WO2014010219A1 - Thin-film laminate having self-assembled monolayer - Google Patents

Abstract

The present invention addresses the problems of providing a primer layer having excellent adhesion to a substrate and being even more capable of forming a self-assembled monolayer/monomolecular film on a surface, and of providing a molded article having excellent functions such as hardness, solvent resistance, lubricity, slip properties, and low friction properties. This thin-film laminate is a thin-film laminate in which a first layer and a second layer are formed in this order on a substrate, wherein the first layer is an organic-inorganic composite thin film containing a) a condensate of an organic silicon compound represented by formula (I): R_nSiX_4-n (1) (In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, each R may be the same or different when n is 2, and each X may be the same or different when (4-n) is 2 or greater.), and b) a cured product of a thermosetting compound, and the second layer contains a self-assembling monolayer which is a hydrolysis condensate of a metal surfactant.

Description

Thin film laminate with self-assembled film

The present invention relates to a thin film laminate having a self-assembled film. This application claims priority to Japanese Patent Application No. 2012-154442 filed on July 10, 2012, the contents of which are incorporated herein by reference.

Conventionally, a method of forming a self-assembled film on the surface of a base material has been studied as a method for making the surface of metal, ceramic, glass, plastic, fiber, paper, wood, etc. water and oil repellent (patents). Reference 1). Since these films react with hydroxyl groups, imino groups, or carboxyl groups on the substrate surface and are chemically bonded to the substrate surface via —SiO— or —SiN <bond, When using a base material having a functional group, it was easy to form a self-assembled film on the base material. However, it has been difficult to form a self-assembled film on a substrate such as a resin or a metal that is difficult to oxidize.
Therefore, in Patent Document 2, a photocurable primer layer has been proposed as a primer layer of a fluorine-based monomolecular film or a thin film similar thereto. However, with this primer layer, it is difficult to form a dense self-assembled film or monomolecular film thereon, and it is difficult to impart sufficient hardness and solvent resistance to the substrate. It was. Further, since the primer layer is cured by irradiating ultraviolet rays or the like, it is difficult to apply it to a three-dimensional substrate.

JP-A-8-224536 JP 2001-270050 A

The present invention has been made in view of the above circumstances, is excellent in adhesiveness with a substrate, and provides a primer layer sufficient to form a self-assembled film / monomolecular film on the surface, hardness, It is an object to provide a molded article having excellent functions such as solvent resistance, lubricity, slipperiness, and low friction.

As a result of tackling the above problems and earnestly studying the present inventors, an organic-inorganic composite film containing a thermosetting compound and a polysiloxane compound is laminated on a substrate, and the surface of the organic-inorganic composite film is further plasma-treated. Or improve the mineralization by applying UV ozone treatment, and by forming a self-assembled film on it using a silane coupling agent, etc., on the substrate, together with hardness, solvent resistance, lubricity, slipperiness, It has been found that functions such as low friction and water / oil repellency can be imparted, and the present invention has been completed.

That is, the present invention
(1) In the thin film laminate formed in the order of the first layer and the second layer on the substrate,
The first layer is
a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) An organic-inorganic composite thin film containing a cured product of a thermosetting compound,
A thin film laminate, wherein the second layer is a layer containing a self-assembled film that is a hydrolysis condensate of a metal surfactant;
(2) The thin film stack according to (1), wherein the weight ratio of a) to b) in the first layer is 50:50 to 5:95, preferably 25:75 to 5:95 body,
(3) The thin film as described in (1) or (2), wherein the condensate of the compound in which R in the formula (I) is a vinyl group is contained in an amount of 55% by mass or more of the total condensate of the organosilicon compound. Laminate,
(4) The thin film laminate according to any one of (1) to (3), wherein the substrate is a resin, and (5) the metal-based surfactant is represented by the formula (II)
R ¹ _m MX ¹ _tm (II)
[Wherein, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a linking group. Represents a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group, and M represents a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom. Represents at least one metal atom selected from the group consisting of X ¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. m represents a positive integer from 1 to (t−1). When m is 2 or more, R ^{1 s} may be the same or different from each other. When (tm) is 2 or more, X ¹ may be the same or different, but at least one of X ¹ is a hydrolyzable group. The thin film laminate according to any one of (1) to (4), which is a compound represented by the formula:

The organic-inorganic composite thin film of the first layer of the present invention is characterized in that the surface of the film is almost completely mineralized while the base side of the film is rich in organic resin due to the thermosetting compound, It has excellent adhesion to the substrate and can impart physical strength and chemical, thermal and optical stability to the substrate. Furthermore, since a dense monomolecular film made of a hydrolytic condensate of a metal surfactant can be formed on the surface of the film, according to the present invention, hardness, solvent resistance, Functions such as thermal stability, light stability, lubricity, slipperiness, low friction, water repellency and oil repellency can be imparted.

It is a figure which shows distribution of each film | membrane component in the film thickness direction measured by ESCA about the thin film laminated body of Example 2. FIG. It is a figure which shows distribution of each film | membrane component in the film thickness direction measured by ESCA about the thin film laminated body of Example 3. FIG.

The thin film laminate of the present invention comprises a structure in which the following layers A), B) first layer, and C) second layer are laminated in the order of A), B), and C) on at least one surface of the substrate. It is a thin film laminate. The laminated body of the present invention may further include a case where one or more other layers are laminated as long as the effects of the present invention are exhibited.
A) Substrate B) First layer a) Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
b) an organic-inorganic composite thin film containing a cured product of a thermosetting compound,
C) Layer containing a self-assembled film which is a hydrolyzed condensate of the second layer metal surfactant.

(1) Substrate The substrate used in the present invention is not particularly limited as long as the laminate of the present invention can be formed, but a resin is particularly preferable. For example, polyamideimide, polyetherimide, polyimide, polyaminobismaleimide Polyimide resins such as polyethylene terephthalate, polyester resins such as polyethylene 2,6-naphthalate; Epoxy resins such as phenolic epoxy resins, alcoholic epoxy resins, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins; polyethers Polyether resins such as ether ketone, polyether ketone, polyether nitrile, and polyether sulfone; Cellulosic resins such as cellulose triacetate, cellulose diacetate, and nitrocellulose; polystyrene, Shinji Polystyrene resins such as tactic polystyrene; polyolefin resins such as homopolymers or copolymers of olefins such as ethylene, propylene and butene; cycloolefin resins such as norbornene resins; nylon 6, nylon 12, copolymer nylon Polyamide resins such as ethylene-polyvinyl alcohol copolymers; ethylene-tetrafluoroethylene copolymers, polytetrafluoroethylene ethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, Fluorine resins such as polyvinyl fluoride and perfluoroethylene-perfluoropropylene-perfluorovinyl ether copolymer; polycarbonate, polyvinyl butyrate resin, polyarylate resin and the like.

Further, as a resin, a resin composition made of an acrylic compound having a radical reactive unsaturated compound, a resin composition made of a mercapto compound having an acrylic compound and a thiol group, epoxy acrylate, urethane acrylate, polyester acrylate, poly A photocurable resin such as a resin composition in which an oligomer such as ether acrylate is dissolved in a polyfunctional acrylate monomer, a mixture thereof, or the like can be used.

The size and shape of the substrate are not particularly limited, and any flat plate, three-dimensional object, film, etc. can be used.

Further, various organic and / or inorganic additives may be added to the substrate for the purpose of imparting other functions. Furthermore, a coated article can also be used as a substrate.

The film-like substrate may be made of an unstretched film or may be made of a stretched film.
Examples of the resin substrate include a single layer film and a laminated film obtained by laminating two or more layers by means such as laminating or coating.

The film-like plastic substrate can be produced by a conventionally known general method. For example, a substrate made of an unstretched film that is substantially amorphous and not oriented can be produced by melting a material resin with an extruder, extruding it with an annular die or a T die, and quenching. In addition, a substrate made of an unstretched film is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular-type simultaneous biaxial stretching, or the like. A substrate made of a stretched film can be produced by stretching in a direction perpendicular to the flow direction of the substrate (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
The thickness of the film-like resin substrate is not particularly limited, but is usually 1 to 1000 μm, preferably 3 to 500 μm.

(2) First layer The organic-inorganic composite thin film that is the first layer of the present invention contains at least a condensate of an organosilicon compound and a thermosetting compound as essential components, but also contains a metal compound or the like. May be.

