KR101690847B1 - Organic-inorganic composite thin film - Google Patents

Abstract

An object of the present invention is to further mineralize the surface of a film made of a polysiloxane-based organic-inorganic hybrid substance whose surface has a hardness higher than that of the inside.
In the organic-inorganic hybrid thin film of the present invention,
a) a compound of formula (I)
R _n SiX _{4 -n} (I)
(Wherein R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, and when n is 2, each R may be the same or different, and 4 - n) is 2 or more, each X may be the same or different, a condensate of an organosilicon compound represented by the formula
b) Organic Polymer Compound
Inorganic composite thin film,
(I) is formed on the surface of the film, and the concentration of carbon atoms at a depth of 10 nm from the surface is at least 20% or more than the concentration of carbon atoms at a depth of 100 nm from the surface And the O / Si source consumption of 2 nm depth from the surface of the film is 1.8 to 2.5.

Description

Organic-inorganic composite thin film {ORGANIC-INORGANIC COMPOSITE THIN FILM}

More specifically, the present invention relates to an organic / inorganic hybrid thin film, and more particularly to an organic / inorganic hybrid thin film which has a carbon atom content at a depth of 10 nm from the surface of a film smaller than a carbon atom content at a depth of 100 nm from the surface of the film, Si source consumption of 1.8 to 2.5.

The present application claims priority to Japanese Patent Application No. 2012-25024 filed on Feb. 8, 2012 and Japanese Patent Application No. 2012-86540 filed on Apr. 5, 2012, do.

As a raw material for the commercial silane-based coating material, mainly trifunctional silane is used, and polysiloxane having suitable hardness and flexibility is formed by such trifunctional silane. However, hard coatability is not sufficient in a film of trifunctional silane. Thus, the hard coat property is supplemented by mixing the tetrafunctional silane or colloidal silica with the trifunctional silane. However, if the film is made hard, cracks tend to occur and cracks tend to occur, which results in poor adhesion.

As the silane-based coat agent, for example, there is a composition for forming an antifouling film containing a trifunctional alkoxysilane compound having an epoxy group (see Patent Document 1). In addition, a silane-based coating system containing a photocatalyst is proposed, and the film is cured by using a photoacid generator, a crosslinking agent, a curing catalyst, or the like (see, for example, Patent Documents 2 and 3). Also, a silane-based organic-inorganic composite inclined material having a component gradient structure in which the content of the metal-based compound in the material continuously changes from the surface of the material in the depth direction has also been proposed (for example, see Patent Document 4).

The present inventors have found that by irradiating an organosilicon compound with ultraviolet rays in the presence of a photosensitive compound, an organic-inorganic hybrid material having an extremely high hardness on its surface and having an appropriate hardness on its inner and back sides, (See Patent Document 5). Further, by making the surface of the film an inorganic substance, it is possible to prevent degradation, which is a defect of the organic resin, and to provide a thin film excellent in moisture resistance and heat resistance (see Patent Document 6). Although these exhibit certain effects, it has been desired to produce thin films that further improve the adhesion of the film and the mineralization of the film surface.

On the other hand, as the hard coat film, it is known to use an acrylate resin or the like as the UV curable resin. For example, Patent Document 7 discloses a method in which a (meth) acrylic acid ester mixture (A), a photopolymerization initiator (B), an ethylenically unsaturated urethane oligomer (C), a colloidal silica sol (D), and a diluent , And that the resulting film has good pencil hardness, curl, and adhesion to the substrate.

Patent Document 8 discloses that (A) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium, (B) a compound having a urethane bond and at least two polymerizable unsaturated groups in the molecule, and (C) a photopolymerization initiator is used as the binder resin, (Coating) excellent in scratch resistance and adhesion to the substrate and the low refractive index layer can be formed on the surface of various substrates, and also has a high hardness and a high refractive index.

Patent Document 9 discloses a photocurable composition comprising (A) a mixture of a hydrolyzate of an organic silicon compound and fine metal oxide particles, (B) a polyfunctional acrylate or methacrylate, and (C) a photopolymerization initiator. Hard coat resin composition is disclosed, and it is possible to make the hardness of the antistatic agent to be within a practically acceptable range such as bleeding on the surface of the antistatic agent, deterioration of transparency and deterioration of moisture resistance, , Moisture resistance, solvent resistance, chemical resistance, etc.).

However, since hard coat films using these acrylate resins and the like are lower in the abrasion resistance than inorganic films, they are improved by adding metal oxide sol, and as a result, the hardness is improved, but the transparency, flexibility Is lowered.

On the other hand, plasma treatment and UV ozone treatment are generally used as a method of cleaning surfaces of various substrates (for example, Patent Document 10). Patent Document 11 discloses that the surface of metal particles and resin layer is imparted with hydrophilicity by plasma treatment or UV ozone treatment in a wiring board using copper plating. However, in general, when the plasma treatment or the UV ozone treatment is applied to an organic resin, there is a disadvantage that the organic compound on the resin surface is decomposed and the surface of the resin is roughened.

Japanese Patent Application Laid-Open No. 10-195417 Japanese Patent Application Laid-Open No. 2002-363494 Japanese Patent Application Laid-Open No. 2000-169755 Japanese Patent Application Laid-Open No. 2000-336281 WO2006 / 088079 pamphlet WO2008 / 069217 pamphlet Japanese Patent Application Laid-Open No. 2002-235018 Japanese Patent Application Laid-Open No. 2005-272702 Japanese Patent Application Laid-Open No. 2001-214092 Japanese Patent Application Laid-Open No. 2008-279363 Japanese Laid-Open Patent Publication No. 2010-080527

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to further mineralize the film surface of a film comprising a polysiloxane-based organic-inorganic hybrid substance whose surface has a hardness higher than that of the inside.

As a result of intensive studies on the above problems, the present inventors have found that by performing plasma treatment or UV ozone treatment as the organic / inorganic hybrid thin film, further inorganicization of the film surface can be attained, and further, Thereby further promoting the further mineralization of the film surface. Thus, the present invention has been completed.

That is,

(1) a)

R _n SiX _{4 -n} (I)

(Wherein R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, and when n is 2, each R may be the same or different, and 4 - n) is 2 or more, each X may be the same or different, and a condensate of the organosilicon compound represented by the formula

b) Organic Polymer Compound

Inorganic composite thin film,

(I) is formed on the surface of the film, and the concentration of carbon atoms at a depth of 10 nm from the surface is at least 20% or more than the concentration of carbon atoms at a depth of 100 nm from the surface , Preferably not less than 30%, and an O / Si source consumption of 2 nm depth from the surface of the film is 1.8 to 2.5, preferably 1.9 to 2.4,

(2) The organic electroluminescent device according to the above item (1), further comprising a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, Inorganic complex thin film,

(3) The organic / inorganic hybrid thin film according to (1) or (2) above, wherein the condensate of the compound in which R in the formula (I) is a vinyl group is contained in an amount of 70 mass% or more of the total condensate of the organosilicon compound ,

(4) The organic / inorganic hybrid thin film according to any one of (1) to (3), wherein the Si / C source consumption at a depth of 100 nm from the surface is 0.2 or less, preferably 0.15 or less,

(5) The organic / inorganic hybrid thin film according to any one of (1) to (4), further comprising a layer containing a hydrolyzed condensate of a metal surface active agent on the organic / inorganic hybrid thin film,

(6) The organic / inorganic hybrid thin film according to (5), wherein the metal surface active agent is a silane coupling agent.

Further, according to the present invention,

(7) a)

R _n SiX _{4 -n} (I)

(Wherein R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, and when n is 2, each R may be the same or different, and 4 - n) is 2 or more, each X may be the same or different, and a condensate of the organosilicon compound represented by the formula

b) Organic Polymer Compound

Inorganic composite thin film comprising a thin film of an organic-inorganic hybrid thin film, which is subjected to a plasma treatment or a UV ozone treatment.

Conventionally, a siloxane-enriched layer exists on the surface of a surface-hardened hard coat, but is completely hydrolyzed and does not become SiO ₂ , so the O / Si source consumption at a depth of 2 nm from the surface of the film is only about 1.5. On the other hand, according to the present invention, the O / Si source consumption at a depth of 2 nm from the surface of the film is almost completely hydrolyzed to 1.8 to 2.5 to form SiO ₂ .

