JP2016016641A - Laminate having functionality - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having practically usable functionality even on the surface of a substrate having unevenness on its surface.SOLUTION: A laminate having practically usable functionality can be obtained by (A) providing an organic and inorganic composite thin-film comprising an organosilicon compound represented by the formula (I): RSiX(I) (wherein, R represents an organic group in which a carbon atom is directly bound to Si; X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2; each R may be same or different when n is 2; each X may be same or different when (4-n) is 2 or more) and/or a condensate thereof, and at least one compound selected from the group consisting of a chelated or coordinated metal compound, an organic acid metal salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof and a condensate thereof on a substrate and further providing a layer which is a hydrolysis condensate of a metal surfactant.SELECTED DRAWING: None

Description

  The present invention relates to a functional laminate, and more particularly to a laminate having a layer containing a hydrolytic condensate of a metal surfactant provided on a base material via a base film.

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.
Further, on the substrate, the first layer, in order to form a thin layer laminate of the second layer, the first layer, a) Formula _{(I) R n SiX 4-} n (I) ( wherein, R Represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group, and a condensate of an organosilicon compound represented by b) and a cured product of a thermosetting compound. There is known a thin-layer laminate in which the second layer is a layer containing a self-assembled film that is a hydrolytic condensate of a metal surfactant (Patent Document 2). By adopting such a structure, a molded body having excellent functions such as hardness, solvent resistance, lubricity, slipperiness, low friction and the like is provided with a relatively simple structure. It is described that it can be.
Also, condensates of organosilicon compounds represented by the formula (I) as described above, b) metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, their hydrolysates A photo-sensitive compound and / or a compound derived therefrom that is sensitive to light having a wavelength of at least 350 nm selected from the group consisting of a decomposed product and a condensate thereof; and c) a cured product of an ultraviolet curable compound. An organic-inorganic composite containing benzene is known, and it is described that the surface can be surface-treated with a silane coupling agent to change the surface to water / oil repellency (Patent Document 3).

JP-A-8-224536 WO2014 / 010219 pamphlet WO2008 / 069217 pamphlet

However, any of the above-described laminates does not necessarily provide satisfactory functionality when applied as a primer layer for forming a water- and oil-repellent film on the surface of a substrate having uneven surfaces, for example. There was a problem that it was not possible.
This invention is made | formed in view of the said situation, and makes it a subject to provide the laminated body which has a practical function.

  As a result of tackling the above problems and earnestly studying the present inventors, the group consisting of an organosilicon compound and / or a condensate thereof, a metal chelate compound or a coordination compound and the like, a hydrolyzate thereof, and a condensate thereof. By forming a base film on a substrate using an organic / inorganic composite thin film forming solution containing at least one compound selected from the above, a denser self-assembled monolayer can be formed and is practical. The present inventors have found that a laminate having excellent performance can be obtained and have completed the present invention.

That is, the present invention
(1) In the laminate formed in the order of the first layer and the second layer on the substrate,
The first layer is of 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 in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n is 2. , R may be the same or different, and when (4-n) is 2 or more, X may be the same or different.) From the group consisting of chelated or coordinated metal compounds, organic acid metal salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, their hydrolysates, and their condensates as the main component A laminate comprising an organic-inorganic composite thin film containing at least one selected compound and / or a compound derived therefrom, wherein the second layer is a layer containing a hydrolysis condensate of a metal surfactant, as well as,
(2) The metal surfactant is represented by the formula (II)
^{_{R 11 S M 11 X 11 t}} -s (II)
[Wherein, R ¹¹ 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 ¹¹ 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 ¹¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. s represents any positive integer from 1 to (t−1), and when s is 2 or more, R ¹¹ may be the same as or different from each other. When (ts) is 2 or more, X ¹¹ may be the same or different, but at least one of X ¹¹ is a hydrolyzable group. ] It is related with the laminated body as described in (1) which is a compound shown by these.

The present invention also provides:
(3) (A) On the substrate, the 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 may be the same. May be different, and when (4-n) is 2 or more, each X may be the same or different.) And / or its condensate, and chelation or coordination A metal compound, an organic acid metal salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and at least one compound selected from the group consisting of condensates thereof An organic-inorganic composite thin film is prepared by applying a composition for forming an organic-inorganic composite thin film having a solid content of 0.01 to 20.0% by mass,
(B) It is related with the manufacturing method of the laminated body which produces the layer which is a hydrolysis-condensation product of a metal surfactant, after giving the said organic-inorganic composite thin film plasma treatment or UV ozone treatment.

  By using the laminate of the present invention, it has become possible to provide a laminate having a function that can be used even on a substrate having an uneven surface.

The laminate of the present invention has a configuration 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 laminated body. 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.
This will be described in detail below.