1) Condensate of organosilicon compound The organosilicon compound of the present invention is represented by the following formula (I).
R _n SiX _4-n (I)
In the formula, 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. n represents 1 or 2, and 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.

Here, examples of the “organic group in which a carbon atom is directly bonded to Si” represented by R include a hydrocarbon group which may be substituted, a group composed of a polymer of a hydrocarbon which may be substituted, and the like. Can do.
The hydrocarbon group in the above “optionally substituted hydrocarbon group” and “group consisting of an optionally substituted hydrocarbon polymer” is usually a hydrocarbon group having 1 to 30 carbon atoms, for example, , Alkyl group, cycloalkyl group, cycloalkylalkyl group, alkenyl group, alkynyl group, aryl group, arylalkyl group, arylalkenyl group and the like. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, and a carbon number of 3 are preferable. A cycloalkenyl group of ˜8.

The “hydrocarbon group” or “group consisting of a hydrocarbon polymer” 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, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl. Group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group and the like. Examples of the long chain alkyl group having more than 10 carbon atoms include lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

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

“Straight or branched alkenyl group having 2 to 10 carbon atoms” means a straight or branched alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more positions. For example, an ethenyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, a prop-1-en-2-yl group, a but-1-en-1-yl group, But-2-en-1-yl group, but-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-ene- 1-yl group, penta-4-en-1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-ene-1- Yl group, hexa-1-en-1-yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl group, hepta-6 En-1-yl group, oct-1-en-1-yl group, oct-7-en-1-yl group, buta-1,3-dien-1-yl group.

The “C3-C8 cycloalkenyl group” means a C3-C8 alkenyl group having a carbon-carbon double bond at any one or more positions and having a cyclic portion. And cyclopenten-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 alkynyl groups having 2 to 10 carbon atoms, such as ethynyl group, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1- In-1-yl group, but-3-in-1-yl group, penta-1-in-1-yl group, penta-4-in-1-yl group, hexa-1-in-1-yl group A hexa-5-in-1-yl group, a hepta-1-in-1-yl group, an octa-1-in-1-yl group, an octa-7-in-1-yl group, and the like.
Examples of the “cycloalkylalkyl group” include a group in which a cycloalkyl group having 3 to 8 carbon atoms and an alkyl group having 1 to 8 carbon atoms are bonded, and examples thereof include a cyclopropylmethyl group, a cyclopropylpropyl group, and cyclobutylmethyl. Group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylethyl group, cycloheptylmethyl group and the like.

Examples of the “aryl group” include aryl groups having 6 to 10 carbon atoms, such as phenyl group and naphthyl group.
Examples of the “arylalkyl group” include a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 8 carbon atoms are bonded, such as a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, Examples include 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like.
Examples of the “arylalkenyl group” include a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are bonded, such as a styryl group, 3-phenyl-prop-1-ene-1- Yl, 3-phenyl-prop-2-en-1-yl, 4-phenyl-but-1-en-1-yl, 4-phenyl-but-3-en-1-yl, 5- Phenyl-pent-1-en-1-yl group, 5-phenyl-pent-4-en-1-yl group, 8-phenyl-oct-1-en-1-yl group, 8-phenyl-oct-7 -En-1-yl group, naphthylethenyl group and the like.

Examples of the “hydrocarbon group having an oxygen atom” include a group having an oxirane ring (epoxy group) such as an alkoxyalkyl group, an epoxy group, an epoxyalkyl group, a glycidoxyalkyl group, an acryloxymethyl group, a methacryloxymethyl group, etc. Is mentioned.

Here, the “alkoxyalkyl group” is usually a group in which an alkoxy group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms are bonded, such as a methoxymethyl group, 2-methoxyethyl group, 3- And ethoxy-n-propyl group.
Here, the “epoxyalkyl group” is preferably a linear or branched epoxyalkyl group having 3 to 10 carbon atoms, such as a glycidyl group, a glycidylmethyl group, a 2-glycidylethyl group, a 3-glycidylpropyl group, a 4- An alkyl group containing a linear epoxy group such as a glycidylbutyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, or a 5,6-epoxyhexyl group;
β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, 2-glycidylpropyl group, 2-glycidylbutyl group, 3-glycidylbutyl group, 2-methyl-3-glycidylpropyl group, 3-methyl- 2-glycidylpropyl group, 3-methyl-3,4-epoxybutyl group, 3-ethyl-3,4-epoxybutyl group, 4-methyl-4,5-epoxypentyl group, 5-methyl-5,6- Examples thereof include an alkyl group containing a branched epoxy group such as an epoxy hexyl group.
Examples of the “glycidoxyalkyl group” include glycidoxymethyl group and glycidoxypropyl group.

As the “hydrocarbon group having a nitrogen atom”, a group having —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group or an aryl group, and each R ′ may be the same as or different from each other). Or a group having —N═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ may be the same as or different from each other). Examples of the aryl group include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.

For example, the group having —NR ′ ₂ includes a —CH ₂ —NH ₂ group, a —C ₃ H ₆ —NH ₂ group, a —CH ₂ —NH—CH ₃ group, and the like. -N = Examples of the group having a _{CR '' 2, -CH 2 -N} = CH-CH 3 _{group, -CH 2 -N = C (CH} 3) 2 _{group, -C 2 H 4 -N = CH} -CH ₃ groups etc. are mentioned.

Examples of the “hydrocarbon having a silicon atom” include groups containing a polymer such as polysiloxane, polyvinylsilane, polyacrylsilane and the like.

Examples of the above-mentioned “optionally substituted” substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a methacryloxy group. Examples of the alkyl group, alkenyl group, and aryl group are the same as those in R.

Among the above, a vinyl group, a group having an oxirane ring, —NR ′ ₂ (wherein R ′ represents a hydrogen atom, an alkyl group or an aryl group, and each R ′ may be the same as or different from each other). Or a group having —N═CR ″ ₂ (wherein R ″ represents a hydrogen atom or an alkyl group, and each R ″ may be the same as or different from each other) From the viewpoint of mineralization of the body surface, this is a preferred group.

In the formula (I) of the organosilicon compound, n represents 1 or 2, and n = 1 is particularly preferable. When n is 2, each R may be the same or different. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) in formula (I) is 2 or more, each X may be the same or different. A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group atom, an isocyanate group, and the like can be mentioned. An alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms Is preferred.

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, a t-butyloxy group, and the like. Examples of the acyloxy group (however, the carbon number does not include carbon of the carbonyl group) include an acetyloxy group and a benzoyloxy group. Examples of the halogen atom 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, and an aryl group. And an isocyanate group bonded to the alkyl group.

Specifically, the raw material organosilicon compounds include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethylsilane. Methoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, Dibutyldimethoxysilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxy Tanmethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl-3- Oxetanemethoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropi Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane. These can be used alone or in combination of two or more.

Examples of the organosilicon compound having a group composed of a hydrocarbon polymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl. (Meth) acrylate and other (meth) acrylic acid esters; (meth) acrylic acid, itaconic acid, fumaric acid and other carboxylic acids and maleic anhydride and other acid anhydrides; glycidyl (meth) acrylate and other epoxy compounds; diethylaminoethyl Amino compounds such as (meth) acrylate and aminoethyl vinyl ether; amino compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, and N-butoxymethyl (meth) acrylamide Compound: A compound in which a vinyl polymer obtained by copolymerizing a vinyl compound selected from acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate and the like is used as the R component of formula (I) can be mentioned. .
In addition, the condensate of the organosilicon compound used as the main component in the organic-inorganic composite thin film of the present invention means a product obtained by further condensing these organosilicon compounds and / or the condensate thereof.
The blending ratio of the organosilicon compound condensate is 2 to 98% by mass, preferably 5 to 50% by mass, more preferably 5 to 30% by mass, based on the solid content of the whole organic-inorganic composite thin film.