That is, since the organic / inorganic hybrid thin film of the present invention is characterized in that the inside of the film is rich in organic resin, whereas the surface of the film is almost completely inorganic, the surface of the organic / inorganic hybrid thin film has chemical, thermal and optical stability and hydrophilicity And an organic-inorganic hybrid thin film excellent in adhesion with a gas can be provided.

Although the organic / inorganic hybrid thin film of the present invention is a film material containing a large amount of organic resin, it is possible to prevent the surface of the film from being roughened even if a treatment for decomposing organic matter such as an atmospheric pressure plasma treatment is performed.

In addition, since the organic / inorganic hybrid thin film of the present invention is an inorganic film surface, a dense monomolecular film comprising a hydrolyzed condensate of a metal surface active agent can be further formed on the outside.

Fig. 1 is a diagram showing the distribution of each film component in the film thickness direction measured by ESCA in the organic / inorganic hybrid thin film of Example 1. Fig.
2 is an image of the surface of the film surface before the atmospheric pressure plasma treatment is performed by the AFM in the organic-inorganic hybrid thin film of Example 1. Fig.
3 is an image obtained by measuring the unevenness of the film surface after the atmospheric pressure plasma treatment in the organic-inorganic hybrid thin film of Example 1 by AFM.
4 is a diagram showing the distribution of each film component in the film thickness direction measured by ESCA in the organic-inorganic hybrid thin film of Example 2. Fig.
5 is a photograph of a cross section of the film of the organic / inorganic hybrid thin film of Example 2 taken by a transmission electron microscope.

1 Composition of organic / inorganic composite thin film

The organic / inorganic hybrid thin film of the present invention contains a condensate of an organic silicon compound and an organic polymer compound as essential components, and may further contain a metal compound, a photopolymerization initiator, and the like.

(Condensate of organosilicon compound)

The organic-inorganic hybrid thin film of the present invention is represented by the following formula (I).

R _n SiX _{4 -n} (I)

In the formulas, R represents an organic group in which a carbon atom is directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group. When n is 2, each R may be the same or different, and when (4-n) is 2 or more, each X may be the same or different.

Examples of the "organic group to which a carbon atom is directly bonded to Si" represented by R include a hydrocarbon group which may be substituted, and a group which is composed of a hydrocarbon polymer which may be substituted.

The hydrocarbon group of the "hydrocarbon group which may be substituted" and "the hydrocarbon group which may be substituted" is usually a hydrocarbon group of 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, , An alkenyl group, an alkynyl group, an aryl group, an arylalkyl group, and an arylalkenyl group. Of these, preferred are linear or branched alkyl groups of 1 to 10 carbon atoms, cycloalkyl groups of 3 to 8 carbon atoms, alkenyl groups of 2 to 10 carbon atoms in the linear or branched chain, cycloalkenyl groups of 3 to 8 carbon atoms to be.

The "hydrocarbon group" or "hydrocarbon group-containing group" may contain an oxygen atom, a nitrogen atom, or a silicon atom.

Examples of the "linear or branched alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, N-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group and n-decyl group.

Examples of the long-chain alkyl group having more than 10 carbon atoms include a lauryl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group and a stearyl group.

Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

The "straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms" means a straight-chain or branched-chain alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at one or more positions, 1-yl group, prop-1-en-1-yl group, prop-1-en-1-yl group, 1-yl group, but-1-en-2-yl group, 1-yl group, hex-1-en-1-yl group, penta-1-en-2-yl group, 1-yl group, hepta-1-en-1-yl group, hepta-6-en-1-yl group, octa- .

"Cycloalkenyl group having 3 to 8 carbon atoms" means an alkenyl group having 3 to 8 carbon atoms having a carbon-carbon double bond at a certain point or more and having a cyclic moiety, and for example, 1-cyclopentene- 1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group and 3-cyclohexen-1-yl group.

Examples of the "alkynyl group" include an ethynyl group, a prop-1-yne-1-yl group, a prop- -1-yl group, hex-5-yn-1-yl group, hepta-1-yl group, 1-yl group, octa-1-in-1-yl group and octa-7-in-1-yl group.

Examples of the "cycloalkylalkyl group" include a cyclopropylmethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylethyl group, and a cycloheptylmethyl group.

"Arylalkyl group" roneun, e.g., C _{6 - 10} aryl C _{1 - 8} as an alkyl group, a benzyl group, a phenethyl group, a 3-phenyl -n- propyl, 4--n- butyl group, 5-phenyl- n-pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like.

Roneun "arylalkenyl group", e.g., C _{6 - 10} aryl C _{2 - 8} as an alkenyl group, a styryl group, 3-phenyl-profile-1-ene-1-yl group, 3-phenyl-profile -2 1-yl group, 4-phenyl-but-1-en-1-yl group, 4-phenyl- Octyl-7-en-1-yl group, a naphthylethenyl group, and the like. have.

Examples of the "hydrocarbon group having an oxygen atom" include a group having an oxirane ring (epoxy group) such as an epoxy group, an epoxyalkyl group and a glycidoxypropyl group, an acryloxymethyl group, and a methacryloxymethyl group.

The epoxy alkyl group is preferably a linear or branched epoxyalkyl group having 3 to 10 carbon atoms, and examples thereof include an epoxy methyl group, an epoxy ethyl group, an epoxy-n-propyl group, an epoxy isopropyl group, Butyl group, an epoxy-n-pentyl group, an epoxy isopentyl group, an epoxy neopentyl group, an epoxy-2-methylbutyl group, an epoxy- Epoxy-n-hexyl group and the like.

Examples of the "hydrocarbon group having a nitrogen atom" include a group having -NR ' ₂ (wherein R' represents a hydrogen atom, an alkyl group or an aryl group, each R 'may be the same or different) CR " ₂ (wherein R" represents a hydrogen atom or an alkyl group, and each R "may be the same or different) is preferable. Examples of the alkyl group include the same groups as described above. , A phenyl group, a naphthyl group, an anthracene-1-yl group, and a phenanthrene-1-yl group.

Examples of the group having -NR ' ₂ include -CH ₂ -NH ₂ group, -C ₃ H ₆ -NH ₂ group, -CH ₃ -NH-CH ₃ group and the like. The group having -N = CR " ₂ includes a -CH ₂ -N═CH-CH ₃ group, a -CH ₂ -N═C (CH ₃ ) ₂ group, a -C ₂ H ₅ -N═CH-CH ₃ group And the like.

Examples of the " hydrocarbon having a silicon atom " include a group containing a polymer such as polysiloxane, polyvinylsilane, or polyacrylsilane.

Examples of the above substituent which may be substituted include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a methacryloxy group. Examples of the halogen atom, the alkyl group, the alkenyl group and the aryl group are the same as those of R. [

A group having a vinyl group or an oxirane ring, -NR ' ₂ (wherein R' represents a hydrogen atom, an alkyl group or an aryl group, each R 'may be the same or different from each other) N = CR " ₂ (wherein R" represents a hydrogen atom or an alkyl group, and each R "may be the same or different) is a preferable group from the viewpoint of inorganicization of the surface of the organic-

In the formula (I) of the organosilicon compound, n represents 1 or 2, and particularly preferably n = 1. When n is 2, each R may be the same or different. These may be used singly or in combination of two or more.

In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) in the formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group means, for example, a group capable of hydrolyzing to form a silanol group or a siloxane condensate by heating at 25 ° C to 100 ° C in the presence of an uncatalyzed or excess water, Specific examples include an alkoxy group, an acyloxy group, a halogen group and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms is preferable.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group and a t-butyloxy group. Examples of the acyloxy group of (6) include an acetyloxy group, a benzoyloxy group and the like. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, an isocyanate group bonded to an alkyl group substituted with an aryl group, .

Specifically, examples of the organic silicon compound to be used as the starting material include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltriethoxysilane, Butoxy silane, butyl trimethoxy silane, pentafluorophenyl trimethoxy silane, phenyl trimethoxy silane, nonafluorobutyl ethyl dimethoxy silane, trifluoromethyl trimethoxy silane, dimethyldiaminosilane, dimethyldichloro Silane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl- (Meth) acryloxyethoxy] silane, methyltriglycidyloxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltriethoxysilane, , Methyltris (3- Vinyl trichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- Silane. These may be used alone or in combination of two or more.

