -O- (CH ₂ ) _2- (CF ₂ ) k- (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -O-
CH = CH ₂ CH ₂ = CH-O- (CH ₂ ) ₂ -O- (CH ₂ ) _3- (CF ₂ ) k- (CH ₂ ) ₃ -O- (CH ₂ ) ₂ -O-
CH = CH _{2 In} the above formula, k is preferably an integer of 2 or more and 12 or less, and in order to reduce the refractive index and maintain a certain degree of hardness, k is preferably 4 or more and 10 or less. .

In order to increase the crosslinking density, fluorine-free vinyl ether compounds such as aliphatic, alicyclic,
Bifunctional or more than aromatic monofunctional vinyl ether compounds, 1,3-propanediol divinyl ether, 2-methyl-1,3-propanediol divinyl ether, diethylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, etc. Vinyl ether compounds, vinyl ether group-containing silane compounds, and fluorine-containing vinyl ether compounds can also be added.

As the vinyl ether group curing agent, a cation-providing compound is preferably used. Examples of the cation-providing compound include protonic acids, acidic metal halides, organometallic compounds, and stable carbonium ion salts. Among them, compounds having a photolytic cation imparting system are suitable for curing because of their long pot life and high curing speed, and aromatic diazonium salts, diallyliodonium salts, triallylsulfonium salts, triallylselenonium salts, triallylpyridinium salts Salts, benzylpyridinium thioisocyanate, dialkylphenacylsulfonium salts, dialkylhydroxyphenylsulfonium salts, dialkylhydroxyphenylphosphonium salts, metallocene compounds and the like.

Further, as examples of the organosilicon compound used as the binder resin of the low refractive index film of the present invention, those having the following structure are generally preferred because they can form a crosslinked structure.

Si (R1) _i (R2) _j (R3) _k (OR4) _{4- (i + j + k)} wherein R1, R2 and R3 are at least one selected from hydrogen, oxygen and fluorine atoms. Represents an organic group. R4
Represents at least one selected from aliphatic, alicyclic and aromatic residues. i = 0 or 1, j is 0 or 1, k
Represents an integer of 0 or 1, respectively. Examples include methyl silicate, ethyl silicate, n-propyl silicate
I-propyl silicate, n-butyl silicate,
Tetraalkoxysilanes such as sec-butyl silicate and t-butyl silicate and hydrolysates thereof, further, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,
Vinyltrimethoxyethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,
3,3-trifluoropropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ- Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycid Xylethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β
-Glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, diethoxy-3-glycidoxypropylmethylsilane, dimethoxy-3-glycidoxypropylmethylsilane, 3-glycidoxypropyldimethoxysilane, γ-
(Meth) acryloyloxypropyldimethylethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltri Methoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane,
α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3 4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-
Trialkoxysilanes, such as epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilane or triphenoxysilane Or a hydrolyzate thereof and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane,
γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ -Mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane,
γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-gly Sidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxy Propyl methyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyl Dimethoxysilane, dialkoxysilane or diacyloxysilanes such as γ-glycidoxypropylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane,
Tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-
sec-butoxysilane, tetra-tert-butoxysilane, tetrapentaethoxysilane, tetrapenta-
iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-t
silane compounds such as tert-butoxysilane, methyltripropoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, hexyltrimethoxysilane, and γ- (meth) acryloyloxypropyltrimethoxysilane Or a hydrolyzate thereof is an example.

The hydrolysis is achieved by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid, followed by stirring. Further, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution. At the time of hydrolysis, addition of pure water or an acidic aqueous solution in an amount equal to or more than 3 moles of the hydrolyzable group is particularly preferable from the viewpoint of promoting curing.

In addition, organic silicon compounds containing a polymerizable functional group such as an epoxy group in the middle of the molecular chain may be used.

These compounds can be used alone or in combination of two or more. In particular, in the structure of the organosilicon compound, it is more preferable that at least one of R1, R2 and R3 has a polymerizable functional group from the viewpoint of film strength.

Further, it is more preferable that at least one of R1, R2 and R3 is a (meth) acryloyloxy group, a vinyl group, an epoxy group or a vinyl ether group because of high reactivity.

Among them, an organosilicon compound having an epoxy group or a (meth) acryloyloxy group which can be easily polymerized by heat or an electron beam in a molecule is particularly preferable.