A) Substrate Examples of the substrate on which the thin film of the present invention can be formed include metals, ceramics, glass, and plastics.
Although there is no restriction | limiting in particular as a metal base material, Aluminum, copper, stainless steel, nickel etc. can be illustrated preferably. A base material in which a metal layer or a metal-based layer is provided on the surface of ceramic, paper, fiber, or the like may be used.
The plastic base material is not particularly limited as long as the material is a polymer base material, and specifically, polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, polycrystal resin, Examples include ether sulfone. A base material in which a polymer layer or a polymer-based layer is provided on the surface of ceramic, paper, fiber, metal or the like may be used.
The glass base material is not particularly limited as long as the material is a base material mainly composed of silicon oxide, and a silicon oxide layer is formed on the surface of ceramic, paper, fiber, etc. in the same manner as a plastic base material. Or the base material which provided the layer which has a silicon oxide as a main component may be sufficient.
The size and shape of the substrate are not particularly limited, and any of a flat plate, a three-dimensional object, a film, and the like can be used, but particularly when the laminate of the present invention is applied to a substrate having uneven surfaces. Can be used.

B) First layer: Organic-inorganic composite thin film The organic-inorganic composite thin film as the first layer of the present invention contains at least a condensate of an organosilicon compound as a main component, and is a chelated or coordinated metal compound, organic It contains at least one compound selected from the group consisting of acid metal salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof as essential components. These components may also be contained as subcomponents.

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 an optionally substituted hydrocarbon group, a hydrocarbon group containing a polymer portion, and the like.
The hydrocarbon group of the “optionally substituted hydrocarbon group” is usually a hydrocarbon group having 1 to 30 carbon atoms, such as an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, An alkynyl group, an aryl group, an arylalkyl group, an arylalkenyl group, etc. are mentioned.

  The “hydrocarbon group” may contain an oxygen atom, a nitrogen atom, or a silicon atom.

  As the alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 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, etc. Examples of the long-chain alkyl group exceeding the above include lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.

  The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  As the alkenyl group, a linear or branched alkenyl group having 2 to 10 carbon atoms is preferable, and it is a linear or branched alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more positions. Meaning, for example, ethenyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, 1-buten-1-yl group, 2-butene- 1-yl group, 3-buten-1-yl group, 1-buten-2-yl group, 3-buten-2-yl group, 1-penten-1-yl group, 4-penten-1-yl group, 1-penten-2-yl group, 4-penten-2-yl group, 3-methyl-1-buten-1-yl group, 1-hexen-1-yl group, 5-hexen-1-yl group, 1 -Hepten-1-yl group, 6-hepten-1-yl group, 1-octen-1-y Group, 7-octen-1-yl group, 1,3-butadiene-1-yl group.

  As the cycloalkenyl group, a cycloalkenyl group having 3 to 8 carbon atoms is preferable, which means an alkenyl group having 3 to 8 carbon atoms having a carbon-carbon double bond at one or more positions and having a cyclic portion. For example, 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group and the like can be mentioned. It is done.

As the alkynyl group, an alkynyl group having 2 to 10 carbon atoms is preferable. For example, ethynyl group, 1-propyn-1-yl group, 2-propyn-1-yl group, 1-butyn-1-yl group, 3- Butyn-1-yl group, 1-pentyn-1-yl group, 4-pentyn-1-yl group, 1-hexyn-1-yl group, 5-hexyn-1-yl group, 1-heptin-1-yl Group, 1-octyn-1-yl group, 7-octyn-1-yl group and the like.
The cycloalkylalkyl group is preferably a group in which a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded, for example, cyclopropylmethyl group, cyclopropylpropyl group, cyclobutylmethyl group, cyclopentyl. Examples thereof include a methyl group, a cyclopentylethyl group, a cyclohexylethyl group, and a cycloheptylmethyl group.

The aryl group means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, in addition to a fully unsaturated group, a partially saturated group is also included. Specifically, a phenyl group, a naphthyl group, Examples include an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group, and an aryl group having 6 to 10 carbon atoms is preferable.
The arylalkyl group is preferably a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded, such as benzyl group, phenethyl group, 3-phenyl-n-propyl group, 4-phenyl group. -N-butyl group, 5-phenyl-n-pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like can be mentioned.
As the arylalkenyl group, a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are bonded is preferable. For example, a styryl group, a 3-phenyl-1-propen-1-yl group, a 3- Phenyl-2-propen-1-yl group, 4-phenyl-1-buten-1-yl group, 4-phenyl-3-buten-1-yl group, 5-phenyl-1-penten-1-yl group, Examples include 5-phenyl-4-penten-1-yl group, 8-phenyl-1-octen-1-yl group, 8-phenyl-7-octen-1-yl group, and naphthylethenyl group.

  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 preferably 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. For example, a methoxymethyl group, 2-methoxyethyl group, 3-ethoxy-n -Propyl group etc. are mentioned.
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-glycidylbutyl group, Alkyl groups containing linear epoxy groups such as 3,4-epoxybutyl group, 4,5-epoxypentyl group, 5,6-epoxyhexyl group; β-methylglycidyl group, β-ethylglycidyl group, β- Propyl glycidyl group, 2-glycidyl propyl group, 2-glycidyl butyl group, 3-glycidyl butyl group, 2-methyl-3-glycidyl propyl group, 3-methyl-2-glycidyl propyl group, 3-methyl-3,4- Epoxybutyl group, 3-ethyl-3,4-epoxybutyl group, 4-methyl-4,5-epoxypentyl group, 5- Such as an alkyl group containing branched epoxy groups, such as chill-5,6 epoxy hexyl group.
Examples of the glycidoxyalkyl group include a glycidoxymethyl group and a glycidoxypropyl group.