Examples of the organosilicon compound having a group consisting of a polymer of hydrocarbon include (meth) acrylate, methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (Meth) acrylic acid esters such as (meth) acrylic acid, itaconic acid, and fumaric acid, acid anhydrides such as maleic anhydride, epoxy compounds such as glycidyl (meth) (Meth) acrylamide, itaconic acid diamide,? -Ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (Meth) acrylamide, and the like; amide compounds such as acrylonitrile, styrene,? -Methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, A vinyl-based polymer can be given to the R component of the formula (I).

Further, the condensate of the organic silicon compound as the main component in the organic / inorganic hybrid thin film of the present invention means that the organic silicon compound and / or its condensate as a raw material are further condensed.

The blend ratio of the condensate of the organosilicon compound is 2 to 40 mass%, preferably 5 to 30 mass%, based on the solid content of the entire organic-inorganic hybrid thin film.

(Organic polymer compound)

The organic-inorganic hybrid thin film of the present invention further contains an organic polymer compound in addition to the condensate of the organic silicon compound.

The organic polymer compound of the present invention is not particularly limited, but it is preferable to use a compound or resin (ultraviolet ray curable compound) having a functional group which causes polymerization reaction by irradiation of ultraviolet rays in the presence of a photopolymerization initiator, In the presence of ultraviolet rays. For example, a (meth) acrylate compound, an epoxy resin, a vinyl compound other than an acrylate compound, and the like may be exemplified. The number of functional groups is not particularly limited as long as it is one or more.

Examples of the acrylate compound as a raw material include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol propane tri (meth) acrylate, (Meth) acryloyloxy group, and the like. Of these, polyester (meth) acrylate, polyurethane (meth) acrylate and epoxy poly Is a polyurethane (meth) acrylate.

The molecular weight is not limited as far as it can be dissolved in the composition for forming an organic-inorganic hybrid substance, but usually the weight average molecular weight is 500 to 50,000, preferably 1,000 to 10,000.

Also, the polymerized product resulting from the polymerization reaction by ultraviolet irradiation is a cured product.

The polyester (meth) acrylate is obtained, for example, by esterifying a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals thereof with acrylic acid, which is obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. Or by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.

The polyurethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol and a diisocyanate and an acrylate monomer having a hydroxyl group. Examples of the polyol include a polyester polyol, a polyether polyol and a polycarbonate diol .

The epoxy (meth) acrylate can be obtained, for example, by an esterification reaction of an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin with acrylic acid.

Examples of commercial products of urethane (meth) acrylate used in the present invention include commercially available products such as Beam Set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM UA-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA manufactured by Shin Nakamura Chemical Industry Co., M-1110, M-1200, M-1210, M-1310, M-1600, M-1960 manufactured by Toa Seisakusho Co., UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101 manufactured by Nippon Kayaku Co., Ltd., trade name: AH-600, AT606, UA- UV-6000B, UV-6300B, UV-7000, UV-7600B, UV-2010B, manufactured by Nippon Synthetic Chemical Industry Co., UN-3320H, UN-3320HS, UN-3320HS, H-61, HDP-M20, and HDP-M20. Celllux Co., Ltd. trade name: there may be mentioned Ebecryl 6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301 and so on.

Examples of the vinyl compound other than the acrylate compound include N-vinylpyrrolidone, N-vinylcaprolactam, vinyl acetate, styrene, and unsaturated polyester. Examples of the epoxy resin include hydrogenated bisphenol A diglycidyl Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methane -Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, and the like.

The compounding ratio of the organic polymer compound is 60 to 98% by mass, preferably 70 to 95% by mass, based on the solid content of the entire organic-inorganic hybrid substance.

(Photopolymerization initiator)

The photopolymerization initiator of the present invention includes (a) a compound generating a cationic species by light irradiation and (b) a compound generating an active radical species by light irradiation.

As a compound which generates a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (II) can be mentioned as a preferable example.

[R ¹ _a R ² _b R ³ _c R ⁴ _d W] ^{+ e} [ML _{e + f} ] ^-e (II)

(Formula (II) wherein a cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N-, R ^1, R ² , R ³ and R ⁴ are the same or different organic group, a, b, c, and d is the equivalent to the valence of W, (a + b + c + d) an integer of 0 to 3, respectively. M is a metal or metalloid constituting the central atom of the halide complex [ML _{e + f],} for example, B, P, as, Sb , Fe, Sn, Bi, Al, Ca, in, Ti, Zn, Sc, V, Cr, Mn, Co, etc. L is, for example, a halogen atom such as F, Cl or Br, e is the net charge of the halide complex ion and f is the valence of M.

This onium salt is a compound that releases Lewis acid by accepting light.

Specific examples of the anions ML _{e + f in} the formula (II) include tetrafluoroborate (BF ₄ ^- ), hexafluorophosphate (PF ₆ ^- ), hexafluoroantimonate (SbF ₆ ^- ), Hexafluoroarsenate (AsF ₆ ^- ), and hexachloroantimonate (SbCl ₆ ^- ).

An onium salt having an anion represented by the formula [ML _f (OH) ^- ] may also be used. In addition, other anions such as perchlorate ion (ClO ₄ ^- ), trifluoromethanesulfonate ion (CF ₃ SO ₃ ^- ), fluorosulfonate ion (FSO ₃ ^- ), toluenesulfonate ion, trinitrobenzenesulfonate anion and trinitrotoluenesulfonate anion . These may be used alone or in combination of two or more.

Examples of the compound capable of generating an active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane- 1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2- ) Phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzo Trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methyl Vinyl) phenyl) propanone).

The blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the ultraviolet-curing compound as a raw material of the organic polymer compound.

In the present invention, a sensitizer may be added if necessary. For example, there may be mentioned trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid isoamyl, N, N-dimethylbenzylamine, -Bis (diethylamino) benzophenone, and the like.

(Metal compound)

The organic-inorganic hybrid thin film of the present invention may contain a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead.

Among these, titanium, zirconium, aluminum and tin are preferable, and titanium is particularly preferable. These may be used alone or in combination of two or more.

The metal compound of the present invention is at least one compound selected from the group consisting of a metal chelate compound, an organic acid metal salt, a metal compound having two or more hydroxyl groups or hydrolysable groups, a hydrolyzate thereof, and a condensate thereof, / Or a condensate, and in particular, a hydrolyzate and / or a condensate of a metal chelate compound is preferable.

The metal compound in the thin film may be a compound which is present as a raw material compound or a compound in which the compound is further condensed and chemically bonded with the above-described organic silicon compound.

The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, more preferably a metal chelate compound having at least two hydroxyl groups or a hydrolyzable group. The metal chelate compound is preferably a? -Ketocarbonyl compound, a? -Ketoester compound, and an? -Hydroxy ester compound. Specific examples thereof include methyl acetoacetate, n-propyl acetoacetate, acetoacetic acid Butyl ester of acetoacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3-dione, , Β-diketones such as 5-dione, octane-2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid And the like.

The organic acid metal salt is a compound comprising a metal ion and a salt obtained from an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid, sulfuric acid, sulfuric acid and sulfuric acid such as thiophenol, An oxime compound, an imide compound, an aromatic sulfonamide and the like.

The metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include hydroxides of metals and metal alcoholates.

Examples of the hydrolyzable group in the metal compound of the present invention include an alkoxy group, an acyloxy group, a halogen group, an isocyanate group, an alkoxy group having 1 to 4 carbon atoms and an acyloxy group having 1 to 4 carbon atoms Do. The term "having two or more hydroxyl groups or hydrolysable groups" means that the sum of the hydroxyl groups and the hydrolyzable groups is two or more.

The hydrolyzate and / or condensate of the metal chelate compound is preferably hydrolyzed using 5 to 100 moles of water per 1 mole of the metal chelate compound, and is preferably hydrolyzed with 5 to 20 moles of water More preferable.

The hydrolyzate and / or condensate of the metal organic acid salt compound is preferably hydrolyzed using 5 to 100 moles of water with respect to 1 mole of the metal organic acid salt compound and is preferably hydrolyzed with 5 to 20 moles of water Is more preferable.