Examples are (meth) acrylate compounds,
Those capable of forming a chemical bond with a polymerizable functional group such as an epoxy compound and a vinyl ether compound, and specific examples thereof include vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane Γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane and the like are more preferred.

The following are preferably used as examples of the organosilicon compound having an epoxy group.

(Ep-CH ₂ 0 (CH ₂ ) _l ) _m Si (R 5) _n (R 6) _p (OR 7) _{4- (m + n + p)} where R 5 and R 6 are hydrogen, oxygen and fluorine atoms Represents an organic group containing at least one selected from the group; R7 represents at least one selected from aliphatic, alicyclic and aromatic residues. l is 0-4, m is 0-3, n is 0-3, p
Represents an integer of 0 to 3, respectively.

As examples of the organosilicon compound having a (meth) acryloyloxy group, the following compounds are preferably used.

(CH_Two= CRCOO (CH_Two)_q)_rSi (R8)_s(R9)_t(OR10)_{4- (r + s + t)}  Provided that R8 and R9 represent hydrogen, oxygen and fluorine atoms
Represents an organic group containing at least one selected from the group; R10 is
Table represents one selected from aliphatic, alicyclic and aromatic residues
You. q is 0-4, r is 0-3, s is 0-3, t is 0-3
Represents an integer.

In addition, one-terminal vinyl functional polysilane compound having a polymerizable reactive group, a two-terminal vinyl functional polysilane, a one-terminal vinyl functional polysiloxane, a two-terminal vinyl functional polysiloxane, or a reaction of these compounds Vinyl functional polysilane or vinyl functional polysiloxane.

For these, a curing method by heat is usually used. For the purpose of accelerating the curing rate, use of alkali metal salts of carboxylic acids, various metal alkoxides such as aluminum, titanium and zirconium, or chelate compounds may be mentioned.

When a silane compound and an epoxy compound are used in combination, it is preferable to use various metal chelate compounds such as aluminum, titanium, zirconium, iron and copper as the curing agent, since both can be cured simultaneously.

Among these curing agents, metal chelate compounds can be suitably used for the purpose of the present invention. In particular, the following aluminum chelate compounds are useful from the viewpoint of the stability of paints and the like.

The aluminum chelate compound referred to here is, for example, an aluminum chelate compound represented by the general formula AlX _V Y _3-V .

In the formula, X represents OL (L is a lower alkyl group), and Y represents a compound derived from a compound represented by the general formula M ¹ COCH ₂ COM ² (M ¹ and M ² (both are lower alkyl groups)). At least one selected from ligands and ligands derived from compounds represented by the general formula M ³ COCH ₂ COOM ⁴ (M ³ and M ⁴ are both lower alkyl groups).
Or 2.

As the aluminum chelate compound represented by the general formula AlX _V Y _3-V , various compounds can be mentioned.
Particularly preferred from the viewpoint of solubility in the composition, stability and the like, aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum-di-n-butoxide monoethylacetoacetate, aluminum-di-iso -Propoxide monoethyl acetoacetate and the like. These are 2
It is also possible to use a mixture of more than one species. At that time, acetylacetone can be added to the paint solvent from the viewpoint of the storage stability of the paint. In addition, various epoxy resin curing agents or various organic silicon resin curing agents are used, and these compounds are used in an amount of about 0.1 to 20 parts by weight based on 100 parts by weight of the epoxy compound and the silane-based compound in total. Can be

Here, the entirety of these binder components was 1
A preferred composition ratio of each binder component in the present invention when the content is 00 parts by weight will be described.

Preferred as the binder component are 1 to 99 parts by weight of a fluorine compound and 99 to 1 part by weight of an organosilicon compound. More preferably, the content is 10 to 90 parts by weight of a fluorine compound and 90 to 10 parts by weight of an organic silicon compound. More preferably, the amount is 20 to 80 parts by weight of a fluorine compound and 80 to 20 parts by weight of an organic silicon compound. When the amount of the fluorine compound is less than 10 parts by weight, the refractive index tends to hardly decrease, and when the amount exceeds 90 parts by weight, the strength of the film tends to be insufficient.