2) Cured product of thermosetting compound The thermosetting compound of the present invention is not particularly limited as long as it is a compound having a functional group capable of thermosetting, and it may be a thermosetting resin or a thermosetting low molecular compound. Good.
Examples of the thermosetting resin include phenolic novolac resins, cresol novolac resins, novolac type phenol resins such as bisphenol A novolac resins, phenol resins such as resol type phenol resins; bisphenol types such as bisphenol A epoxy resins and bisphenol F epoxy resins. Epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, etc. novolac epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, Epoxy resins such as dicyclopentadiene-modified phenolic epoxy resins, and epoxies such as 2,2-bis (4-glycidyloxyphenyl) propane Compounds having the like. In addition, urea (urea) resin; resin having triazine ring such as melamine resin; unsaturated polyester resin; bismaleimide resin; polyurethane resin; diallyl phthalate resin; silicone resin; resin having benzoxazine ring; The raw material compound of these resin is mentioned, Among these, the 1 type (s) or 2 or more types of mixture can be used.

Examples of the thermosetting low molecular compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. Bifunctional (meth) acrylate compounds such as bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tri (meth) acrylate Reaction product with acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone modified dipenta Erythritol hexa (meth) acrylate, ethylene oxide modified pentaerythritol tetra (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, propylene oxide modified dipentaerythritol penta ( Trifunctional such as (meth) acrylate, propylene oxide modified dipentaerythritol hexa (meth) acrylate Polyfunctional (meth) acrylate compounds above: polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate di Examples include acrylate compounds such as acrylate and siloxane polymers having a (meth) acryloyloxy group, and one or a mixture of two or more of these can be used.

The amount of the cured product of the thermosetting compound in the organic-inorganic composite thin film of the present invention is the solid content of the whole organic-inorganic composite thin film (condensate of organosilicon compound, cured product of thermosetting compound, and blended as necessary. 2 to 98% by mass, preferably 50 to 95% by mass, more preferably 70 to 95% by mass, based on the total mass of other components to be produced.
In the organic-inorganic composite thin film of the present invention, the blending ratio of the condensate of the organosilicon compound and the cured product of the thermosetting compound is preferably 50:50 to 5:95, more preferably 25: 75-5: 95.

3) Thermal polymerization initiator or curing agent In the present invention, if necessary, a thermal polymerization initiator can be added.
The thermal polymerization initiator refers to a compound that generates radicals upon heating, and examples thereof include organic peroxides, azo compounds, and redox initiators.
Examples of the organic peroxide include benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, t-butyl hydroperoxide and dicumyl peroxide, acetyl peroxide, lauroyl peroxide, cyclohexanone peroxide, dibenzoyl Peroxides, peroxides such as tert-butylpermaleate; peroxycarbonates such as 1,6bis (t-butylperoxycarbonyloxy) hexane; peroxyketals; potassium persulfate, sodium persulfate, ammonium persulfate, etc. Examples include persulfates.

Examples of the azo compound include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, and 2,2′-azo. Bisisobutane, 2,2′-azobisisobutyramide, 2,2′-azobisisobutyronitrile (AIBN), methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2 2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 2,2′- Azobis-2-methylvaleronitrile, dimethyl 4,4′-azobis-4-cyanovalerate, 2,2′-azobis-2,4-dimethylvaleronitrile and the like can be mentioned.

Examples of the redox initiator include a combination of hydrogen peroxide-iron (II) salt, organic oxide-dimethylaniline, cerium (IV) salt-alcohol, and the like.

The blending amount of the polymerization initiator used in the present invention is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the solid content of the polymer.

In the present invention, a curing agent or a curing accelerator can be added if necessary when using an epoxy resin or the like.
Curing agents include amine, imidazole, amide, ester, alcohol, thiol, ether, thioether, phenol, phosphorus, urea, thiourea, acid anhydride, and Lewis acid. Onium salt type, active silicon compound-aluminum complex type, etc., but there is no particular limitation, and any one of those conventionally used as curing agents and curing accelerators such as conventional epoxy resins can be selected. Can be used.

Examples of amine compounds include aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, and modified amines. For example, aliphatic amines: ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, Pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ′, N ′ -Tetramethylhexamethylenediamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylethylenediamine, N, N-dimethylsilane Alicyclic and heterocyclic amines such as rohexylamine, dimethylaminoethoxyethoxyethanol, dimethylaminohexanol: piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ', N "-tris ( Dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethyl Aromatic amines such as piperazine, bis (4-aminocyclohexyl) methane, N, N′-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) undecene-7: o-phenylenediamine, m-phenylenediamine, p-Phenylenedia , Diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline and other modified polyamines: epoxy compound-added polyamine, Michael-added polyamine, Mannich-added polyamine, thiourea-added polyamine, ketone blockade Other amines such as polyamines include dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, and the like.

Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2- Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl- -Methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ′)]-Ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl-)-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl- 4-imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenyl Imidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazo 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazo Examples include lithium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

Examples of imidazoline compounds include 2-methylimidazoline and 2-phenylimidazoline.

Examples of the amide compounds include polyamides obtained by condensation of dimer acids and polyamines, and examples of the ester compounds include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids. Further, phenol, alcohol-based, thiol-based, ether-based and thioether-based compounds include phenol novolak, cresol novolak, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4,6-tris ( And dimethylaminomethyl) phenol and 2,4-6-tris (dimethylaminomethyl) phenol tri-2-ethylhexyl hydrochloride.
Examples of urea-based, thiourea-based, and Lewis acid-based curing agents include butylated urea, butylated melamine, butylated thiourea, and boron trifluoride.

Examples of phosphorus curing agents include organic phosphine compounds, for example, alkylphosphines such as ethylphosphine and butylphosphine, first phosphines such as phenylphosphine, dialkylphosphines such as dimethylphosphine and dipropylphosphine, diphenylphosphine, and methylethylphosphine. Secondary phosphine, trimethylphosphine, triethylphosphine, and the like. Examples of acid anhydride curing agents include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydroanhydride. Phthalic acid, Endomethylenetetrahydrophthalic anhydride, Methylendomethylenetetrahydrophthalic anhydride, Maleic anhydride, Tetramethylene maleic anhydride, Trimellitic anhydride, Chlorendic anhydride, None Pyromellitic acid, dodecenyl succinic anhydride, anhydrous benzophenone tetracarboxylic acid, ethylene glycol bis (anhydrotrimellitate), methylcyclohexene tetracarboxylic anhydride, polyazelaic acid anhydride, and the like.

Curing agents for onium salts and active silicon compounds-aluminum complexes include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, silyl peroxide-aluminum complexes. And triphenylsilanol-tris (salicylaldehyde) aluminum complex.
The content of the curing agent 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 polymer.

4) Metal compound The metal compound of the present invention is contained for adjusting the refractive index, strengthening the affinity with the second layer, maintaining the shape, and adjusting the hardness. Titanium, zirconium, aluminum, tin, lead, tantalum or A metal compound containing at least one element composed of silicon is preferable, titanium, zirconium, aluminum, and tin are more preferable, and titanium is particularly preferable. These may be used alone or in combination of two or more.
The metal compound is at least one compound selected from the group consisting of metal chelate compounds, organic acid metal salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. Etc. A metal compound can be used individually by 1 type or in combination of 2 or more types. In particular, it is preferably a metal chelate compound, an organic acid metal salt, a hydrolyzate and / or condensate of a metal compound having two or more hydroxyl groups or hydrolyzable groups. Or a condensate is preferable.
Examples of the metal compound in the thin film include those existing as a raw material compound, those obtained by further condensing the compound, and those chemically bonded to the above-described organosilicon compound.

The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. The metal chelate compound is preferably a β-ketocarbonyl compound, a β-ketoester compound, or an α-hydroxyester compound. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetate β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; compounds coordinated with hydroxycarboxylic acids such as glycolic acid and lactic acid Can be mentioned.

The organic acid metal salt is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfonic acid, sulfinic acid, thiophenol, and the like. Organic compounds exhibiting acidity such as phenolic compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides;

The metal compound having two or more hydroxyl groups or hydrolyzable groups is other than the metal chelate compound and the organic acid metal salt, such as hydroxide, propoxide, isopropoxide, butoxide and the like. Examples thereof include metal alcoholates.

Examples of the hydrolyzable group in the metal compound, the metal chelate compound, or the organic acid metal salt include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and include an alkoxy group having 1 to 4 carbon atoms and a carbon number. 1-4 acyloxy groups are preferred. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.

As a hydrolyzate and / or condensate of a metal compound, one obtained by hydrolyzing 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is more preferable that it is hydrolyzed with 0.5 to 2 mol of water.

The hydrolyzate and / or condensate of the metal chelate compound is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal chelate compound. More preferably, it is hydrolyzed with water.