The “hydrocarbon group having a nitrogen atom” has —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, an alkyl group or an aryl group, and each R ″ may be the same as or different from each other). Examples of the alkyl group include the same groups as described above, and 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 —CH ₂ (CH ₂ ) ₂ NH ₂ group, a —CH ₂ NHCH ₃ group, and the like. -N = Examples of the group having a _{CR '' 2, -CH 2 N} = CHCH 3 _{group, -CH 2 N = C (CH} 3) 2 _{group, -CH 2 CH 2 N = CHCH} 3 group, _-CH 2 N ═CHPh group, —CH ₂ N═C (Ph) CH ₃ group and the like.

  Examples of the “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, vinyl group, a group having an oxirane ring, -NR 'group having ₂ or -N = CR,' group with _'2, from the viewpoint of mineralization of the surface of the organic-inorganic composite, preferred groups It is.

  In the formula (I), 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) of 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 atom, an isocyanate group, an unsubstituted or substituted amino group, and the like can be mentioned. The acyloxy group of number 1-6 is preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a t-butoxy group. Examples of the group (however, the carbon number does not include carbon of the carbonyl group) include an acetoxy group and a benzoyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the compound represented by the formula (I) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, and ethyltributoxysilane. , Butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyl Dimethoxysilane, dibutyldimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (3-methyl-3-oxy) Tanmethoxy) propyltrimethoxysilane, 4-oxacyclohexyltrimethoxysilane, methyltris [(meth) acryloxy] silane, methyltris [2- (meth) acryloxyethoxy] silane, methyl-triglycidyloxysilane, methyltris (3-methyl) -3-Oxetanemethoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldi Ethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-meta Acryloxypropyltriethoxysilane, 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, 3-anilinopropyltri Mention may be made of methoxysilane. These can be used alone or in combination of two or more.

An organosilicon compound in which R is a hydrocarbon group containing a polymer moiety is, for example, a copolymerization of an organosilicon compound having a polymerizable functional group with a monomer having another polymerizable functional group, if necessary. Specifically, a polymer obtained by copolymerizing 3-methacryloxypropyltrimethoxysilane with methacrylic acid esters such as methyl methacrylate and butyl methacrylate, methacrylic acid and the like can be exemplified. Another example of an organosilicon compound that is a hydrocarbon group containing a polymer moiety is a polymer obtained by introducing an organosilicon moiety in a polymer reaction, specifically, with respect to polymethacrylic acid. An example is a polymer obtained by reacting 3-glycidoxypropyltrimethoxysilane to introduce an alkoxysilane moiety in the side chain.
Specific examples of monomers that can be polymerized with an organosilicon compound having a polymerizable functional group include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2. -(Meth) acrylic acid esters such as ethylhexyl and cyclohexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride; epoxy such as glycidyl (meth) acrylate Compounds; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide Amides such as Compound; acrylonitrile, styrene, alpha-methyl styrene, vinyl chloride, vinyl acetate, can be exemplified vinyl propionate.
Specific examples of the polymer capable of introducing an organosilicon moiety by a polymer reaction include poly (meth) acrylic acid, p-hydroxystyrene, polybutadiene, and the like.
In addition, the condensate of the organosilicon compound used as the main component in the organic inorganic composite thin film of this invention means the further condensate of the condensate of these organosilicon compounds and / or the condensate of organosilicon compounds.
The blending ratio of the organosilicon compound condensate is 2 to 98 mass%, preferably 5 to 50 mass%, more preferably 5 to 30 mass%, based on the solid content of the whole organic-inorganic composite thin film.

Specific examples of preferred embodiments of the organosilicon compound used in the present invention include the following mixtures a-1), a-2) and a-3).
a-1) Formula (I-1)
R ¹ _n SiX _4-n (I-1)
(In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ contains a vinyl group) Represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.) Compound a-2) Formula (I-2)
R ² _n SiX _4-n (I-2)
(In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² is a vinyl group-containing carbonization in which a carbon atom is directly bonded to Si in the formula. Represents an organic group other than a hydrogen group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other. Decomposition condensate

  The compound represented by the formula (I-2) and the hydrolysis condensate containing the compound as a unit do not necessarily exist. The hydrolysis condensate is a dimer or the like in which compounds are hydrolyzed and condensed to form a siloxane bond, and only a compound of formula (I) or formula (II) is hydrolyzed and condensed. It may be a product obtained by hydrolytic condensation of the compound of formula (I) and the compound of formula (II), or two or more of these may be mixed.