As the fine particles used in the thin film of the present invention, those having a relatively low refractive index are preferred.
Examples of the inorganic particles include inorganic oxides containing at least one element selected from Si, Al, Sn, Sb, Zn and Ti, magnesium fluoride, calcium fluoride, and organic emulsion particles. Preferred are inorganic fine particles. Further, the average particle size of the fine particles measured by the BET method is 1 nm or more and 100 nm or less, preferably 5 to 40 nm. If the average particle size exceeds 100 nm, the formed film becomes large in haze and has poor transparency. Tend. When these particles are used, they are usually used in the form of a sol, but in order to obtain a sol having a higher dispersibility, usually, those dispersed in a dispersion medium such as water, alcohol, ester, or hydrocarbon are used. These fine particles are 5 parts by weight to 200 parts by weight, preferably 15 parts by weight to 100 parts by weight of the binder resin in the low refractive index film.
150 parts by weight are added. When the amount of the fine particles is less than 5 parts by weight or more than 150 parts by weight with respect to 100 parts by weight of the binder resin, voids are difficult to be formed, and the refractive index tends not to decrease.

The fine particles and the binder of the present invention, and the curing agent and the polymerization initiator added as required, include alcohol, ester, ether alcohol, ketone, hydrocarbon, aromatic solvents and dimethylformamide ( DM
F) and the like, and in some cases, such as a solvent containing a small amount of water, are not particularly limited. However, they are uniformly dispersed or dissolved in a single or mixed solvent selected from the viewpoint of solubility and uniform coating property. , Paint.

A surfactant, a leveling agent, a coupling agent, a polymer, and the like can be added to the above-mentioned paint to improve coating uniformity and adhesion.

The coatings prepared as described above are prepared by spin coating, dipping, die coating, bar coating,
Spray method, roll coating method, meniscus coater method,
Flexographic printing, screen printing, bead coater and the like can be mentioned. As a substrate on which the thin film or the antireflection film of the present invention is formed, polymethyl methacrylate (PMM)
A), polycarbonate (PC), polyethylene terephthalate (PET), diethylene glycol bisallyl carbonate, polyether sulfone (PES), styrene / maleic acid resin, styrene / acrylonitrile copolymer, polychlorostyrene, polyvinylidene oxide, polyarylate , Vinyl chloride resin, transparent resin such as polystyrene resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), diacetyl cellulose, polyethylene, diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, polyacrylic resin film, Polyurethane resin film,
Films such as polycarbonate film, polysulfone film, trimethylpentene film, polyetherketone film, (meth) acrylonitrile film, polypropylene, vinyl chloride film and the like, glass, etc., are not particularly limited.

In particular, in recent years, thin films or antireflection articles such as the present invention have been used for film applications in which large areas can be easily coated, especially transparent substrates used for liquid crystal displays,
Often used in the manufacture of polarizing plates, protective plates, optical filters or adhesive films for the same purpose,
It is suitably applied to a tri- or diacetyl cellulose film, a saponified triacetyl cellulose film or a polyethylene terephthalate film.

The thin film of the present invention is suitably used as an optical thin film. Here, an optical thin film means that when a light beam enters a base material on which a thin film is present, the light beam reaches a boundary having a different refractive index. A thin film that crosses and causes interference. In an optical thin film, reflected light appears as interference light of incident light. For example, when one layer of a transparent optical thin film is provided on a transparent substrate,
Part of the incident reflected light is reflected at the boundary between the air and the thin film, part is reflected at the interface between the thin film and the base material, and the reflected light as a whole becomes their interference light. The interference light results in a reduction or increase in the reflectivity of the substrate. The optical thin film is thin enough to cause interference of light, and the reflectance of the substrate depends on the refractive index and the thickness of the optical thin film.

Although the present invention is not limited in application, one of the objects is to provide an optical thin film having a low refractive index mainly for the purpose of reducing the reflectance, and the thickness of the low refractive index layer is reduced. Is preferably an integral multiple of λ / 4n, where λ is the wavelength of light whose reflectance is to be reduced and n is the refractive index of the layer. Usually, since it is intended for the visible light region, it is preferable to set λ to 500 to 550 nm, so that the film thickness is 70 to 200 nm, more preferably 80 to 130 n.
m, more preferably 85 to 115 nm. When the film thickness is less than 70 nm or more than 200 nm, the reduction of the reflectance due to light interference in the visible light region may be insufficient, and only the reduction of the reflectance due to the low refractive index of the substrate surface. Therefore, the reflectivity is higher and the antireflection effect is inferior to the case where an optical thin film is provided. However,
For example, when used as a low dielectric substance, the thickness is not particularly limited to these, and may be about 10 nm.