In addition, the hydrolyzate and / or condensate of the organic acid metal salt is preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt. More preferably, it is hydrolyzed with molar water.
The above metal compound also has a function as a silanol condensation catalyst.

Furthermore, examples of the metal compound for improving the hardness include tetrafunctional silane and colloidal silica.
Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) acryloxysilane, tetrakis [2 -(Meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane be able to. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.
The compounding ratio of the metal compound is 0 to 50% by mass with respect to the solid content of the whole organic-inorganic composite thin film.

5) Other additives In addition, in order to develop various properties such as coloring prevention of the first layer, thickening, prevention of UV transmission to the base, provision of corrosion resistance, heat resistance, etc. It is also possible to disperse. Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate and fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of this filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, carbonic acid Magnesium, Barium sulfate, Bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bituminous, Rock ultramarine, Cobalt blue, Cerulean Blue, copper borate, molybdenum blue, copper sulfide, koval Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, sulfuric acid Examples thereof include lead, graphite, bone black, diamond black, thermostatic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

In addition, known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling agents, etc. These additives can also be added.

6) Manufacturing method of organic / inorganic composite thin film 6-1) Preparation of organic / inorganic composite thin film forming solution The organic / inorganic composite thin film forming solution in the present invention may be appropriately polymerized in addition to the organic silicon compound and the thermosetting compound. It is prepared by mixing an initiator, a metal compound, a silanol condensation catalyst, water and / or a solvent.
In addition, when using the metal compound which functions also as a silanol catalyst as a metal compound of this invention, it is not necessary to use a silanol catalyst.

Specifically, for example, when using a metal compound as a silanol catalyst, the metal compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added. (Partial) Hydrolyze. On the other hand, a thermosetting compound is dissolved in a solvent, a thermal polymerization initiator or a curing agent is added as necessary, and then both solutions are mixed. These four components can be mixed at the same time, and the method of mixing the organosilicon compound and the metal compound, after mixing the organosilicon compound and the metal compound, adding water (partially), A method of mixing separately (partially) hydrolyzed organosilicon compounds and metal compounds can be mentioned. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 0.5 with respect to 1 mol of the metal compound. It is preferable to use at least mol of water, and more preferably 0.5 to 2 mol of water. When the metal compound is a metal chelate compound or an organic acid metal salt, it is preferable to use 5 to 100 mol of water with respect to 1 mol of the metal chelate compound or organic acid metal salt, and 5 to 20 mol of water is used. It is more preferable.

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

The composition for forming an organic-inorganic composite thin film in the present invention preferably contains water and / or a solvent in addition to the above components.
The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, 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; dimethyl sulfoxide And the like; alcohols such as methanol and ethanol; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents can be used alone or in combination of two or more.

Examples of the silanol condensation catalyst include acids and bases in addition to the metal compounds.
Examples of the acid include organic acids and mineral acids. Specific examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. Examples of the mineral acid include hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, and the like.
Here, a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like are also included.
Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines, carboxylic acid neutralized salts of organic amines, quaternary ammonium salts and the like.

The solid content (organic silicon compound and / or condensate thereof, raw material of organic polymer compound, etc.) in the solution for forming an organic-inorganic composite thin film in the present invention is 1 to 98% by mass, 10 to 60% by mass. It is preferably 15 to 45% by mass.
Organosilicon compound and / or its condensate, thermosetting compound, metal compound with respect to the total mass of the solid content (organosilicon compound and / or its condensate, thermosetting compound, etc.) in the organic / inorganic composite thin film forming solution The compounding amounts of the metal oxide particles, the thermal polymerization initiator and the like are the same as the content in the organic-inorganic composite film.

6-2) Method for producing organic-inorganic composite thin film The organic-inorganic composite thin film of the present invention comprises (A) a step of applying the above-mentioned organic-inorganic composite thin film-forming solution onto a substrate, drying and / or heating, (B) It can be manufactured through a step of performing plasma treatment or UV ozone treatment.

The organic-inorganic composite thin film of the present invention is a film in which the concentration of carbon atoms at a depth of 10 nm from the surface measured by ESCA analysis is 20% or less less than the concentration of carbon atoms at a depth of 100 nm from the surface. preferable.
Here, the “carbon atom concentration” means the molar concentration of carbon atoms when (total metal atom + oxygen atom + carbon atom) is 100%. The same applies to the concentrations of other elements.
In addition, the “layer in which the condensate of the organosilicon compound is concentrated” is defined by the concentration of carbon atoms by ESCA analysis, but the concentration in the concentrated layer is also high in the silicon concentration.

In the present invention, the lower the carbon concentration, the higher the silicon concentration.
Note that in this specification, the value of the film thickness used when defining the carbon content in the thin film is a value calculated when sputter etching is performed in ESCA analysis, but the actual film thickness value is not necessarily the same. It does not match. This is because the film thickness etched by sputter etching depends on the material of the film. Therefore, the actual film thickness value can be obtained by converting the etching rate for each film material.
In the ESCA analysis in this specification, a SiO ₂ equivalent film thickness using a thermally oxidized SiO ₂ film as a standard sample was used. The standard sample is a thermally oxidized SiO ₂ film formed on a silicon wafer. An etching rate was calculated by ESCA analysis of a standard sample whose thickness was previously measured by an ellipsometer while performing sputter etching.

When the organosilicon compound represented by the formula (I) contains a condensate of a compound in which R is a vinyl group in an amount of 55% by mass or more, preferably 70% by mass or more, based on the total condensate of the organosilicon compound, the surface is particularly inorganic. The organic / inorganic composite thin film of the present invention can be easily produced.

As a coating method of the organic / inorganic composite thin film forming solution, a known coating method can be used. For example, dipping method, spray method, bar coating method, roll coating method, spin coating method, curtain coating method, gravure printing method. , Silk screen method, ink jet method and the like. Further, the film thickness to be formed is not particularly limited and is, for example, about 0.1 to 200 μm.

The drying / heating treatment of the film formed by applying the organic / inorganic composite thin film forming solution is preferably performed, for example, at 40 to 200 ° C. for about 0.5 to 120 minutes, and at 60 to 160 ° C. for 1 to 1 minute. More preferably, it is performed for about 60 minutes, more preferably for about 1 to 60 minutes at 60 to 120 ° C.

When a thin film after heating is formed on a glass substrate, the pencil hardness specified in the JIS K 5600-5-4 pencil method is about 1H to 4H, and 2H to 4H in terms of adhesion to the substrate and hardness. It is preferable that

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 plasma by applying a high voltage at a high frequency between parallel plate electrodes in which at least one of the electrode pairs is coated with a dielectric, and holding a base material layer between the electrodes, Or the method of moving this base material layer between these electrodes is mentioned. Plasma processing includes atmospheric pressure plasma processing and vacuum plasma processing, but since the density of active species is higher in atmospheric pressure plasma processing than in vacuum plasma processing, electrode surfaces can be processed at high speed and high efficiency. In addition, since there is no need to use a vacuum during processing, there is an advantage that processing can be performed with a small number of steps.

Atmospheric pressure plasma treatment is performed using an atmospheric pressure plasma generator (for example, atmospheric pressure plasma apparatus S-5000 manufactured by Sakai Semiconductor Co., Ltd., atmospheric pressure plasma surface treatment apparatus RD series manufactured by Sekisui Chemical Co., Ltd.). It can be carried out.

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

The UV light source is not particularly limited as long as oxygen can be changed to ozone by UV irradiation. Examples of the UV light source include a low-pressure mercury lamp. Low pressure mercury lamps generate UV light at 185 nm and 254 nm, and the 185 nm line can convert oxygen to ozone. The illuminance upon irradiation varies depending on the light source used, but generally several tens to several hundreds mW / cm ² are used. Moreover, illumination intensity can be changed by condensing or diffusing. The irradiation time varies depending on the illuminance of the lamp and the type of the untreated layer, but is usually 1 minute to 24 hours. The treatment temperature is usually 10 to 200 ° C. The irradiation amount of UV (i.e., ultraviolet amount) is usually 1000 mJ / cm ² or more, preferably 1000 ~ 100000mJ / cm ^2, more preferably 1000 ~ 30000mJ / cm ^2.