{[Compound of Formula (I-1)] + [If present, a unit derived from the compound of Formula (I-1) in the hydrolysis condensate]} / {[Compound of Formula (I-1)] + [Compound of formula (I-2)] + [if present, unit derived from compound of formula (I-1) in hydrolysis condensate] + [if present, formula (I in hydrolysis condensate) The unit derived from the compound of I-2)]} × 100 is preferably 30 to 100 mol%, more preferably 30 to 95 mol%,
{[Compound of formula (I-2)] + [if present, unit derived from compound of formula (I-2) in hydrolysis condensate]} / {[compound of formula (I-1)] + [Compound of formula (I-2)] + [if present, unit derived from compound of formula (I-1) in hydrolysis condensate] + [if present, formula (I in hydrolysis condensate) The unit derived from the compound of I-2)]} × 100 is preferably 0 to 70 mol%, more preferably 5 to 70 mol%.
The average particle size of the hydrolysis-condensation product is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. If the average particle size is larger than 100 nm, the film becomes cloudy, the solution becomes unstable, and gelation tends to occur. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.

Examples of the organic group and hydrolyzable group in R ¹ are the same as the organic group and hydrolyzable group in formula (I).
Examples of the vinyl group-containing hydrocarbon group in R ¹ include alkenyl groups (preferably C 2-8 alkenyl groups) such as vinyl group, allyl group, 3-butenyl group, 4-hexenyl group, 2-cyclopropenyl. Group, a cycloalkenyl group (preferably a C3-8 cycloalkenyl group) such as a 2-cyclopentenyl group, a 3-cyclohexenyl group, and a 4-cyclooctenyl group.

  Specifically, the compound represented by the formula (I-1) includes vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, 3- Butenyltrimethoxysilane, 2-cyclopropenyltrimethoxysilane, 2-cyclopentenyltrimethoxysilane, 2-cyclohexenyltrimethoxysilane, divinyldiaminosilane, divinyldichlorosilane, divinyldiacetoxysilane, divinyldimethoxysilane, diallyldimethoxy Examples include silane, di-3-butenyldimethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, allylmethyltrimethoxysilane, and allylethyltriethoxysilane.

  Examples of the compound represented by the formula (I-2) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyl Trimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxy Silane, dibutyldimethoxysilane, trimethylchlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimeth Sisilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyl Examples include loxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane, and the like.

These can be used alone or in combination of two or more.
When organic silicon compounds are used in combination, for example, a combination of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane and a combination of vinyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane can be preferably exemplified.

Further, among the organosilicon compounds represented by the formula (I-1), those in which R ¹ has 3 or less carbon atoms are 30 mol% or more, preferably 50 to 100 mol%, and the carbon of R ¹ Those having a number of 4 or more are 70 mol% or less, preferably 0 to 50 mol%.

2) selected from the group consisting of chelated or coordinated metal compounds, organic acid metal salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. At least one compound The other compound used in the organic-inorganic composite thin film of the present invention is a metal compound having a chelate or a coordination, an organic acid metal salt compound, a metal having two or more hydroxyl groups or hydrolyzable groups. It is at least one compound selected from the group consisting of compounds, their hydrolysates and their condensates, preferably hydrolysates and / or condensates, in particular chelated or coordinated. A hydrolyzate and / or condensate of a metal compound is preferred.
Examples of the compound derived therefrom include those obtained by further condensing a condensate or the like of a chelated or coordinated metal compound. As described above, the photosensitive compound and / or derivative thereof may be chemically bonded to the organosilicon compound, dispersed in a non-bonded state, or in a mixed state thereof. .

  Examples of the metal in the metal compound having two or more hydroxyl groups or hydrolyzable groups, the chelated or coordinated metal compound, or the organic acid metal salt compound include titanium, zirconium, aluminum, silicon, germanium, indium, tin, Tantalum, zinc, tungsten, lead and the like can be mentioned. Among these, titanium, zirconium and aluminum are preferable, and titanium is particularly preferable. Two or more of these may be used.

  The chelated or coordinated metal compound is preferably a chelated or coordinated metal compound having a hydroxyl group or a hydrolyzable group, or chelated or having two or more hydroxyl groups or hydrolyzable groups. More preferably, it is a coordinated metal compound. 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. Examples of the metal chelate compound or metal coordination compound include compounds in which a β-ketocarbonyl compound, a β-ketoester compound, and an α-hydroxyester compound are chelated or coordinated, more specifically. , Β-ketoesters such as methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, Β-diketones such as heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione And hydroxycarboxylic acids such as glycolic acid and lactic acid; and the like.

  The organic acid metal salt compound is a compound comprising 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 and thiophenol. Organic compounds exhibiting acidity such as sulfur-containing organic acids such as phenol compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like.

  Further, the metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the chelated or coordinated metal compound and the organic acid metal salt compound. For example, a metal hydroxide or a metal Examples include alcoholates.

  Examples of the hydrolyzable group in a metal compound having two or more hydroxyl groups or hydrolyzable groups, or a chelated or coordinated metal compound include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group. A C1-C4 alkoxy group and a C1-C4 acyloxy group are preferable. 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 having two or more hydroxyl groups or hydrolyzable groups, 0.5 mol or more is used per 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferably one that has been hydrolyzed with water, and more preferably one that has been hydrolyzed with 0.5 to 2 moles of water.