The antireflection effect of the low refractive index film is as follows.
It is known that performance can be enhanced by laminating multilayer films having different refractive indexes with an optical film thickness. When used as a constituent film of a multilayer laminated film, a layer having a higher refractive index than the low refractive index film can be provided as a lower layer of the low refractive index film. In the present invention, when a high refractive index layer higher than the refractive index of the transparent substrate or the hard coat layer is provided between the transparent substrate or the hard coat layer and the low refractive index film, the performance of the antireflective article is further improved. It is possible. In this case, the refractive index of the high-refractive-index layer is required to be 1.56 or more, preferably 1.6 or more, as measured at 20 ° C. by D-line.

The high refractive index layer is formed by forming a conductive compound such as titanium oxide or tin-doped indium oxide (ITO) on the film by a vacuum evaporation method or a sputtering method, or by using an organic or inorganic binder or a mixed binder of both. By forming a thin film in which ultrafine particles of a metal compound having a high refractive index such as antimony, selenium oxide, titanium oxide, tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, zinc oxide, zinc antimonate, and tin-doped indium oxide are dispersed. obtain. Although the present invention is not limited thereto, as the organic binder, a cured epoxy resin or a resin subjected to radical cross-linking polymerization is used, and as the inorganic binder, a hydrolyzed cured product of a silane compound is used.

When the wavelength of light whose reflectance is to be reduced is λ and the refractive index of the layer is n, the thickness of the high refractive index layer is λ /
It is preferably an integer multiple of 4n. Although it depends on the refractive index of the film, it is specifically in the range of 90 to 400 nm, more preferably 110 to 180 nm.

[0067] ultrafine particles used in the high refractive index layer, tin oxide, antimony-doped tin oxide, phosphorus-doped tin oxide, zinc antimonate has a conductivity as indium tin oxide, 10 ¹⁰ the high refractive index layer itself -10Ω /
It is preferable to have a degree of conductivity of about □ because the antireflective article can be provided with an antistatic function and further an electromagnetic wave shielding function. Here, the conductivity refers to a sheet resistance measured according to JIS K6911.

In some applications, the substrate is required to have abrasion resistance. Although a resin substrate is often used, a hard coat layer is provided between the substrate and the low refractive index film by a wet coating method as a means for improving the scratch resistance of the substrate. Usually, the hard coat layer is made of an organic or inorganic binder or a mixed binder of both, and if necessary, fine particles of a metal compound such as silicon oxide, antimony oxide, selenium oxide, titanium oxide, etc. A coating film to which fine particles having a small particle diameter are added is used. Examples of the organic binder include the above-described cured epoxy resin and radical cross-linked polymer, and examples of the inorganic binder include a hydrolyzed cured product of a silane compound, but are not particularly limited.

The hard coat layer is usually 0.5 to 10 μm
It is formed to a film thickness of about a degree, and it is possible to balance the abrasion resistance function and other performances (for example, crack generation prevention).

The low-refractive-index film may be provided with a fluorine-based or silicone-based antifouling layer in order to impart a property such as fingerprint smear or the like and a property of easy wiping during use.

[0071]

EXAMPLES The present invention will be described in more detail with reference to Examples, but it should not be construed that the invention is limited thereto. The evaluation means and measurement means used in the following Examples and Reference Examples are as follows.

A. Refractive index and film thickness: measured value by ellipsometer b. Single-sided reflectance: measured value of reflectance at 540 nm by a spectrophotometer A conductive hard coat film was prepared according to the following Reference Examples 1 to 4.

(Reference Example 1) One side of a 80 μm-thick triacetyl cellulose film (“Fujitac” manufactured by Fuji Photo Film Co., Ltd.) was gravure coated with the following paint having a solid content of 20% by weight. 1 UV below
Irradiation at 000 mJ yielded a conductive hard coat film.

Cellnax CXZ-300M1F (manufactured by Nissan Chemical Industries, 230 parts by weight methanol sol containing 30% by weight of zinc antimonate) Pentaerythritol triacrylate 30 parts by weight CG-907 (manufactured by Ciba Geigy) 2 parts by weight The obtained hard coat The thickness of the film was about 3 μm, the conductivity was about 6 × 10 ⁸ Ω / □, and the refractive index was 1.66.

Reference Example 2 One side of a 75 μm thick polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) was gravure coated with the following paint having a solid content of 20 wt%, and after removing the solvent, under nitrogen purge. UV 1000mJ
Irradiation gave a conductive hard coat film.