The hydrolyzate and / or condensate of the metal compound having at least two hydroxyl groups or hydrolysable groups is preferably hydrolyzed by using at least 0.5 mol of water per mol of the metal compound having at least two hydroxyl groups or hydrolysable groups, And more preferably hydrolyzed using ~2 moles of water.

The compounding amount of the metal compound used in the present invention may vary depending on the kind thereof, but generally the metal atom in the metal compound is 0.01 to 0.5 molar equivalent, preferably 0.05 to 0.2 molar equivalent, based on Si in the organosilicon compound.

(Other components)

Tetrafunctional silane or colloidal silica may be added for the purpose of improving the hardness of the resulting coating film. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (Meth) acryloxy silane, tetrakis [2- (meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis Silane, and tetrakis (3-methyl-3-oxetanemethoxy) silane. Examples of the colloidal silica include water-dispersed colloidal silica, and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

It is also possible to separately add and disperse a filler in order to exhibit various properties such as coloring, thickening of the coating film to be obtained, prevention of ultraviolet ray penetration to the lower surface, impartation of anticorrosion, and heat resistance. Examples of the filler include non-water-soluble pigments such as organic pigments and inorganic pigments, or particulate, fibrous or scaly metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides and sulfides thereof . Specific examples of the filler include particulate, fibrous or scaly iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, Cobalt oxide, synthetic mullite, aluminum hydroxide, iron oxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, mica, Zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, shellac green, natto, manganese green, pigment green, gray, blue, cobalt blue, cerulean blue, copper borate, molybdenum blue , Copper sulfide, cobalt violet, mas violet, manganese violet, pigment violet, lead oxide, calcium lead, zinc yellow, lead sulfide, chrome yellow, loess, cadmium yellow Zinc white, antimony white, basic sulfuric acid lead, titanium white, lithopone, lead silicate, lead oxide, lead oxide, lead oxide, strontium yellow, titanium yellow, litharge, pigment yellow, copper oxide, cadmium red, selenium red, chromium vermillion, Zircon, tungsten white, lead zinc white, bunch white, phthalate lead, manganese white, lead sulfate, graphite, black black, diamond black, samatomic black, vegetable black, potassium titanate whisker and molybdenum disulfide.

Other additives such as known dehydrating agents such as methyl orthoformate, methyl orthoacetate and tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners and leveling agents may also be added have.

2 Manufacturing method of organic / inorganic composite thin film

1) Preparation of a solution for forming an organic / inorganic composite thin film

The solution for forming the organic / inorganic hybrid thin film in the present invention is prepared by mixing an organic silicon compound, a raw material of an organic polymer compound and a photopolymerization initiator and, if necessary, other components such as a metal compound, water and / or a solvent.

Concretely, for example, a metal compound is mixed with a solvent, and a predetermined amount of water is added to perform (partial) hydrolysis, followed by addition of an organosilicon compound (partial) to hydrolysis. On the other hand, a raw material for an organic polymer compound is dissolved in a solvent, a photo polymerization initiator is added, and then both solutions are mixed. These four components may be mixed at the same time. The mixing method of the organosilicon compound and the metal compound may be a method of mixing the organosilicon compound and the metal compound, and then adding water to (partial) And a method of separately mixing (partially) hydrolyzing the metal compound. It is not always necessary to add water or a solvent, but it is preferable to add water to make it a (partial) hydrolyzate. The amount of water in a predetermined amount varies depending on the kind of the metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or a hydrolysable group, 0.5 mol or more of water is used relative to 1 mol of the metal compound , And it is more preferable to use 0.5 to 2 moles of water. When the metal compound is a metal chelate compound or an organic acid metal salt, 5 to 100 moles of water is preferably used per 1 mole of the metal chelate compound or the organic acid metal salt, more preferably 5 to 20 moles of water .

As the condensate of the organosilicon compound of the present invention, a (partially) hydrolyzed organosilicon compound may be used by using a known silanol condensation catalyst.

The composition for forming the organic / inorganic hybrid thin film in the present invention preferably contains water and / or a solvent in addition to the above components.

Examples of the solvent to be used include, but are not limited to, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane and cyclopentane, Methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Alcohols such as methanol and ethanol, polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate, and the like. These solvents may be used singly or in combination of two or more.

The solid content (raw material of the organic silicon compound and / or its condensate and organic polymer compound) in the solution for forming an organic / inorganic hybrid thin film in the present invention is preferably 1 to 75% by mass, more preferably 10 to 60% Is more preferable.

The mixing ratio of each component in the solid content in the solution for forming an organic / inorganic hybrid thin film is the same as that in the organic / inorganic hybrid thin film.

2) Manufacturing method of organic-inorganic hybrid thin film

The organic-inorganic hybrid thin film of the present invention comprises (A) a step of applying a solution for forming an organic / inorganic hybrid thin film described above onto a substrate and drying by heating, (B) a step of irradiating light having a wavelength of 350 nm or less, And (C) plasma treatment or UV ozone treatment.

In the case of performing the UV ozone treatment in the step (C), the step B may be omitted.

The organic-inorganic hybrid thin film of the present invention is characterized in that the concentration of carbon atoms at a depth of 10 nm from the surface is 20% or more, preferably 30% or less, more than the concentration of carbon atoms at a depth of 100 nm from the surface, And the O / Si source consumption of 2 nm depth from the surface of the film is 1.8 to 2.5, preferably 1.9 to 2.4.

The Si / C source consumption at a depth of 100 nm from the surface is preferably 0.2 or less, more preferably 0.15 or less.

Here, the " concentration of carbon atoms " means the molar concentration of carbon atoms when (total metal atom + oxygen atom + carbon atom) is taken as 100%. The concentrations of other elements are the same.

In addition, the "layer in which the condensate of the organosilicon compound is concentrated" is defined as the concentration of carbon atoms by the ESCA analysis. In the concentrated layer, the concentration is also high in the silicon concentration.

In the present invention, the lower the carbon concentration is, the higher the silicon concentration is.

In the present specification, the value of the film thickness used when defining the carbon content in the thin film is a value calculated by sputter etching in the ESCA analysis, but it does not necessarily correspond to the value of the actual film thickness. This is because the film thickness to be etched by the sputter etching depends on the material of the film. Therefore, the actual film thickness value is obtained by converting the etching rate for each film material.

In the ESCA analysis in the present specification, the SiO ₂ film thickness was used as a standard sample of a thermally oxidized SiO ₂ film. The standard sample is a thermally oxidized SiO ₂ film formed on a silicon wafer. The etch rate was calculated by ESCA analysis while sputter etching a standard sample having a film thickness measured in advance by an ellipsometer.

If the condensation of the compound in which R is a vinyl group in the organosilicon compound represented by the formula (I) is contained in an amount of 70% by mass or more of the total condensate of the organosilicon compound, the step (C) The degree of mineralization of the surface is further advanced.

Examples of the gas capable of forming the thin film of the present invention include metals, ceramics, glass, and plastic. Conventionally, it is difficult to form a thin film into a plastic substrate, and the substrate is limited to an inorganic substrate such as glass. However, a thin film of the present invention can be easily formed even on a plastic substrate which is difficult to form, . Examples of such plastics include polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin and polyethersulfone.

As a method of applying the solution for forming an organic-inorganic hybrid thin film, a known coating method can be used. For example, a dip coating method, a spray coating method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, A silk screen method, an ink jet method, and the like. The thickness of the film to be formed is not particularly limited, and is, for example, about 0.1 to 200 mu m.

The drying treatment of the film formed by applying the solution for forming an organic / inorganic hybrid thin film is preferably carried out at a temperature of, for example, 40 to 200 DEG C for 0.5 to 120 minutes, preferably 60 to 120 DEG C for 1 to 60 minutes Is more preferable.

In the present invention, " light containing a wavelength of 350 nm or less " means not only a wavelength of 350 nm or less, but also ultraviolet light having a wavelength longer than 350 nm. This is because the ultraviolet curable compound has a photosensitivity at a wavelength exceeding 350 nm, preferably around 365 nm, while the photosensitizer compound requires a wavelength of 350 nm or less.