  Further, as a hydrolyzate and / or condensate of a chelated or coordinated metal compound, 5 to 100 mol of water is added to 1 mol of the chelated or coordinated metal compound. It is more preferable that it is decomposed, and it is more preferable that it is hydrolyzed using 5 to 20 moles of water.

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

  The content of the chelated or coordinated metal compound or the like shown above depends on the type, but generally the metal atom in the metal compound or the like is 0 with respect to Si in the organosilicon compound. 0.01 to 0.5 molar equivalent, preferably 0.05 to 0.2 molar equivalent.

3) Other additives In addition, tetrafunctional silane and colloidal silica can be added to the organic-inorganic composite thin film of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) 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.

  In addition, in the composition for forming an organic-inorganic composite of the present invention, in order to express various properties such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, imparting corrosion resistance, and heat resistance. It is also possible to add and disperse the filler separately. 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.

  The composition for forming an organic-inorganic composite of the present invention includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than the above, titanium Additives such as coupling agents, dyes, dispersants, thickeners and leveling agents can also be added.

4) Production method of organic-inorganic composite thin film 4-1) Preparation of organic-inorganic composite thin film forming solution The organic-inorganic composite thin film-forming solution of the present invention contains an organosilicon compound represented by the formula (I) and / or Or a condensate thereof, a chelated or coordinated metal compound, a metal organic acid salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensate thereof. At least one compound selected from the group consisting of: Furthermore, you may contain water and another additive as needed.

  The organosilicon compound represented by the formula (I) is the same as described above, preferably a condensate, and preferably has an average particle size of 10 nm or less and 4 nm or less. More preferred. Also selected from the group consisting of chelated or coordinated metal compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. The at least one compound (hereinafter also referred to as “metal compound”) is the same as described above, and is preferably a hydrolyzate and / or a condensate, and in particular, a hydrolyzate of a metal chelate compound and The average particle size is preferably 10 nm or less, and more preferably 7 nm or less. Thereby, the transparency of the organic-inorganic composite (thin film) can be improved. These average particle diameters can be measured using, for example, HPPS manufactured by Malvern Instruments Ltd.

  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; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; and the like. These solvents can be used alone or in combination of two or more.

The solid content (organosilicon component and metal compound component) in the composition for forming an organic-inorganic composite thin film of the present invention is preferably 0.01 to 20.0% by mass, and 0.01 to 10.0% by mass. %, 0.01 to 5.0 mass%, 0.01 to 1.0 mass%, 0.01 to 0.75 mass%, and 0.01 to 0.6 mass% are more preferable.
The content of the metal compound relative to the organosilicon compound is the same as the content in the organic-inorganic composite thin film.

As a method for preparing the composition for forming an organic-inorganic composite thin film of the present invention, specifically, a metal compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then organic silicon is synthesized. Method of adding (partial) hydrolysis by adding a compound, method of adding (partial) hydrolysis by adding water after mixing organosilicon compound and metal compound, or (partial) of organosilicon compound and metal compound separately The method of mixing the hydrolyzed thing can be mentioned. Although it is not always necessary to add water, it is preferable to add water to form a (partial) hydrolyzate.
The amount of water depends on the type of metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, 0.5 mol or more is used per 1 mol of the metal compound. It is preferable to use water, and it is more preferable to use 0.5 to 2 mol of water. In the case of a metal compound or metal organic acid salt compound in which the metal compound is chelated or coordinated, 5 to 100 mol per 1 mol of the chelated or coordinated metal compound or metal organic acid salt compound It is preferable to use 5 to 20 moles of water.

4-2) Manufacturing method of organic-inorganic composite thin film The organic-inorganic composite thin film of the present invention is obtained by (a) applying the above-described organic-inorganic composite thin film-forming solution on a substrate, drying and / or heating, (b ) It can be manufactured through a process of plasma treatment or UV ozone treatment.

  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. Moreover, it does not restrict | limit especially as a film thickness to form, Specifically, the range of 0.1-200 micrometers can be illustrated.

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

  When the 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. From the viewpoint of adhesion and hardness with the substrate, 2H It is preferably ˜4H.

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.

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

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

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. Processing temperature is 10-200 degreeC normally. 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.

C) Second layer: a layer containing a hydrolyzed condensate of a metal surfactant In the present invention, a layer containing a hydrolyzed condensate of a metal surfactant is further provided outside the organic-inorganic composite thin film. The layer is preferably a self-assembled film, and more preferably a monomolecular film.

  The method for producing the layer containing the hydrolytic condensate of the metal surfactant is not particularly limited, and specifically, described in WO03 / 077604, WO2004 / 091810, WO2006 / 009292, WO2009 / 104424, WO2008 / 059840, etc. As described above, 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 added to the organic inorganic solution. Examples thereof include a method of contacting a substrate on which a composite thin film is laminated. Further, as 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, specifically, Nippon Soda Examples thereof include SAMLAY (registered trademark) manufactured by Co., Ltd.