ELECOM W-32 (manufactured by Kasei Kasei Co., Ltd., phosphorus-doped oxide 230 parts by weight benzyl alcohol sol containing 30 wt% tin) pentaerythritol triacrylate 35 parts by weight CG-907 (manufactured by Ciba Geigy) 2 parts by weight The obtained hard coat The thickness of the film was about 3 μm, the conductivity was about 3 × 10 ⁸ Ω / □, and the refractive index was 1.67.

REFERENCE EXAMPLE 3 One side of a 80 μm-thick triacetylcellulose film (“Fujitac” manufactured by Fuji Photo Film Co., Ltd.) was gravure coated with the following coating composition having a solid content of 18% by weight. The reaction was carried out in a hot air drier for 20 seconds and then in a 110 ° C. hot air drier for 2 hours to obtain a conductive hard coat film.

Cellnax CXZ-300M1F (manufactured by Nissan Chemical Industries, 183 parts by weight methanol sol containing 30% by weight of zinc antimonate) Epicoat 827 (manufactured by Yuka Shell Epoxy, 25 parts by weight bisphenol A epoxy resin) γ-glycid Xylpropyltrimethoxysilane hydrolyzate 5 parts by weight Aluminum acetylacetonate 5 parts by weight The thickness of the obtained hard coat film is about 3 μm, the conductivity is about 5 × 10 ¹⁰ Ω / □, and the refractive index is 1.63. there were.

REFERENCE EXAMPLE 4 One side of a 75 μm thick polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries Co., Ltd.) was gravure coated with the following paint having a solid content of 20% by weight. 30 seconds in the dryer,
The reaction was performed to obtain a conductive hard coat film.

ELECOM W-32 (manufactured by Tokasei Kasei Co., Ltd., phosphorus-doped oxide 230 parts by weight Benzyl alcohol sol containing 30 wt% tin) Trimethylolpropane triglycidyl ether 5 parts by weight γ-glycidoxypropyltrimethoxysilane hydrolyzate 25 parts by weight Part 5 parts by weight aluminum acetylacetonate The thickness of the obtained hard coat film was about 3 μm, the conductivity was about 2 × 10 ⁸ Ω / □, and the refractive index was 1.66.

Next, according to Reference Examples 5 to 11, low refractive index films were prepared.

(Example 1) A coating material having a solid content of 1.5 wt% was prepared with an organic solvent using the following composition, gravure coated, and after removing the solvent, the substrate was thermally damaged in a hot air oven at 130 ° C. The composition was heat-cured under the conditions (about 1 minute) during which no low refractive index film was obtained.

[0083]

Embedded image 50 parts by weight Silicon oxide fine particles (average particle diameter 10 nm) 50 parts by weight γ-glycidoxypropyltrimethoxysilane hydrolyzate 50 parts by weight Aluminum acetylacetonate 5 parts by weight The obtained low refractive index film has a thickness of about 90 nm. And the refractive index was 1.35.

(Example 2) A paint having a solid content of 1.5 wt% was prepared using an organic solvent using the following composition, gravure coated, and after desolvation, the substrate was damaged in a hot air oven at 130 ° C. The composition was heat-cured under the conditions (about 1 minute) during which no low refractive index film was obtained.

[0085]

Embedded image 70 parts by weight Magnesium fluoride (average particle diameter 15 nm) 50 parts by weight γ-glycidoxypropyltrimethoxysilane hydrolyzate 30 parts by weight Aluminum acetylacetonate 5 parts by weight The resulting low refractive index film has a thickness of about 90 nm. And the refractive index was 1.32.

(Example 3) A paint having a solid content of 1.5 wt% was prepared using an organic solvent using the following composition, gravure coated, and after removal of the solvent, the substrate was thermally damaged in a hot air oven at 130 ° C. The composition was heat-cured under the conditions (about 1 minute) during which no low refractive index film was obtained.

[0087]

Embedded image 50 parts by weight Silicon oxide fine particles (average particle diameter 20 nm) 25 parts by weight γ-glycidoxypropyltrimethoxysilane hydrolyzate 50 parts by weight Aluminum acetylacetonate 5 parts by weight The resulting low refractive index film has a thickness of about 90 nm. And the refractive index was 1.33.