In the organic-inorganic composite thin film according to the present invention, the carbon atom content in the film surface portion is compared with the carbon atom content in the inside of the film (near the joint with the base material) through the heating step (A). Therefore, a concentrated layer of silane compounds is formed on the film surface.
Therefore, even if the plasma treatment and UV ozone treatment in the step (B) are performed, only the silane compound on the film surface reacts and the organic polymer compound in the film is hardly affected.
Instead of plasma treatment and UV ozone treatment, alkaline aqueous solution treatment, hydrogen peroxide solution treatment, and sodium metasilicate aqueous solution treatment may be performed.

(3) Second layer
A layer containing a self-assembled film that is a hydrolyzed condensate of a metal surfactant Further, in the present invention, on the outside of the organic-inorganic composite thin film, a self-assembled that is a hydrolyzed condensate of a metal surfactant. A layer containing a film is provided. The self-assembled film is preferably a monomolecular film.
Here, the self-assembled film means a film formed with an ordered structure without external forcing. The molecule forming the self-assembled film is obtained from the metal surfactant used for preparing the solution for forming the self-assembled film. The molecules of the metal-based surfactant are not solvated by the solvent alone in the self-assembled film forming solution, but some of them gather together to form an aggregate.

The form of the aggregate is a form in which molecules are assembled by hydrophobic forces or hydrophilic parts by intermolecular force, coordination bond, hydrogen bond, etc .; the molecules forming the membrane are bonded by covalent bonds Aggregated form; Form in which other medium such as water forms micelles or the like as a nucleus or mediation; or form in which these are combined;

Below, the preparation methods of the layer containing the hydrolysis-condensation product of a metal surfactant are demonstrated.
The layer containing the hydrolytic condensate of the metal surfactant is, for example, “at least as described in WO03 / 076064, WO2004 / 091810, WO2006 / 009292, WO2009 / 104424, WO2008 / 059840, etc. Produced by bringing the organic-inorganic composite thin film into contact with an organic solvent solution containing “a metal-based surfactant having one or more hydrolyzable groups”, “a compound capable of interacting with the metal-based surfactant” and water. can do. An organic solvent solution containing “a metal surfactant having at least one hydrolyzable group”, “a compound capable of interacting with the metal surfactant” and water is commercially available, for example, Japan SAMLAY (registered trademark) manufactured by Soda Co., Ltd. can be used.

Examples of the “metal surfactant having at least one hydrolyzable group” include formula (II)
R ¹ _m MX ¹ _tm (II)
[Wherein, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a linking group. Represents a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group, and M represents a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom. Represents at least one metal atom selected from the group consisting of X ¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. m represents a positive integer from 1 to (t−1). When m is 2 or more, R ^{1 s} may be the same or different from each other. When (tm) is 2 or more, X ¹ may be the same or different, but at least one of X ¹ is a hydrolyzable group. ] The metal-type surfactant shown by these is preferable.
In the formula (II), the hydrocarbon group of the hydrocarbon group having 1 to 30 carbon atoms which may have a substituent is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, alkyl groups such as n-decyl group and n-octadecyl group; alkenyl groups such as vinyl group, propenyl group, butenyl group, pentenyl group, n-decynyl group and n-octadecynyl group; phenyl group, 1-naphthyl group, 2- An aryl group such as a naphthyl group is exemplified.

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 and a halogenated alkenyl group having 1 to 30 carbon atoms. And a halogenated aryl group having 1 to 30 carbon atoms. Among these, a group in which two or more hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are substituted with a halogen atom is preferable, and two or more hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are fluorine atoms. A fluorinated alkyl group substituted with is more preferable. Further, when the fluorinated alkyl group has a branched structure, the branched portion is preferably a short chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

Specific examples of the hydrocarbon group of the hydrocarbon group containing a linking group and the halogenated hydrocarbon group of a halogenated hydrocarbon group containing a linking group include the hydrocarbon groups that may have the above-mentioned substituents. The thing similar to what was mentioned as a halogenated hydrocarbon group of the halogenated hydrocarbon group which may have a hydrogen group and a substituent is mentioned.
The linking group is preferably present between carbon-carbon bonds of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of the hydrocarbon group and a metal atom M described later.
Specific examples of the linking group include —O—, —S—, —SO ₂ —, —CO—, —C (═O) O— or —C (═O) NR ⁵¹ — (wherein R ⁵¹ represents A hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group;
Among these, from the viewpoint of water repellency and durability, an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group containing a linking group is preferable.

X ¹ represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. For example, an optionally substituted alkoxy group having 1 to 6 carbon atoms; an optionally substituted acyloxy group; a halogen atom such as a fluorine atom, chlorine atom, bromine atom or iodine atom; an isocyanate group Cyano group; amino group; or amide group.
Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, and n-to A xyloxy group etc. are mentioned. 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 these substituents include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group. Among these, 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 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, a silicon atom is preferable from the viewpoint of availability of raw materials and reactivity.

Examples of the metal surfactant represented by the above formula (II) include 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.

CH ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₃ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₇ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₉ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₂₁ Si (OCH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₇ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ (CH ₂ ) ₁₇ SiCl ₃ , CH ₃ (CH ₂ ) ₉ Si (OCH ₂ CH ₃ ) ₃ , CH ₃ (CH ₂ ) ₉ SiCl ₃ , _{CH 3 (CH 2) 9 Si} (CH 3) (OCH 2 CH 3) 2, CH 3 (CH 2) 9 Si (CH 3) (OCH 3) 2, CH 3 CH 2 O (CH 2) 15 Si ( OC _{3) 3, CH 3 (CH} 2) 2 Si (CH 3) 2 (CH 2) 15 Si (OCH 3) 3, CH 3 (CH 2) 6 Si (CH 3) 2 (CH 2) 9 Si (OCH _{3) 3, CH 3 COO (} CH 2) 15 Si (OCH 3) 3, CH 3 CH 2 O (CH 2) 15 Si (OC 2 H 5) 3, CH 3 (CH 2) 2 Si (CH 3) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ , CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃ , CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃ ,

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂ , CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂ , CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) (OH) ₂ , CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂ , CH ₃ CH ₂ O ( _{CH 2) 15 Si (OC 2} H 5) (OH) 2, CH 3 (CH 2) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) (OH) 2, CH 3 (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) (OH) ₂ , CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) (OH) ₂ ,

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH), CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH), CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₂ (OH), CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH), CH ₃ CH ₂ O ( _{CH 2) 15 Si (OC 2} H 5) 2 (OH), CH 3 (CH 2) 2 Si (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 2 (OH), CH 3 (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₂ (OH), CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH),

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃ , CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OH) ₃ , CH ₃ (CH ₂ ) ₆ Si (CH _{3) 2 (CH 2) 9} Si (OH) 3, CH 3 COO (CH 2) 15 Si (OH) 3, CH 3 CH 2 O (CH 2) 15 Si (OH) 3, CH 3 (CH 2) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OH) ₃ , CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OH) ₃ , CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃ , CH ₃ (CH ₂ ) ₉ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₀ Si (NCO) ₃ , CH ₃ (CH ₂ ) ₁₁ Si (NCO) _{3 and the} like.
Moreover, these compounds can be used individually by 1 type or in combination of 2 or more types.

Examples of the “compound capable of interacting with a metal-based surfactant” include metal oxides; metal hydroxides; metal alkoxides; metal alkoxides partial hydrolysis products; metal alkoxides hydrolysis products; A coordinated metal compound; at least one selected from other silanol condensation catalysts is used.

Specific examples of metal oxides include methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, and XBA-ST. And PMA-ST (all of which represent the trade names of organosilica sol manufactured by Nissan Chemical Industries, Ltd.).

As the metal hydroxide, any metal hydroxide may be used as long as it is a metal hydroxide. As a manufacturing method of a metal hydroxide, the method of hydrolyzing the below-mentioned metal alkoxide, the method of making a metal salt react with a metal hydroxide, etc. are mentioned. Moreover, what is marketed as a metal hydroxide can also be refine | purified and used if desired.