As the “metal surfactant having at least one hydroxyl group or hydrolyzable group”, if it has at least one hydroxyl group or hydrolyzable functional group and hydrophobic group in the same molecule, Although it does not restrict | limit in particular, What has a hydrolysable group which can react with the active hydrogen on the base-material surface and can form a bond is preferable. A hydroxyl group, particularly a hydroxyl group directly bonded to a metal atom can react with active hydrogen to form a bond.
As the metal surfactant having at least one hydroxyl group or hydrolyzable group, specifically, the formula (II)
^{_{R 11 S M 11 X 11 t}} -s (II)
[Wherein, R ¹¹ 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 ¹¹ 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 ¹¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. s represents any positive integer from 1 to (t−1), and when s is 2 or more, R ¹¹ may be the same as or different from each other. When (ts) is 2 or more, X ¹¹ may be the same or different, but at least one of X ¹¹ is a hydrolyzable group. The metal-type surfactant shown by this can be illustrated preferably.

  Examples of the hydrocarbon group of the “optionally substituted hydrocarbon group having 1 to 30 carbon atoms” include methyl group, ethyl group, n-propyl group, isopropyl group, 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, n-decyl An alkyl group having 1 to 30 carbon atoms such as a group; an alkenyl group having 2 to 30 carbon atoms such as a vinyl group, an allyl group and a propenyl group; and an aryl group such as a phenyl group and a naphthyl group.

  Examples of the halogenated hydrocarbon group of the “optionally substituted halogenated hydrocarbon group having 1 to 30 carbon atoms” include a halogenated alkyl group having 1 to 30 carbon atoms and a halogen having 1 to 30 carbon atoms. Alkenyl group, halogenated aryl group and the like. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable. Specific examples include groups in which one or more of the hydrogen atoms in the hydrocarbon groups exemplified above are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Among these, the halogenated hydrocarbon group having 1 to 30 carbon atoms is preferably a group in which two or more hydrogen atoms in the alkyl group having 1 to 30 carbon atoms are substituted with halogen atoms. More preferred is a fluorinated alkyl group in which two or more of the hydrogen atoms in 30 alkyl groups are substituted with fluorine atoms. In addition, 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.

As the fluorinated alkyl group, a group in which one or more fluorine atoms are bonded to the terminal carbon atom is preferable, and a group having a CF ₃ group portion in which _three fluorine atoms are bonded to the terminal carbon atom is more preferable. The terminal may be a hydrocarbon group that is not substituted by a fluorine atom, and may be a carbon chain in which a fluorine atom is substituted on an internal carbon chain. The terminal portion has a perfluoroalkyl portion in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and-(CH ₂ ) _h- (wherein h is 1) with the metal atom M described later. Represents an integer of ˜6, preferably an integer of 2 to 4.), and particularly preferred is a group having an alkylene group.

  The number of fluorine atoms in the fluorinated alkyl group is [(number of fluorine atoms in the fluorinated alkyl group) / (number of hydrogen atoms present in the alkyl group having the same carbon number corresponding to the fluorinated alkyl group) × 100]%. Is preferably 60% or more, and more preferably 80% or more.

  As the substituent of the “optionally substituted hydrocarbon group having 1 to 30 carbon atoms” or the “optionally substituted halogenated hydrocarbon group having 1 to 30 carbon atoms”, Examples thereof include a carboxyl group; an amide group; an imide group; an ester group; an alkoxy group such as a methoxy group and an ethoxy group; or a hydroxyl group. The number of these substituents is preferably 0-3.

  Specifically, the hydrocarbon group of the “hydrocarbon group having 1 to 30 carbon atoms including a linking group” is the “hydrocarbon group having 1 to 30 carbon atoms which may have a substituent”. The thing similar to what was mentioned as a hydrocarbon group is mentioned.

  In addition, as the halogenated hydrocarbon group of the “halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group”, specifically, the “optionally substituted substituent having 1 to 30 carbon atoms” may be used. The thing similar to what was mentioned as a halogenated hydrocarbon group of a "halogenated hydrocarbon group" 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 or an isopropyl group).

Among these, R ¹¹ is a C 1-30 alkyl group, a C 1-30 fluorinated alkyl group, or a fluorinated alkyl group containing a linking group from the viewpoint of water repellency and durability. Is preferred.