Irradiation of light having a wavelength of 350 nm or less can be carried out by using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp or an excimer lamp, To 350 nm, and more preferably a light having a wavelength of 250 to 310 nm as a main component. If it is sensitive to such a range of wavelengths and does not react with light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight. The amount of irradiation light irradiated may be, for example, about 0.1 to 100 J / cm 2. Considering the film curing efficiency (the relationship between the irradiation energy and the film hardening degree), about 0.2 to 20 J / , And more preferably about 0.5 to 10 J / cm 2.

The irradiation of light having a wavelength of 350 nm or shorter refers to irradiation with light having a wavelength of 350 nm or less as a component, preferably irradiation with light having a wavelength of 350 nm or less as a main component , That is, the irradiation using a light source having a wavelength of 350 nm or less with the largest component amount.

The pencil hardness specified by the JIS K 5600-5-4 pencil method when a thin film after drying (corresponding to the inside of the film in a light-irradiated thin film) is formed on a glass substrate is about 1 H to 4 H, It is preferably 2 H to 4 H in terms of adhesion and hardness. The pencil hardness specified by the JIS K 5600-5-4 pencil method when the thin film after light irradiation is formed on a glass substrate is preferably 5 H or more, and more preferably 7 H or more.

In the present invention, the plasma treatment is a corona discharge treatment in a nitrogen gas atmosphere or a glow plasma treatment in a rare gas atmosphere such as helium or argon.

More specifically, a method of generating a plasma by applying a high voltage of a high frequency between parallel plate electrodes coated with a dielectric at least one of the electrode pairs and holding the base layer between the electrodes, or a method of moving the base layer between the electrodes . The atmospheric pressure plasma treatment has a higher density of active species than the vacuum plasma treatment, so that the surface of the electrode can be treated at a high speed and with a high efficiency. There is an advantage that it is possible to perform processing with a small number of process water.

The atmospheric pressure plasma treatment is carried out by using an atmospheric pressure plasma generator (for example, an atmospheric pressure plasma apparatus S-5000 manufactured by Sakigake Semiconductor, an atmospheric pressure plasma surface treatment apparatus RD series manufactured by Sekisui Chemical Co., Ltd.) .

In the present invention, UV ozone treatment means that UV rays (ultraviolet rays) are applied to a thin film, oxygen in the air is changed to ozone, and the thin film is modified by ozone and ultraviolet rays.

The UV light source is not particularly limited as long as it can change oxygen to ozone by UV irradiation. As a UV light source, a low-pressure mercury lamp can be mentioned. Low pressure mercury lamps generate UV light at 185 nm and 254 nm, and the 185 nm line can change oxygen to ozone. The illuminance at the time of irradiation differs depending on the light source to be used, and is generally from several tens to several hundreds mW / cm < 2 >. In addition, the illuminance can be changed by condensing or diffusing light. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, and is usually 1 minute to 24 hours. The treatment temperature is usually 10 to 200 占 폚. The amount of UV irradiation (i.e., ultraviolet ray amount) is usually 1 J / cm2 or more, preferably 1 to 100,000 J / cm2, and more preferably 10 to 100,000 J / cm2.

The organic / inorganic hybrid thin film of the present invention has a structure in which the content of carbon atoms in the surface portion of the film is smaller than the content of carbon atoms in the inside of the film (in the vicinity of the bonding portion with the substrate) by the step (B) It can be said that a concentrated layer of the compound is formed.

Therefore, even when the plasma treatment and the UV ozone treatment in the step (C) are performed, only the silane compound on the surface of the film reacts, and the organic polymer compound in the film is hardly affected. As a result, no change can be seen even after comparing the average roughness measured by the AFM measurement before and after the step (C).

Since the organic compound is generally decomposed by plasma treatment or UV ozone treatment, the treatment has been mainly used for cleaning contamination originating from an organic compound on an inorganic compound such as glass. In the organic-inorganic hybrid thin film of the present invention, it is also possible that the silane compound-enriched layer on the surface of the film serves as a protective layer against plasma treatment or UV ozone treatment.

3 Preparation of a layer containing a hydrolyzed condensate of a metal surface active agent

Further, in the present invention, a layer containing a hydrolysis-condensation product of a metal surface-active agent can be further formed on the organic-inorganic hybrid thin film. The layer containing the hydrolyzed condensate of the metal surface active agent is preferably a monomolecular film.

Hereinafter, a method for producing a layer containing a hydrolyzed condensate of a metal surface active agent will be described.

The layer containing the hydrolysis-condensation product of the metal surface-active agent is preferably a layer containing at least one hydrolyzable group-containing metal-based surfactant, as described in, for example, WO2008-059840, Compound capable of reacting with an organic solvent " and water.

As the " metal-based surfactant having at least one hydrolyzable group "

R ³ _S Mx _{t -s} (III)

Wherein R ³ is a hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group of 1 to 30 carbon atoms which may have a substituent, a hydrocarbon group of 1 to 30 carbon atoms containing a linking group, or a linking group And M represents at least one kind of metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom and a zirconium atom, X represents a hydroxyl group or a hydrolyzable group, t represents the valence of M; s represents any positive integer from 1 to (t-1), and when s is 2 or more, R ³ may be mutually the same or different. (ts) is 2 or more, X may be the same or different, and at least one of X is a hydrolyzable group.

Examples of the hydrocarbon group of the hydrocarbon group having 1 to 30 carbon atoms which may have a substituent in the formula (III) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-hexyl group, an n-hexyl group, An alkenyl group such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a n-decynyl group or an n-octadecynyl group, an aryl group such as a phenyl group, a 1-naphthyl group, .

Examples of the halogenated hydrocarbon group of the halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent include a halogenated alkyl group having 1 to 30 carbon atoms, a halogenated alkenyl group having 1 to 30 carbon atoms, and a halogenated aryl group having 1 to 30 carbon atoms. Among them, a group in which at least two hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are substituted with a halogen atom is preferable, and a fluorinated alkyl group in which at least two hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are substituted with a fluorine atom is more preferable. When the fluorinated alkyl group has a branched structure, it is preferable that the branched portion is a single chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

Examples of the halogenated hydrocarbon group of the hydrocarbon group and the halogenated hydrocarbon group including the linking group include a hydrocarbon group of a hydrocarbon group which may have such a substituent and a halogenated hydrocarbon of a halogenated hydrocarbon group which may have a substituent May be the same as those exemplified above.

The linking group is preferably present between the carbon-carbon bond of the hydrocarbon group or the halogenated hydrocarbon group, or the carbon of the hydrocarbon group and the metal atom M described later.

Specific examples of the linking group is for _{example, -O-, -S-, -SO 2 -} , -CO-, -C (= O) O- or ^{-C (= O) NR 51 -} ( wherein, R ⁵¹ is hydrogen An alkyl group such as methyl group, ethyl group, n-propyl group or isopropyl group).

Among these, from the viewpoint of water repellency and durability, each is preferably an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group having a linking group.

X represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group which is decomposed by reaction with water. Examples of the substituent include an alkoxy group having 1 to 6 carbon atoms which may have a substituent, an acyloxy group which may have a substituent, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an isocyanate group, Or an amide group.

Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, And the period of time when the painting is finished. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group. Examples of the substituent include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group. Among them, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an acyloxy group, a halogen atom, or an isocyanate group is preferable, and an alkoxy group or an acyloxy group having 1 to 4 carbon atoms is more preferable.

M represents one kind of atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom and a zirconium atom. Among these, silicon atoms are preferable from the viewpoints of availability of raw materials, reactivity, and the like.

The metal-based surfactant represented by the formula (III) includes, for example, the following silane coupling agents. In the following, M is Si and R ¹ is a hydrocarbon group, but the present invention is not limited thereto.

These compounds may be used singly or in combination of two or more.

Examples of the compound capable of interacting with the metal-based surfactant include metal oxides, metal hydroxides, metal alkoxides, partially hydrolyzed products of metal alkoxides, hydrolyzed products of metal alkoxides, chelated or coordinated metal compounds, silanol condensation At least one selected from a catalyst and an acid catalyst is used.

Examples of the metal oxides include methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK- ST, MIBK- -ST (all trade names of organosilica sol manufactured by NISSAN CHEMICAL INDUSTRIES, LTD.), And the like.