Examples of metal alkoxides include silicon alkoxides such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ -i) ₄ , Si (OC ₄ H ₉ -t) ₄ ; Ti ( Titanium alkoxides such as OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₃ H ₇ -i) ₄ , Ti (OC ₄ H ₉ ) ₄ ; Ti [OSi (CH ₃ ) ₃ ] ₄ , Ti Tetrakistrialkylsiloxytitanium such as [OSi (C ₂ H ₅ ) ₃ ] ₄ ; Zr (OCH ₃ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ zirconium such _{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 aluminum alkoxide; Ge (OC H _{5) 4} and the like of germanium _{alkoxide; In (OCH 3) 3,} In (OC 2 H 5) 3, In (OC 3 H 7 -i) 3, In (OC 4 H 9) 3 , etc. of indium alkoxides; Sn Tin alkoxides such as (OCH ₃ ) ₄ , Sn (OC ₂ H ₅ ) ₄ , Sn (OC ₃ H ₇ -i) ₄ , Sn (OC ₄ H ₉ ) ₄ ; Ta (OCH ₃ ) ₅ , Ta (OC ₂ Tantalum alkoxides such as H ₅ ) ₅ , Ta (OC ₃ H ₇ -i) ₅ , Ta (OC ₄ H ₉ ) ₅ ; W (OCH ₃ ) ₆ , W (OC ₂ H ₅ ) ₆ , W (OC ₃ H _7- i) tungsten alkoxides such as ₆ and W (OC ₄ H ₉ ) ₆ ; zinc alkoxides such as Zn (OC ₂ H ₅ ) ₂ ; lead alkoxides such as Pb (OC ₄ H ₉ ) ₄ ; These metal alkoxides can be used alone or in combination of two or more.

The metal alkoxide partial hydrolysis product is obtained before the metal alkoxide is completely hydrolyzed, and examples thereof include a metal oxide sol precursor or an oligomer present in the state of oligomer. Can do.
Specifically, the metal alkoxide partial hydrolysis product is stably dispersed without aggregation in an organic solvent in the absence of at least one selected from the group consisting of acids, bases and dispersion stabilizers. Preferred examples include dispersoids having the above properties. In this case, the dispersoid refers to fine particles dispersed in the dispersion system, and specific examples include colloidal particles. Here, the state of stable dispersion without agglomeration means that in the absence of acid, base and / or dispersion stabilizer in the organic solvent, the dispersoid of the hydrolysis product coagulates and becomes heterogeneous. The state which is not isolate | separated is said, Preferably the transparent and homogeneous state is said. Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is organic. This is a state in which the transmittance is preferably 80 to 100%, expressed as a spectral transmittance measured under the condition of using a solvent and a light wavelength of 550 nm. The particle size of the dispersoid of the hydrolysis product is not particularly limited, but is preferably in the range of 1 to 100 nm and more preferably in the range of 1 to 50 nm in order to obtain a high visible light transmittance. More preferably, it is in the range of 1 to 10 nm.
As a method for producing a partial hydrolysis product of a metal alkoxide, an organic solvent is used in the absence of an acid, a base, and / or a dispersion stabilizer in an amount of 0.5 to 2.0 with respect to the metal alkoxide exemplified above. A preferred example is a method of hydrolyzing in an organic solvent reflux temperature range from −100 ° C. using less than double moles of water.

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 alkoxides. Even if the hydrolysis product is obtained by hydrolyzing a metal alkoxide with water at least twice as much as the metal alkoxide, the metal alkoxide is less than twice the equivalent of the metal alkoxide. The partial hydrolysis product of the metal alkoxides was obtained by partial hydrolysis with water, and the partial hydrolysis product was further mixed with a predetermined amount of water (the amount of water used in the previous partial hydrolysis and In a total amount of 2 times the equivalent of metal alkoxides).

The chelated or coordinated metal compound can be prepared by adding a chelating agent or a coordination compound capable of forming a complex with the metal of the metal compound to a solution of the metal compound. As a chelating agent or coordination compound, a metal hydroxide, metal alkoxide, or metal alkoxide is chelated or coordinated to the metal of the hydrolysis product obtained by treating with water to form a complex. If it can do, it will not specifically limit.
Chelating agents or coordination compounds include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid; oxalic acid, malonic acid, succinic acid, glutaric acid Saturated aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, array acid, maleic acid; benzoic acid, toluic acid, Aromatic carboxylic acids such as phthalic acid; halogenocarboxylic acids such as chloroacetic acid and trifluoroacetic acid; β-diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; β-ketoesters such as methyl acetoacetate and ethyl acetoacetate; Tetrahydrofuran, furan, furancarboxylic acid, thi And heterocyclic compounds such as offene, thiophenecarboxylic acid, pyridine, nicotinic acid, and isonicotinic acid. These can be used alone or in combination of two or more.

Examples of other silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanic acid esters and titanic acid ester chelates, and acid catalysts.
Specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyllaurate , Titanium tetraethoxide, titanium tetrabutoxide, titanium tetraisopropoxide, titanium bis (acetylacetonyl) dipropoxide, etc. .

Examples of the acid catalyst include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borofluoric acid, and organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. In addition, photoacid generators that generate an acid upon irradiation with light, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like can be exemplified.

The content of water in an organic solvent solution containing a metal surfactant having at least one hydrolyzable group, a compound capable of interacting with the metal surfactant, and water is preferably 10 ppm to 2000 ppm.

In order to provide a layer containing a hydrolytic condensate of a metal surfactant on an organic-inorganic composite thin film having an organic-inorganic composite thin film, the above organic solvent solution is prepared by dipping, spin coating, spraying, roller coating, It can be carried out by contacting the organic-inorganic composite thin film on the organic-inorganic composite thin film by a method such as the Mayer bar method, screen printing, brush coating method, etc., preferably by a dip method.

Examples of the present invention are shown below, but the technical scope of the present invention is not limited thereto.
[Example 1]
1-1. Preparation of polysiloxane solution [A-1] To 15.0 g of diisopropoxybisacetylacetonate titanium, 28.93 g of vinyltrimethoxysilane which is an organosilicon compound and 3-methacryloxypropyltrimethoxysilane 20. 78 g was added and stirred for about 1 minute. Next, 36.71 g of MEK was added so that the solid content in [A-1] was 30 wt%, and then 1.5 times mol of pure component (Ti + Si) mol in [A-1] was added. 8.38 g of water was added. This solution was stirred at room temperature for 2 hours for hydrolysis. After completion of the reaction, the reaction solution was allowed to stand until the temperature of the reaction solution reached about room temperature to obtain 109.80 g of a polysiloxane solution [A-1] having a solid content of 30 wt%.
* Vinyltrimethoxysilane (KBM-1003, Shin-Etsu Chemical Co., Ltd.)
* 3-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical KBM-503)
* Diisopropoxybisacetylacetonate titanium (Nippon Soda Co., Ltd. T-50, TiO ₂ equivalent solid content: 16.5 wt%)
* Methyl ethyl ketone (MEK) Wako Pure Chemical Industries, Ltd.

1-2. Preparation of organic / inorganic composite thin film forming solution [A-2]
YD-128: Weigh 15.50 g of YD-128 and 12.92 g of polysiloxane solution [A-1] so that the polysiloxane solution [A-1] = 80 wt%: 20 wt% (solid content ratio). did. Next, 20.96 g of MEK was added and mixed so that the solid content concentration in the organic-inorganic composite thin film forming solution [A-2] was 40 wt%. To this mixed solution, 0.62 g of 4-ethyl-4-methylimidazole of 4 wt% based on the solid content of YD-128 was added and stirred at room temperature for about 1 hour. 50.0 g of an organic-inorganic composite thin film forming solution [A-2] having a solid content concentration of 40 wt% was obtained.
* YD-128 (Nippon Steel Chemical, BPA type epoxy resin)
* 2-Ethyl-4-methylimidazole (Shikoku Chemicals Co., Ltd.)
* Solvent: Methyl ethyl ketone (MEK), Methyl isobutyl ketone (MIBK), Toluene, etc. (all Wako Pure Chemical Industries, Ltd.)

1-3. Dip coating is formed on the silicon wafer and iron material so that the thickness is 0.6 μm or more, and is heated at 130 to 150 ° C. for 5 to 10 minutes with a hot air circulating dryer to form a coating film. .

1-4. Formation of self-assembled monolayer (SAM) The coating film obtained in 1-3 above is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (Iwasaki Electric Co., Ltd.), It was immersed in the SAM forming solution for 10 minutes. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.
* SAM formation solution: SAMLAY (registered trademark) Nippon Soda Co., Ltd. Octadecyltrimethoxysilane

[Comparative Example 1]
The silicon wafer and the iron material were subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (manufactured by Iwasaki Electric Co., Ltd.) and immersed in the SAM forming solution for 10 minutes. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.