More preferred specific examples of R ¹¹ include CH ₃ —, CH ₃ CH ₂ —, (CH ₃ ) ₂ CH—, (CH ₃ ) ₃ C—, CH ₃ (CH ₂ ) ₂ —, CH ₃ (CH _{2 ) 3 -, CH 3 (CH} 2) 4 -, CH 3 (CH 2) 5 -, CH 3 (CH 2) 6 -, CH 3 (CH 2) 7 -, CH 3 (CH 2) 8 -, CH _{3 (CH 2) 9 -,} CH 3 (CH 2) 10 -, CH 3 (CH 2) 11 -, CH 3 (CH 2) 12 -, CH 3 (CH 2) 13 -, CH 3 (CH 2) _{14 -, CH 3 (CH 2} ) 15 -, CH 3 (CH 2) 16 -, CH 3 (CH 2) 17 -, CH 3 (CH 2) 18 -, CH 3 (CH 2) 19 -, CH 3 _{(CH 2) 20 -, CH} 3 (CH 2) 21 -, CH 3 (C _{2) 22 -, CH 3 (} CH 2) 23 -, CH 3 (CH 2) 24 -, CH 3 (CH 2) 25 -, CF 3 -, CF 3 CF 2 -, (CF 3) 2 CF-, (CF ₃ ) ₃ C—, CF ₃ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ — , CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₇ O (C F ₂ ) ₂ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₃ O [ CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂₋ , CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₁₀ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₁₂ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₁₁ (CH ₂ ) _{3 -, CH 3 CH 2 (CF} 2) 6 (CH 2) 2 -, CH 3 CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ —, CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ —, CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ —, and the like. However, it is not limited to these.

  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 particularly preferable from the viewpoints of availability of raw materials and reactivity.

X ¹¹ represents a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specifically, the C1-C6 alkoxy group which may have a substituent; The hydrocarbon oxy group (however, except an alkoxy group) which may have a substituent; An acyloxy group which may be present; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; isocyanate group; cyano group; amino group;

  Examples of the “C 1-6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n -A hexyloxy group etc. are mentioned.

“Hydrocarbonoxy group” other than alkoxy group includes cycloaliphatic hydrocarbonoxy group such as cyclopropyloxy group, cyclopropylmethyloxy and cyclohexyl group; alkenyloxy group such as vinyloxy group, allyloxy group and norbornyloxy group An alkynyloxy group such as a propargyloxy group; an aryloxy group such as a phenoxy group or a naphthyloxy group; an arylalkyloxy group such as a benzyloxy group or a phenethyloxy group;
Examples of the “acyloxy group” include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group; an alkenylcarbonyloxy group such as a (meth) acryloyloxy group; an arylcarbonyloxy group such as a benzoyloxy group.

Examples of the substituent “may have a substituent” in X ¹¹ include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.
X ¹¹ is particularly preferably a hydroxyl group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, or an isocyanate group, and more preferably an alkoxy group having 1 to 4 carbon atoms or an acyloxy group.

m represents the valence of the metal atom M.
n represents any positive integer from 1 to (m−1). In producing a high-density organic thin film, n is preferably 1. When n is 2 or more, R ¹ may be the same or different. When (mn) is 2 or more, X ¹¹ may be the same or different, but at least one of X is a hydroxyl group or a hydrolyzable group.

Among the compounds represented by formula (II), as one of preferred embodiments, formula (III)
^{(R 23) (R 22)} (R 21) C [C (R 31) (R 32)] p (R 4) q M 11 Y r X 11 m-r-1 (III)
The compound represented by these can be illustrated.
In the formula, M ¹¹ , X ¹¹ and m represent the same meaning as described above. R ^{21 to} R ²³ , R ³¹ and R ³² each independently represent a hydrogen atom or a fluorine atom, and R ⁴ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a silicon atom and / or an oxygen atom. Represents a divalent linking group. Y represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, the groups represented by the formula: C (R ³¹ ) (R ³² ) may be the same or different. r represents a positive integer from 0 or 1 to (m−2), and when r is 2 or more, Y may be the same or different, and (m−r−1) is 2 or more. , X ¹¹ may be the same or different. However, at least one of Y and X ¹¹ is a hydroxyl group or a hydrolyzable group.

Specific examples of R ⁴ in formula (III) include functional groups represented by the following formula.

In the above formula, a and b represent an arbitrary natural number of 1 or more.
Y is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group. Alkyl groups such as n-hexyl group and isohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy Group, an alkoxy group such as n-hexyloxy group; a fluorinated alkyl group in which part or all of the hydrogen atoms in the alkyl group are substituted with fluorine atoms; or a part or all of the hydrogen atoms in the alkoxy group are substituted with fluorine atoms Represents a fluorine-containing alkoxy group.

  r represents a positive integer of 0 or 1 to (m−2), and r is preferably 0 in order to produce a high-density adsorbed film. When r is 2 or more, Y may be the same or different. When (m-r-1) is 2 or more, Xs may be the same or different from each other. However, at least one of Y and X is a hydroxyl group or a hydrolyzable group.

  Specific examples of the compound represented by the formula (II) include those shown below. In the following, compounds in which the metal atom M is a silicon atom are shown as representative examples, but the present invention is not limited to these. Also, the hydrolyzable group is not limited to the exemplified functional groups, and may be one in which another hydrolyzable group is bonded.