The metal hydroxide may be a metal hydroxide obtained by any production method. Examples of the method for producing the metal hydroxide include a method of hydrolyzing a metal alkoxide to be described later, a method of reacting a metal salt with a metal hydroxide, and the like. Further, commercially available metal hydroxides can be used as desired by refining them.

Metal alkoxide _{include, Si (OCH 3) 4,} Si (OC 2 H 5) 4, Si (OC 3 H 7 -i) 4, silicon alkoxides such as _{Si (OC 4 H 9 -t)} 4; Ti ( _{OCH 3) 4, Ti (OC} 2 H 5) 4, Ti (OC 3 H 7 -i) 4, Ti (OC 4 H 9) titanium alkoxides such as _{4; Ti [OSi (CH 3} ) 3] 4, Ti _{[OSi (C 2 H 5)} 3] 4 , such as tetrakis trialkyl siloxy _{titanium; Zr (OCH 3) 4,} Zr (OC 2 H 5) 4, Zr (OC 3 H 7) 4, Zr (OC 4 H _{9) 4} such as zirconium _{alkoxide; Al (OCH 3) 4,} Al (OC 2 H 5) 4, Al (OC 3 H 7 -i) 4, Al (OC 4 H 9) _3, such as an aluminum alkoxide; Ge (OC ₂ H _{5) 4,} such as germanium _{alkoxides; in (OCH 3) 3,} in (OC 2 H 5) 3, in (OC 3 H 7 -i) 3, in , such as indium (OC ₄ H _{9) 3 alkoxide; Sn (OCH 3) 4,} Sn (OC 2 H 5) 4, Sn (OC 3 H 7 -i) 4, Sn (OC 4 H 9) 4 , such as tin _{alkoxide; Ta (OCH 3) 5,} Ta _{(OC 2 H 5) 5,} Ta (OC 3 H 7 -i) 5, Ta (OC 4 H 9) a tantalum alkoxide such as _{5; W (OCH 3) 6} , W (OC 2 H 5) 6, W ( OC ₃ H ₇ -i) ₆ , and W (OC ₄ H ₉ ) ₆ ; Zn (OC ₂ H ₅ ) _2, and lead alkoxides such as Pb (OC ₄ H ₉ ) ₄ . These metal alkoxides may be used singly or in combination of two or more.

Partial hydrolysis products of metal alkoxides are obtained before complete hydrolysis of the metal alkoxide, and examples thereof include a precursor of a metal oxide sol or an oligomer in the form of an oligomer.

Specific examples of the partial hydrolysis product of the metal alkoxide include a dispersion in which an at least one member selected from the group consisting of an acid, a base and a dispersion stabilizer is present in an organic solvent, and which is stably dispersed without aggregation The quality can be preferably exemplified. In this case, the dispersion quality refers to fine particles dispersed in the dispersion system, and specifically, colloidal particles and the like can be exemplified. Here, the state of not being agglomerated and stably dispersed means a state in which, in the organic solvent, the dispersoids of the hydrolysis products are not heterogeneously separated in the absence of an acid, a base and / or a dispersion stabilizer, Preferably a transparent and homogeneous state. The term "transparent" refers to a state in which the transmittance in visible light is high. More specifically, the concentration of the dispersoid is 0.5 wt% in terms of oxide, the optical path length of the quartz cell is 1 cm, , And a spectral transmittance measured under the condition that the wavelength of light is 550 nm, and preferably shows a transmittance of 80 to 100%. The particle diameter of the dispersoid of the hydrolysis product is not particularly limited, but in order to obtain a high transmittance in visible light, it is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm, More preferably in the range of < RTI ID = 0.0 >

The partial hydrolysis product of the metal alkoxide may be prepared by dissolving water in an organic solvent in the absence of an acid, a base and / or a dispersion stabilizer in an amount of 0.5 to 2.0 times less than the molar amount of the metal alkoxide, A method of hydrolyzing at a temperature of -100 ° C to an organic solvent reflux temperature can be preferably exemplified.

The metal alkoxide hydrolysis product used in the present invention is a product obtained by hydrolysis with water equal to or more than twice the metal alkoxide. The hydrolysis product may be obtained by hydrolyzing the metal alkoxide with water equal to or more than twice the equivalent amount of the metal alkoxide, and partially hydrolyzing the metal alkoxide with water less than twice the equivalent amount of the metal alkoxide, The partial hydrolyzate is further hydrolyzed with a predetermined amount of water (water in an amount equal to or more than twice the equivalent amount of the metal alkoxide as the sum of the amount of water used for the above partial hydrolysis) Or may be obtained by decomposition.

The chelated or coordinated metal compound can be prepared by adding a chelating agent or coordination compound capable of forming a complex with the metal of the metal compound to a solution of the metal compound. The chelating agent or coordination compound is not particularly limited as long as it is capable of forming a complex to chelate or dilute a metal of a hydrolysis product obtained by treating a metal hydroxide, a metal alkoxide, or a metal alkoxide with water.

Examples of the chelating agent or coordination compound include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid and stearic acid; oxalic acid, malonic acid, succinic acid, Saturated aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, oleic acid and maleic acid; , Aromatic carboxylic acids such as phthalic acid, halogenocarboxylic acids such as chloroacetic acid and trifluoroacetic acid,? -Diketones such as acetylacetone, benzoyl acetone and hexafluoroacetylacetone, methyl acetoacetate and ethyl acetoacetate Ketones such as tetrahydrofuran, furan, furancarboxylic acid, thiophene, thiophenecarboxylic acid, pyridine, nicotinic acid, isonicotinic acid, etc. Lee may be the compounds and the like. These may be used alone or in combination of two or more.

Examples of the silanol condensation catalyst include a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal salt polymer, a carboxylic acid metal salt chelate, a titanate ester, and a titanate ester chelate.

Specific examples include stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, dioctanic acid 1 tin, lead naphthenate, cobalt naphthenate, 2-ethylhexenyl iron oxide, dioctyltin bis octyl thioglycolic acid ester salt, dioctyltin maleate ester salt, dibutyltin maleate polymer, dimethyl tin mercaptopropionate polymer , Dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, titanium tetraethoxide, titanium tetrabutoxide, titanium tetraisopropoxide, titanium bis (acetylacetonyl) dipropoxide, and the like. have.

Examples of the acid catalyst include mica such as hydrochloric acid, nitric acid, boric acid and hydrobromic acid, and organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p- toluenesulfonic acid and methanesulfonic acid. , Photoacid generators that generate an acid upon irradiation with light, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like.

The content of water in the organic solvent solution containing a metal surfactant having at least one hydrolysable group, a compound capable of interacting with the metal surfactant, and water is preferably 10 to 2000 ppm. Methods for adjusting or maintaining the water content within a predetermined range include (i) a method of forming an aqueous layer by contacting with the organic solvent solution, (ii) a method in which a water-retaining material containing water is allowed to coexist, iii) a method of spraying a gas containing water, and the like.

In order to form the layer containing the hydrolyzed condensate of the metal surface active agent on the organic-inorganic hybrid substance having the organic / inorganic hybrid thin film, the organic solvent solution is applied by a dipping method, a spin coating method, a spraying method, a roller coating method, Inorganic composite thin film on the organic-inorganic hybrid substance by a method such as printing, brush coating or the like, preferably by a dipping method.

Example

Hereinafter, embodiments of the present invention will be described, but the technical scope of the present invention is not limited thereto.

In the present embodiment, the "atmospheric pressure plasma treatment" was conducted by using an atmospheric pressure plasma surface treatment apparatus (manufactured by Sekisui Chemical Co., Ltd.) and irradiating a plasma generated by nitrogen gas to the organic / inorganic hybrid thin film. The substrate conveyance speed for the substrate treatment was 20 m / min.

&Quot; UV ozone treatment " was carried out for 10 minutes using a UV ozone cleaning apparatus (manufactured by Iwasaki Electric Co., Ltd.) for cleaning the organic-inorganic hybrid thin film.

Evaluation of each thin film was carried out by the following method.

The elemental concentration of carbon atoms and the oxygen / silicon source consumption for depth from the thin film surface were determined by ESCA analysis.