[Comparative Example 2]
YD-128 (Nippon Steel Chemical Co., Ltd., BPA type epoxy resin) is diluted with methyl ethyl ketone (MEK) so that the solid content is 30 wt%, and 4 wt% of 2-ethyl is added to the solid content of YD-128. Using a solution to which -4-methylimidazole was added, a Dip coat film was formed on the iron material so that the thickness became 0.6 μm or more, and heated at 130 to 150 ° C. for 5 to 10 minutes with a hot air circulation dryer, A coating film was formed.
The obtained coating film is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (manufactured by Iwasaki Electric Co., Ltd.) and then placed in a SAM forming solution (SAMLAY (registered trademark) Nippon Soda Co., Ltd.) for 10 minutes. Soaked. After pulling up from the SAM liquid, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes in a hot air circulating dryer.

[Evaluation test]
Example 1 and Comparative Examples 1 and 2 were evaluated. The measurement method is as follows. The results are shown in Table 1. However, Example 1 used what was laminated | stacked on the iron material.

1) Liquid repellency (static contact angle measurement):
After 2 μl of water or 7 μl of tetradecane (hereinafter abbreviated as “TD”) is dropped from the microsyringe onto the surface of each sample, the contact angle is measured using Drop Master 700 (manufactured by Kyowa Interface Science Co., Ltd.) 60 seconds later. did.
2) Falling angle:
At the room temperature, the tilt angle of the deposition substrate was changed, and the drop start angle of the droplet was measured. Water was used as the liquid, and the applied amount was 30 μl.
3) Hysteresis (expansion contraction method):
The dynamic contact angle of the thin film was measured using Drop Master 700 (manufactured by Kyowa Interface Science Co., Ltd.) using butyl carbitol acetate as droplets. The measurement of the dynamic contact angle is a method performed based on the difference Δ between the advancing angle θa and the receding angle θr of the droplet, and is described in detail in Japanese Patent Application Laid-Open No. 2007-322181.
4) Average dynamic friction force
Measuring equipment: TRIBOGEAR HHS2000 Load Fluctuation Friction Wear Test System (HEIDON)
Moving distance: 15 mm, moving speed: 3.0 mm / second Indenter: SUS ball (5 mmφ), vertical load: 50 g
Number of measurements: 5 rotational friction force per substrate (F _k ): After the start of sweep, calculate the average friction force from the time when the friction force is stabilized until the end of measurement 5) Rust prevention test Room temperature environment with humidity of 90% or more A storage test was conducted for 2 weeks and 1 month. Since generation | occurrence | production of rust was not seen in the sample of Example 1 and the comparative example 2, it turned out that the anti-corrosion function as an epoxy resin is hold | maintained.
6) Solvent resistance test BCA was dropped onto each coating film, and after a few seconds, it was washed away with NS Clean 100. In Comparative Example 2 where SAM was not applied, dissolution marks were observed in the coating film. On the other hand, in Example 1, no dissolution marks were observed, and it was found that there was an improvement advantage.
7) Evaluation of crystallinity (In-plane measurement (data on a substrate with large roughness))
Using [A-1], the denseness of the SAM formed on the epoxy resin was confirmed by X-ray diffraction measurement. The crystallinity signal of the SAM on the epoxy shows strength at the same position as the SAM [Comparative Example 1] formed on the smooth silicon wafer, indicating that the SAM formed on the epoxy resin is densely formed. It was.

8) Hardness test Ultra-micro hardness test system Using a picodenter (Fischer), the maximum load was 0.5 mN, and the creep speed was 20 s. The results are shown in Table 2. A hardness increase of about 1.8 times was observed after SAM formation.

9) Coating film storage stability test i) Using a saturated aqueous solution of Na ₂ SO ₄ , a high humidity condition was maintained in a desiccator, and the sample of Example 1 was stored for about 1 month to check the state of the coating film. No abnormality was observed visually.
ii) SAM formation was performed using a sample after 1 month of storage, and the influence on the SAM formation speed and liquid repellency was investigated. The results are shown in Table 3 below. From the results, it was found that even a coating film after 1 month of storage had liquid repellency (after SAM formation) almost the same as the state of the coating film before storage, so that there was storage stability during coating.

[Example 2]
2-1. Preparation of polysiloxane solution [B-1]
In a 140 mL mayonnaise bottle, 17.00 g of methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-13) was charged. 3.02 g of diisopropoxybisacetylacetonate titanium (Nippon Soda Co., Ltd., T-50, TiO ₂ equivalent solid content: 16.5 wt%) so as to be 5 mol% in terms of TiO _{2 with} respect to methyltrimethoxysilane Added. 19.91 g of MIBK was charged and stirred for 15 minutes (stirring speed: 100 rpm). Distilled water (4.50 g) was added so as to be 2 mol per mol of methyltrimethoxysilane, and a hydrolysis reaction was carried out (2 hours, stirring speed: 100 rpm). At this time, the liquid temperature rose to 40 ° C. After completion of the reaction, the reaction solution was left for 30 minutes until the temperature of the reaction solution reached 25 ° C. to obtain a polysiloxane solution [B-1].

2-2. Preparation of organic / inorganic composite thin film forming solution [B-2]
Byron 600 (Toyobo Co., Ltd., amorphous polyester resin, SP value of about 10) / polysiloxane solution [B-1] = 90 wt% / 10 wt% 17.37 g of Byron 600 and polysiloxane solution [ B-1] 9.65 g was mixed. This mixture was diluted with 22.29 g of MIBK. An organic-inorganic composite thin film forming solution [B-2] having a solid content of 40 wt% was obtained.

2-3. A bar coat film was formed on the thin film-formed stainless steel plate so as to have a thickness of 5 μm (Dip film formation is also possible), and the film was heated at 150 ° C. for 30 minutes with a hot air circulation dryer.
About the obtained coating film, distribution of each film | membrane component in a film thickness direction was measured by ESCA. The results are shown in FIG.

2-4. Formation of self-assembled monolayer (SAM) The coating film obtained in 2-3 above was subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (Iwasaki Electric Co., Ltd.), It was immersed in the SAM forming solution for 10 minutes. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.
* SAM formation solution: SAMLAY (registered trademark) Nippon Soda Co., Ltd.

[Comparative Example 3]:
Using a solution obtained by diluting Byron 600 (Toyobo Co., Ltd., amorphous polyester resin) with MIBK so that the solid content is 40 wt%, a Dip coat film is formed on the stainless steel plate so that the thickness is 0.6 μm or more. Then, the coating film was formed by heating at 130 to 150 ° C. for 5 to 10 minutes with a hot air circulating dryer.
The obtained coating film is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (manufactured by Iwasaki Electric Co., Ltd.) and then placed in a SAM forming solution (SAMLAY (registered trademark) Nippon Soda Co., Ltd.) for 10 minutes. Soaked. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.

[Evaluation test]
Example 2 and Comparative Example 3 were evaluated. The measurement method is as follows. The results are shown in Table 4.

1) Liquid repellency (static contact angle measurement)
After 2 μl of water or 7 μl of tetradecane (hereinafter abbreviated as “TD”) is dropped from the microsyringe onto the surface of each sample, the contact angle is measured using Drop Master 700 (manufactured by Kyowa Interface Science Co., Ltd.) 60 seconds later. did.

[Example 3]
3-1. Preparation of polysiloxane solution [C-1]
In a 140 mL mayonnaise bottle, 17.00 g of methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-13) was charged. Diisopropoxybisacetylacetonate titanium (Nihon Soda Co., Ltd., T-50, TiO ₂ equivalent solid content: 16.5 wt%) 3.02 g so as to be 5 mol% in terms of TiO _{2 with} respect to methyltrimethoxysilane Added. Next, 19.91 g of MIBK was charged and stirred for 15 minutes (stirring speed: 100 rpm).
Distilled water (4.50 g) was added so as to be 2 mol per mol of methyltrimethoxysilane, and a hydrolysis reaction was carried out (2 hours, stirring speed: 100 rpm). At this time, the liquid temperature rose to 40 ° C. After completion of the reaction, the reaction solution was left for 30 minutes until the temperature of the reaction solution reached 25 ° C. Thereafter, water and alcohol were removed by dehydration to obtain a polysiloxane solution [C-1].