(Example 4) A paint having a solid content of 1.5 wt% was prepared using an organic solvent using the following composition, gravure coated, and after removing the solvent, the substrate was damaged in a hot air oven at 130 ° C. The composition was heat-cured under the conditions (about 1 minute) during which no low refractive index film was obtained.

[0089]

Embedded image 70 parts by weight Silicon oxide fine particles (average particle diameter 10 nm) 50 parts by weight γ-glycidoxypropylmethyldiethoxysilane hydrolyzate 30 parts by weight Aluminum acetylacetonate 5 parts by weight It was 90 nm and the refractive index was 1.35.

(Example 5) A paint having a solid content of 1.5 wt% was prepared using an organic solvent using the following composition, gravure coated, and after removal of the solvent, the substrate was thermally damaged in a hot air oven at 130 ° C. The composition was heat-cured under the conditions (about 1 minute) during which no low refractive index film was obtained.

[0091]

Embedded image 85 parts by weight Silicon oxide fine particles (average particle diameter 10 nm) 50 parts by weight γ-glycidoxypropyltrimethoxysilane hydrolyzate 15 parts by weight Ethyl silicate hydrolyzate 5 parts by weight Aluminum acetylacetonate 5 parts by weight Low refractive index obtained The film thickness of the refractive index film was about 90 nm, and the refractive index was 1.37.

(Example 6) A coating material having a solid content of 1.5 wt% was prepared from the following composition with an organic solvent, gravure coated, heated and desolvated.
By irradiating J, a low refractive index cured film was obtained.

[0093]

Embedded image 70 parts by weight Silicon oxide fine particles (average particle diameter 10 nm) 100 parts by weight γ-acryloyloxypropyltrimethoxysilane 30 parts by weight CG907 4 parts by weight The obtained low refractive index film has a thickness of about 90 nm and a refractive index of 1 .32.

(Example 7) A paint having a solid content of 1.5 wt% was prepared using an organic solvent using the following composition, gravure coated, heated and desolvated.
By irradiating J, a low refractive index cured film was obtained.

[0095]

Embedded image 40 parts by weight Perfluorooctylethyl acrylate 20 parts by weight Silicon oxide fine particles (average particle diameter 10 nm) 100 parts by weight γ-acryloyloxypropyltrimethoxysilane 40 parts by weight CG907 4 parts by weight The thickness of the obtained low refractive index film is about It was 90 nm and the refractive index was 1.36.

(Examples 8 to 35) The results of applying the low refractive index films shown in Examples 1 to 7 to the base material with a conductive hard coat film obtained in Reference Examples 1 to 4 are shown in the tables.

[0097]

[Table 1] The term “single-sided reflectance” as used herein refers to an average value of 500 to 600 nm obtained by measuring the surface reflectance of a sample piece whose back surface is painted black to eliminate reflection on the back surface by a spectrophotometer.

[0098]

According to the present invention, it is possible to provide a thin film excellent in antireflection property which can be easily produced, an antireflection film and an antireflection article using the same.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G02B 1/11 C08J 7/06 Z 4J100 // C08J 7/06 G02B 1/10 A F-term (Reference) 2K009 AA00 AA02 AA15 BB02 BB11 BB13 BB14 BB24 BB28 CC03 CC06 CC09 CC24 CC33 CC47 DD00 DD02 DD03 DD04 DD05 DD06 EE03 4F006 AA02 AA12 AA15 AA16 AA17 AA22 AA35 AA36 AA37 AA40 AB19 A34 ABA ABA ABA AB73 DA07 AA88 AA89 AA98 AC14 AC17 AC20 AC21 AE01 AG07 CB91 DA09 DA20 DA23 DA24 DA47 4F100 AA06A AA06H AA17C AA19A AA19H AA20A AA20H AA21A AA21H AA25A AA25C AA25H AA28A AA28C AA28H AA29A AA29C AA29H AA33C AK01B AK17A AK25A AK52A AK53A AL05A AR00B AR00C BA01 BA02 BA03 BA07 BA10A BA10B CA23A DE01A DE01C DE01H DJ00A GB41 GB90 JG03C JM02A JN01B JN06 JN18C YY00A YY00H 4J036 A J01 AJ06 AJ21 FA03 FA13 GA28 JA15 KA07 4J100 AE64P AL08P AL08Q AL66P AL74P AP16Q AP17Q BA03P BA12P BA15P BA38P BA71Q BA75Q BA77Q BB07Q BB12P BB17P BB18P CA04 JA32 JA46