The adhesion of thin films was evaluated by a 180 degree peel test. The test was carried out in accordance with JIS Z 0237 (adhesive tape, pressure-sensitive adhesive sheet test method). An adhesive tape (polyester 31B tape, width 10 mm, manufactured by Nitto Co., Ltd.) was reciprocated twice by a roller of 1 kg on the organic-inorganic hybrid film cut to a length of 300 mm. The organic-inorganic composite film and the adhesive tape were peeled off at a rate of 300 mm / min by 150 mm, and the average value of the test stresses of 125 mm except for the first 25 mm data was measured.

The static contact angle of the thin film was evaluated by using Drop Master (manufactured by Kyowa Interface Science Co., Ltd.) as a contact angle measuring device, water repellency of 2 占 퐇 of water, and oil repellency of 7 占 퐇 of n-tetradecane.

The average surface roughness of the thin film was measured in the AFM mode using SPI3800N and SPA400 units (all manufactured by SIE A Nano Technology Co., Ltd.). For the AFM measurement, the SN-AF01 cantilever was used and the range of 10 탆 square was measured at a scanning speed of 1 Hz. The size of the surface roughness was obtained from the data of the measured shape image.

The cross-sectional observation of the thin film was carried out by using a transmission electron microscope (FE-TEM; HF-2000 manufactured by Hitachi) after processing a sample piece with a focused ion beam. The cross-sectional observation was carried out at an acceleration voltage of 200 kV and an observation magnification of 100,000 times.

[Example 1]

(Preparation of solution for forming organic / inorganic hybrid thin film)

264.7 g of diisopropoxybisacetyl acetonate titanium ("T-50" manufactured by Nippon Soda Co., Ltd., solid content in terms of titanium oxide: 16.5 mass%) was dissolved in a mixed solvent of industrial ethanol ("Solmics (registered trademark) AP-7 "), 51.1 g of ion-exchanged water was added with stirring. The solution was stirred for 2 hours while being warmed to 40 占 폚, and hydrolyzed to obtain a yellow transparent metal compound hydrolyzate solution [A-1] (solid content in terms of titanium oxide: 5.0% by mass).

(Manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-1003") and 3-methacryloxypropyltrimethoxysilane [B-2] C-1] ([B-1] / [B-2] = 70/30: mol) in which 190.2 g of a polyvinyl alcohol solution (trade name: KBM- Next, 453.1 g of [A-1] and 455.0 g of [C-1] were mixed with stirring, and 92.0 g of ion-exchanged water was added and stirred for 1 day to prepare a condensed solution [D-1].

451.8 g of a urethane acrylate oligomer ("UV7600B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 364.1 g of methyl isobutyl ketone. 18.1 g of 2-methyl-1- (methylthiophenyl) -2-morpholinopropane-1-one (Irgacure (registered trademark) 907 manufactured by BASF) as a photopolymerization initiator was dissolved in this solution, E-1].

166.1 g of [D-1] and 834.0 g of [E-1] were mixed so that the solid content ratio was [D-1] / [E-1] = 10 mass% / 90 mass% Solution [F-1] (solid concentration 52.0 mass%) was prepared.

(Fabrication of organic-inorganic hybrid thin film)

A microgravure coater (manufactured by Yasui Chemical Co., Ltd.) was used under the conditions of a drying temperature of 80 ° C and a cumulative UV irradiation amount of 473 mJ / cm 2 (manufactured by Igraphics Co., Ltd., high pressure mercury lamp) And a film was formed on a PET film (Cosmo Shine (registered trademark) A4300, manufactured by TOYOSEKI CO., LTD.). The surface of the coating film was subjected to an atmospheric pressure plasma treatment to obtain an organic-inorganic hybrid thin film [X-1] having a thickness of 5 탆 (Fig. 1).

As a result of measuring the roughness of the film surface before and after the atmospheric plasma treatment, the average surface roughness was not changed at all 3.0 nm before treatment (Fig. 2) and 2.8 nm after treatment (Fig. 3).

[Example 2]

The solution for forming an organic / inorganic hybrid thin film [F-1] used in Example 1 was applied onto a microgravure coater (Yasui Kogyo Co., Ltd.) under the conditions of a drying temperature of 80 ° C and a cumulative UV irradiation amount of 473 mJ / cm 2 (COSMO SHINE (registered trademark) A4300, manufactured by TOYOSEKI CO., LTD.) Was formed by using a PET film The surface of the coated film was subjected to UV ozone treatment to obtain an organic-inorganic hybrid thin film [X-2] (Fig. 4) having a thickness of 5 mu m.

The cross section of the organic-inorganic hybrid thin film [X-2] was observed by a transmission electron microscope. As a result, a siloxane-enriched layer was observed at a thickness of 40.7 nm from the surface, and an inorganic portion at a thickness of 15.5 nm (Fig. 5).

[Example 3]

(Preparation of solution for forming organic / inorganic hybrid thin film)

130.6 g of diisopropoxybisacetyl acetonate titanium ("T-50", manufactured by Nippon Soda Co., Ltd., solid content in terms of titanium oxide: 16.5% by mass) was dissolved in industrial ethanol ("Solmics (registered trademark) AP-7 "), 48.6 g of ion-exchanged water was added with stirring. This solution was stirred for 2 hours while being warmed to 40 占 폚 to be hydrolyzed to obtain a yellow transparent metal compound hydrolyzate solution [A-2] (solid content in terms of titanium oxide: 5.0% by mass).

179.9 g of vinyltrimethoxysilane [B-1] (KBM-1003, Shin-Etsu Chemical Co., Ltd.) and 3-methacryloxypropyltrimethoxysilane [B-2] C-2] ([B-1] / [B-2] = 50/50: molar ratio) in which 301.6 g of "KBM-503" Next, 431.0 g of [A-2] and 481.5 g of [C-2] were mixed with stirring, and 87.5 g of ion-exchanged water was added and stirred for one day to obtain a condensate [D-2].

486.7 g of a urethane acrylate oligomer ("UV7600B", manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was dissolved in 332.6 g of methyl isobutyl ketone. 19.5 g of 2-methyl-1- (methylthiophenyl) -2-morpholinopropane-1-one (Irgacure (registered trademark) 907 manufactured by BASF) as a photopolymerization initiator was dissolved in this solution, E-2].

161.2 g of [D-2] and 838.8 g of [E-2] were mixed so that the solid content ratio was [D-2] / [E-2] = 10 mass% / 90 mass% Solution [F-2] (solid concentration of 55.5% by mass) was prepared.

(Fabrication of organic-inorganic hybrid thin film)

(Manufactured by Tester Industries, Ltd.) under the conditions of a drying temperature of 80 占 폚 and a cumulative UV irradiation amount of 500 mJ / cm2 (high-pressure mercury lamp manufactured by Igraphics Co., Ltd.) (Cosmo Shine (registered trademark) A4300, manufactured by TOYOSEKI CO., LTD.). The surface of the coating film was subjected to an atmospheric pressure plasma treatment to obtain an organic-inorganic hybrid thin film [X-3] having a thickness of 5 占 퐉.

[Comparative Example 1]

The solution for forming an organic / inorganic hybrid thin film [F-2] used in Example 3 was applied to a microgravure coater (manufactured by Yasui Chemical Co., Ltd.) under the conditions of a drying temperature of 80 ° C and a cumulative UV irradiation amount of 473 mJ / cm 2 ) Was used to form a film on a PET film (Cosmo Shine (registered trademark) A4300, manufactured by TOYOSEKI CO., LTD.) To obtain an organic-inorganic hybrid thin film [Z-1] having a thickness of 5 탆.

Table 1 shows the results of ESCA analysis, adhesion test, and static contact angle test of each organic-inorganic hybrid thin film obtained in Examples 1 to 3 and Comparative Example 1.

[Example 4]

The organic-inorganic hybrid thin film [X-1] prepared in Example 1 was immersed for 30 seconds in a monomolecular film forming agent (SAMLAY-A (registered trademark) manufactured by Nippon Soda Co., Ltd.) , Manufactured by Japan Energy Co., Ltd.). The washed thin film was dried to obtain an organic-inorganic hybrid thin film [Y-1] treated with a monomolecular film.

[Example 5]

Inorganic hybrid thin film [Y-2] obtained by treating monomolecular film by performing the same treatment as in Example 4, using the organic-inorganic hybrid thin film [X-2] prepared in Example 2.