3-2. Preparation of organic / inorganic composite thin film forming solution [C-2]
T-150 (Nippon Soda Co., Ltd., Nisso Chita Bond) + T-122 (Nippon Soda Co., Ltd., Nisso Tita Bond) / polysiloxane = 90 wt% / 10 wt% 16.73 g and 9.29 g of the polysiloxane solution [C-1] were mixed and stirred. It was diluted with 5.90 g of ethyl acetate. An organic-inorganic composite thin film forming solution [C-2] having a solid content of 40 wt% was obtained.

3-3. A bar coat film was formed on the thin film-formed stainless steel plate so as to have a thickness of 5 μm (Dip film formation was also possible), and the film was heated at 150 ° C. for 30 minutes with a hot air circulating dryer.
About the obtained coating film, distribution of each film | membrane component in a film thickness direction was measured by ESCA. The results are shown in FIG.

3-4. Formation of self-assembled monolayer (SAM) The coating film obtained in 3-3 above is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (Iwasaki Electric Co., Ltd.) It was immersed in the SAM forming solution for 10 minutes. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.
SAM-forming drug: SAMLAY (registered trademark) Nippon Soda Co., Ltd.

[Comparative Example 4]
Using a solution obtained by diluting Nisso Titabond with ethyl acetate so that the solid content is 40 wt%, a Dip coat film is formed on a stainless steel plate so that the thickness is 0.6 μm or more, and a hot air circulation dryer is used. The coating film was formed by heating at 130-150 ° C. for 5-10 minutes.
The obtained coating film is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (Iwasaki Electric Co., Ltd.) and immersed in a SAM forming solution (SAMLAY® Nippon Soda Co., Ltd.) for 10 minutes. I let you. After lifting from the SAM forming solution, it was washed with NS Clean 100, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.

[Evaluation test]
Example 3 and Comparative Example 4 were evaluated. The measurement method is as follows. The results are shown in Table 5.
1) Liquid repellency After 5 μl of water or tetradecane (hereinafter abbreviated as “TD”) was dropped from the microsyringe onto the surface of each sample, 60 seconds later, using Drop Master 700 (manufactured by Kyowa Interface Science Co., Ltd.). The contact angle was measured.

[Example 4]
4-1. Preparation of polysiloxane solution [D-1]
28.93 g of vinyltrimethoxysilane and 20.78 g of 3-methacryloxypropyltrimethoxysilane which are organosilicon compounds were added to 15.0 g of diisopropoxybisacetylacetonate titanium, and the mixture was stirred for about 1 minute. Next, 36.71 g of MEK was added so that the solid content in [D-1] was 30 wt%, and then 1.5 times mol of pure component (Ti + Si) mol in [D-1] was added. 8.38 g of water was added. This solution was stirred at room temperature for 2 hours for hydrolysis. After completion of the reaction, the reaction solution was allowed to stand until the temperature of the reaction solution reached about room temperature to obtain 109.80 g of a polysiloxane solution [D-1] having a solid content of 30 wt%.
* Vinyltrimethoxysilane (KBM-1003, Shin-Etsu Chemical Co., Ltd.)
* 3-Methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-503)
* Diisopropoxybisacetylacetonate titanium (Nippon Soda Co., Ltd. T-50, TiO ₂ equivalent solid content: 16.5 wt%)
* Methyl ethyl ketone (MEK) Wako Pure Chemical Industries, Ltd.

4-2. Preparation of organic / inorganic composite thin film forming solution [D-2]
YD-128: Weigh 15.50 g of YD-128 and 12.92 g of polysiloxane solution [D-1] so that the polysiloxane solution [D-1] = 80 wt%: 20 wt% (solid content ratio). did. Next, 20.96 g of MEK was added and mixed so that the solid concentration in the organic-inorganic composite thin film solution [D-2] was 40 wt%. To this mixed solution, 0.62 g of 4-ethyl-4-methylimidazole of 4 wt% based on the solid content of YD-128 was added and stirred at room temperature for about 1 hour. 50.0 g of an organic-inorganic composite thin film forming solution [D-2] having a solid content concentration of 40 wt% was obtained.
* YD-128 (Nippon Steel Chemical, BPA type epoxy resin)
* 2-Ethyl-4-methylimidazole (Shikoku Chemicals Co., Ltd.)
* Solvent: Methyl ethyl ketone (MEK), Methyl isobutyl ketone (MIBK), Toluene, etc. (all Wako Pure Chemical Industries, Ltd.)

4-3. Thin film formation Dip coating is formed on an acrylic substrate and a polycarbonate substrate to a thickness of 0.6 μm or more, and heated at 60 to 100 ° C. for 5 to 20 minutes with a hot-air circulating drier. did.

4-4. Formation of self-assembled monolayer (SAM) The coating film obtained in 4-3 above is subjected to UV ozone cleaning for 10 minutes using a UV ozone cleaning device (Iwasaki Electric Co., Ltd.), It was immersed in the SAM forming solution for 10 minutes. After pulling up from the SAM forming solution, it was washed with NS Clean 100 and ultrasonically washed, drained by air blow, and heated at 60 ° C. for 10 minutes with a hot air circulation dryer.
* SAM-forming drug: SAMLAY (registered trademark) Nippon Soda Co., Ltd.

[Comparative Example 5]
The solution [D-2] for forming the organic / inorganic composite thin film prepared in Example 4 was formed into a Dip coat film on the acrylic substrate so as to have a thickness of 0.6 μm or more, and was heated at 60 to 100 ° C. with a hot air circulation dryer. Heated for 5 to 20 minutes to form a coating film.

[Comparative Example 6]
The solution [D-2] for forming an organic-inorganic composite thin film produced in Example 4 was formed into a Dip coat film on a polycarbonate resin substrate so as to be 0.6 μm or more, and was heated to 60 to 100 ° C. with a hot air circulation dryer. For 5 to 20 minutes to form a coating film.

[Evaluation test]
Example 4 and Comparative Examples 5 to 8 were evaluated. The measurement method is as follows. The results are shown in Table 6. However, Example 4-1 was laminated on an acrylic resin substrate, and Example 4-2 was laminated on a polycarbonate resin substrate. Comparative Example 7 is an untreated acrylic resin substrate, and Comparative Example 8 is an untreated polycarbonate resin substrate.

1) Liquid repellency After 2 μl of water or 7 μl of tetradecane (hereinafter abbreviated as “TD”) is dropped from the microsyringe onto the surface of each sample, 60 seconds later, using Drop Master 700 (manufactured by Kyowa Interface Science Co., Ltd.) The contact angle was measured.
2) Solvent resistance Toluene was dropped on the substrate and the surface after 25 minutes was observed.
3) Heat resistance It heated at 100 degreeC with the warm air circulation type dryer for 60 minutes.
4) Vickers hardness measurement Using a super micro hardness test system Picodenter (Fischer), it was measured at a maximum load of 0.5 mN and a creep speed of 20 s.

Claims (5)

1. In the thin film laminate formed in the order of the first layer and the second layer on the substrate,
   The first layer is
   a) Formula (I)
   R _n SiX _4-n (I)
   (In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R is the same or different. And each X may be the same or different when (4-n) is 2 or more.)
   b) An organic-inorganic composite thin film containing a cured product of a thermosetting compound,
   The thin film laminate, wherein the second layer is a layer containing a self-assembled film that is a hydrolysis condensate of a metal surfactant.
2. The thin film laminate according to claim 1, wherein the mass ratio of a) to b) in the first layer is 50:50 to 5:95.
3. The thin film laminate according to claim 1 or 2, wherein the condensate of the compound in which R in the formula (I) is a vinyl group is contained in an amount of 55% by mass or more based on the total condensate of the organosilicon compound.
4. 4. The thin film laminate according to claim 1, wherein the substrate is a resin.
5. The metal surfactant is represented by the formula (II)
   R ¹ _m MX ¹ _tm (II)
   [Wherein, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a linking group. Represents a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group, and M represents a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom. Represents at least one metal atom selected from the group consisting of X ¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. m represents a positive integer from 1 to (t−1). When m is 2 or more, R ^{1 s} may be the same or different from each other. When (tm) is 2 or more, X ¹ may be the same or different, but at least one of X ¹ is a hydrolyzable group. The thin film laminate according to any one of claims 1 to 4, which is a compound represented by the formula:

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