Claims (21)

[Claims] 1. A thin film comprising a binder resin containing a fluorine compound and an organosilicon compound as main components and fine particles, and having micro voids. 2. The thin film according to claim 1, wherein said fluorine compound has a polymerizable functional group. 3. The thin film according to claim 1, wherein the fluorine compound has two or more functional groups. 4. The thin film according to claim 1, wherein said fluorine compound has at least one selected from a (meth) acryloyloxy group, a vinyl group, an epoxy group and a vinyl ether group. 5. The thin film according to claim 1, wherein said fluorine compound is a fluorine-containing diepoxide having the following structure. Ep-CH _2- (O) _a- (CH ₂ ) _b- (CF ₂ ) _c- (CH ₂ ) _d- (O) _e -CH ₂ -Ep where Ep is an epoxy group, a is 0 to 1, b is 0-2, c
Represents an integer of 2 to 12, d represents an integer of 0 to 2, and e represents an integer of 0 to 1. 6. The thin film according to claim 1, wherein the fluorine compound is a fluorine-containing di (meth) acrylate having the following structure. CH ₂ = CRCOO (CH ₂ ) _f (CF ₂ ) _g (CH ₂ ) _h OCOCR = CH ₂ where R is H or CH ₃ , f is 0-2, g is 2-1
2, h represents an integer of 0 to 2. 7. The thin film according to claim 1, wherein the organosilicon compound has the following structure. Si (R1) _i (R2) _j (R3) _k (OR4) _{4- (i + j + k)} where R1, R2 and R3 are organic groups containing at least one selected from hydrogen, oxygen and fluorine atoms. Represent. R
4 represents at least one selected from aliphatic, alicyclic and aromatic residues. i is 0 or 1, j is 0 or 1,
k represents an integer of 0 or 1, respectively. 8. The thin film according to claim 7, wherein at least one of R1, R2 and R3 has a polymerizable functional group. 9. A thin film wherein the organosilicon compound according to claim 8 is a (meth) acryloyloxy group, a vinyl group, an epoxy group or a vinyl ether group. 10. The thin film according to claim 1, wherein the organosilicon compound has the following structure. _{(Ep-CH 2 0 (CH} 2) l) m Si (R5) n (R6) p (OR7) 4- (m + n + p) , however, at least R5, R6 is selected from hydrogen, oxygen, and fluorine atom Represents an organic group containing one. R7 represents at least one selected from aliphatic, alicyclic and aromatic residues. l is 0-4, m is 0-3, n is 0-3, p
Represents an integer of 0 to 3, respectively. 11. The organic silicon compound has the following structure:
The thin film according to any one of claims 1 to 9, wherein: (CH_Two= CRCOO (CH_Two)_q)_rSi (R8)_s(R9)_t(OR10)_{4- (r + s + t)}  Provided that R8 and R9 represent hydrogen, oxygen and fluorine atoms
Represents an organic group containing at least one selected from the group; R10 is
Table represents one selected from aliphatic, alicyclic and aromatic residues
You. q is 0-4, r is 0-3, s is 0-3, t is 0-3
Represents an integer. 12. The method according to claim 12, wherein the fine particles are Si, Al, Sn, S
The thin film according to any one of claims 1 to 11, wherein the thin film is an inorganic oxide containing at least one element selected from b, Zn and Ti, or magnesium fluoride or calcium fluoride. 13. The thin film according to claim 1, wherein the fine particles have an average particle diameter measured by a BET method of 1 to 100 nm. 14. An antireflective article comprising the thin film according to claim 1 provided on a transparent substrate. 15. The antireflective article according to claim 14, wherein said transparent substrate is a film. 16. An antireflection film, wherein the thin film according to any one of claims 1 to 13 is formed on a layer having a higher refractive index than the film. 17. An antireflection film, wherein the layer having a higher refractive index than the thin film according to claim 16 is made by dispersing inorganic oxide fine particles having an antistatic function. 18. The antireflection film according to claim 17, wherein said inorganic oxide fine particles having an antistatic function contain a component selected from the group consisting of tin, indium, antimony and zinc. 19. The antireflection film according to claim 17, wherein said inorganic oxide fine particles having an antistatic function contain zinc antimonate fine particles. 20. An anti-reflective article comprising the anti-reflection film according to claim 16 on a transparent substrate. 21. The anti-reflective article according to claim 20, wherein said transparent substrate is a film.