[Example 6]

Inorganic hybrid thin film [Y-3] obtained by treating monomolecular film by performing the same treatment as in Example 4 using the organic-inorganic hybrid thin film [X-3] prepared in Example 3 was obtained.

[Comparative Example 2]

(Formation of Ultraviolet Curable Resin Thin Film Containing No Silicon Compound)

(Manufactured by YASUI CHEMICAL CO., LTD.) Under the conditions of a drying temperature of 80 ° C and a cumulative UV irradiation amount of 473 mJ / cm 2 (high-pressure mercury lamp manufactured by Igraphics Co., Ltd.) Was used to form a film on a PET film (Cosmo Shine (registered trademark) A4300, manufactured by TOYOSEKI CO., LTD.) To obtain an ultraviolet curable resin thin film having a thickness of 5 占 퐉. After the atmospheric pressure plasma treatment, a monomolecular film treatment was carried out in the same manner as in Example 5 to obtain a film [Z-2].

Table 2 shows the results of the adhesion test and the static contact angle test of the thin film after the monomolecular film treatment obtained in Examples 4 to 6 and Comparative Example 2.

[Example 7]

[D-1] and [E-1] synthesized in Example 1 were mixed so that the solid content ratio was [D-1] / [E-1] = 30 mass% / 70 mass% To thereby prepare a solution [F-3] (solid content concentration: 40% by mass) for forming an organic / inorganic hybrid thin film.

(Manufactured by Tester Ind. Co., Ltd.) under the conditions of a drying temperature of 60 占 폚 and a cumulative UV irradiation amount of 500 mJ / cm2 (high pressure mercury lamp manufactured by Igraphics Co., Ltd.) (Soft Acryl SA-00 manufactured by CRD Co., Ltd.). The surface of the coated film was subjected to the same atmospheric pressure plasma treatment as in Example 1 to obtain an organic-inorganic hybrid thin film [X-4] having a thickness of 5 占 퐉.

[Comparative Example 3]

[D-1] and [E-1] synthesized in Example 1 were mixed so that the solid content ratio was [D-1] / [E-1] = 50 mass% / 50 mass%, diluted with MEK solvent To prepare a solution [F-4] (solid content concentration: 40% by mass) for forming an organic / inorganic hybrid thin film.

(Manufactured by Tester Ind. Co., Ltd.) under the conditions of a drying temperature of 60 占 폚 and a cumulative UV irradiation amount of 500 mJ / cm2 (high pressure mercury lamp manufactured by Igraphics Co., Ltd.) (Soft Acryl SA-00 manufactured by CRD Co., Ltd.). The surface of the coated film was subjected to the same atmospheric pressure plasma treatment as in Example 1 to obtain an organic-inorganic hybrid thin film [X-5] having a thickness of 5 占 퐉.

Table 3 shows the evaluation results of Example 7 and Comparative Example 3.

Industrial availability

According to the present invention, it is possible to provide an organic-inorganic hybrid thin film having a very high surface hardness, excellent flexibility, excellent adhesion with a gas and moisture resistance.

Since the thin film of the present invention has a SiO ₂ phase structure with a high polarity on the surface, the interlayer adhesion when various films are laminated is excellent. For example, in the case of many commercially available silicone-based cured films, the adhesiveness with printing ink due to their water repellency is a problem, but the thin film of the present invention has good adhesion with ink. In addition, adhesion with the inorganic thin film is excellent. Examples of the inorganic thin film include a photoconductive film such as TiO ₂ , a conductive thin film such as ITO and SnO ₂ thin film, a dielectric / piezoelectric thin film such as Ta ₂ O ₅ and PZT, a low refractive film such as SiO ₂ , MgO, MgF ₂ , A high refractive index film such as TiO ₂ and ZrO ₂ , an inorganic film which is hardly adhered to a resin and is formed on a Si wafer or a glass substrate, a metal film such as a metal Al, a metal Cr, a metal Cu, a metal Ag, Adhesion with a metal film formed by vacuum evaporation, sputtering, plating or the like.

In addition, surface treatment by silane coupling treatment is also possible, and various treatments are easy, such as changing the surface to water and oil repellency, introducing an amino group, and imparting plating adhesion.

The thin film of the present invention is produced in two steps of curing by heat drying and curing by ultraviolet light. In the heat drying treatment, the hydrolysis and polycondensation of the organosilicon compound progresses, and the polysiloxane is changed to cure. However, since the ultraviolet ray hardening compound hardly progresses in heating, the film after the heat drying treatment can be formed by appropriately selecting the kind of the organosilicon compound, the kind of the ultraviolet ray hardening compound and the mixing ratio thereof.

In the thin film of the present invention, for example, the film after the heat treatment may be patterned by a mold to form a concavo-convex pattern. Various patterns can be formed by embossing or nanoimprinting. Thereafter, the surface-inorganic hard coat film characterized by the curing of the ultraviolet curing compound and the SiO ₂ of the siloxane on the surface can be formed by ultraviolet irradiation while keeping the pattern.

In addition, a film can be formed by the transfer method by the same method. The composition of the present invention is coated on a film (for example, a polyester film) having been subjected to a release film treatment, and a film of a heat treatment step is formed. The film is used as a transfer film before ultraviolet irradiation. The film is transferred by the force of an adhesive or the like, and then irradiated with ultraviolet rays.

It can also be used as a transfer foil for in-mold molding. Since the thin film of the present invention is excellent in printing suitability (adhesion with ink), when the composition of the present invention is applied, various patterns are printed in an in-mold shape and then irradiated with ultraviolet rays, the pattern and the hard coat film are simultaneously Can be transferred to a molded article. And is useful as a hard coat film forming method for a molded article having a curved surface.

The thin film thus formed can be used as a gas barrier film, an antistatic film, a UV cut film, an antireflection film, etc. in addition to a hard coat film. Examples of application of the hard coat film include a glass, a headlight, an exterior part, an interior part, an electric part, a sunroof, a front case, a rear case, a battery case, a spectacle lens, A decorative sheet, a film, a television front panel, a CRT cover, and a video reflector.

Further, the thin film of the present invention can be used for a mold for producing a product such as the above, and therefore, the thin film is industrially applicable.

Claims (7)

a) a compound of formula (I)
R _n SiX _4-n (I)
(Wherein R represents a hydrocarbon group in which a carbon atom is directly bonded to Si or a hydrocarbon group containing an oxygen atom, a nitrogen atom or a silicon atom, and X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, and n represents 2, each R is the same or different and each X is the same or different when (4-n) is 2 or more), and a condensate of an organosilicon compound represented by
b) Polymer of UV curable compound
Inorganic composite thin film,
A polymer of the ultraviolet-curing compound in an amount of 60 to 98 mass%
(I) is formed on the surface of the film, and the concentration of carbon atoms at a depth of 10 nm from the surface is at least 20% or more than the concentration of carbon atoms at a depth of 100 nm from the surface And an O / Si source consumption of 2 nm depth from the surface of the film is 1.8 to 2.5. The method according to claim 1,
C) an organic-inorganic hybrid thin film containing a metal compound having a metal element selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. 3. The method according to claim 1 or 2,
Wherein the condensate of the compound wherein R in the formula (I) is a vinyl group is contained in an amount of 70% by mass or more of the total condensate of the organosilicon compound. 3. The method according to claim 1 or 2,
Wherein the Si / C source consumption at a depth of 100 nm from the surface is 0.2 or less. 3. The method according to claim 1 or 2,
Inorganic hybrid thin film characterized by further comprising a layer containing a hydrolyzed condensate of a metal surface active agent on the organic / inorganic hybrid thin film. 6. The method of claim 5,
Wherein the metal surface active agent is a silane coupling agent. a) a compound of formula (I)
R _n SiX _4-n (I)
(Wherein R represents a hydrocarbon group in which a carbon atom is directly bonded to Si or a hydrocarbon group containing an oxygen atom, a nitrogen atom or a silicon atom, and X represents a hydroxyl group or a hydrolysable group, n represents 1 or 2, and n represents 2, each R is the same or different and each X is the same or different when (4-n) is 2 or more), and a condensate of an organosilicon compound represented by
b) Polymer of UV curable compound
Wherein the organic / inorganic hybrid thin film contains 60 to 98% by mass of the polymerizable compound of the ultraviolet curable compound, and the plasma treatment or the UV ozone treatment is carried out.

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