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
CF 3 CH 2 O (CH 2} ) 15 Si (OCH 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
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CF 3 (CF 2) 7 -} (CH = CH) 3 -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
_{CF 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
_{CF 3 COO (CH 2) 15} Si (OC 2 H 5) 3
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OC 2 H 5) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) 2 (OC 2 H 5)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ )

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) _{3
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CH 2) 2 Si} (CH 3) (OCH 3) 2
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) _{2
CF 3 (CF 2) 5 (} CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OCH 3) 2
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) _{2
CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OCH 3) 2
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) _{2
CF 3 (CF 2) 7 CONH} (CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) 2
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) _{3
CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) 3
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 3
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

_{CH 3 CH 2 O (CH 2} ) 15 Si (OCH 3) (OH) 2
_{CF 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
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ 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
_{CF 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
_{CF 3 COO (CH 2) 15} Si (OC 2 H 5) (OH) 2
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) _{2
CF 3 (CF 2) 9 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) _{2
CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
_{CF 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)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OCH ₃ ) 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)
_{CF 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)
CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (OC 2 H 5) 2 (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ (OH)

CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OC 2 H 5) (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)

_{CF 3 (CH 2) 2 Si} (OCH 3) (OH) 2
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) _{2
CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) (OH) 2
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) (OH) _{2
CF 3 (CF 2) 7 (} CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 CONH} (CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 CONH} (CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) (OH) 2

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
_{CF 3 (CF 2) 7 CONH} (CH 2) 3 Si (OCH 3) 2 (OH)
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)

_{CH 3 (CH 2) 7 Si} (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) (OH) 2

_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
_{CF 3 (CH 2) 2 Si} (CH 3) (OCH 3) (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 CONH} (CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 CONH} (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CH 3 (CH 2) 7 Si} (OCH 3) 2 (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) 2 (OH)

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃
CF 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
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ 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
_{CF 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OH) 3
CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OH)
CF ₃ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OH) _{3
CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OH) 3
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CH ₂ ) ₇ Si (OH) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OH) _{3
CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OH) 3
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OH) 3
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OH) _{3
CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OH) 3
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OH) _{2
CF 3 (CH 2) 2 Si} (CH 3) (OH) 2
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (CH ₃ ) (OH) _{2
CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 2 Si (CH 3) (OH) 2
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OH) _{2
CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OH) 2
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (CH ₃ ) (OH) _{2
CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OH) 2

  These compounds can be used alone or in combination of two or more.

  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 the metal oxide include methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, XBA- Examples thereof include ST and PMA-ST (all of which represent 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) ₆ , tungsten alkoxides such as 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 that represents a transmittance of 80 to 100%, preferably 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 in order to obtain high transmittance in visible light, it is preferably in the range of 1 to 100 nm, more preferably in the range of 1 to 50 nm. More preferably, it is in the range of 1 to 10 nm.
As a method for producing a partially hydrolyzed product of metal alkoxide, 0.5 to 2.0 with respect to the metal alkoxide exemplified above in the absence of an acid, a base, and / or a dispersion stabilizer in an organic solvent. 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 at least twice as much as the metal alkoxide. 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 ligand capable of forming a complex with the metal of the metal compound to a solution of the metal compound. As a chelating agent or ligand, 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.
Examples of chelating agents or ligands 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; methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-acetoacetate Β-ketoesters such as butyl; acetylacetone, hexane-2,4-di Β-, such as benzene, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione Diketones; Hydroxycarboxylic acids such as glycolic acid and lactic acid; and heterocyclic compounds such as tetrahydrofuran, furan, furancarboxylic acid, thiophene, 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 the organic solvent solution containing a metal-based surfactant having at least one hydrolyzable group, a compound capable of interacting with the metal-based 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 will be described below, but the technical scope of the present invention is not limited to these examples.

Example 1
1. Preparation of coating composition Diisoporopoxybisacetylacetonate titanium (T-50, manufactured by Nippon Soda Co., Ltd.) was placed in a mixed solvent of 77.76 g of methyl isobutyl ketone and 36.88 g of ethanol, and stirred to dissolve. -26.51 g of methacryloxypropyltrimethoxysilane and then 36.90 g of vinyltrimethoxysilane were added and stirred to dissolve. 12.82 g of ion-exchanged water was added to this solution, and the composition [B-1] having a solid content mass conversion concentration of 20% was prepared by stirring for 2 hours and performing a hydrolysis and condensation reaction.
[B-1] 7.0 g was dissolved in 693.0 g of methyl ethyl ketone to prepare 700.0 g [X-4] of a coating agent having a solid content mass conversion concentration of 0.2%.

2. Preparation of Substrate Treated Substrate The surface of an electroplated nickel substrate (25 mm × 25 mm) previously ultrasonically cleaned with acetone was treated by UV ozone cleaning (about 12000 mJ / cm ² ) for 10 minutes. The nickel substrate was dip-coated with the coating composition [X-4], and then heat-dried at 100 ° C. for 10 minutes to prepare a base treatment substrate [Y-2].

3. Preparation of self-assembled film (SAM) -treated substrate [Y-2] was surface treated by UV ozone cleaning (about 12000 mJ / cm ² ) for 10 minutes to form a SAM-forming solution (SAMLAY (registered trademark), manufactured by Nippon Soda) After immersing for 10 minutes, the surface was ultrasonically cleaned in a hydrocarbon-based cleaning agent (NS Clean 100, manufactured by JX Nippon Mining & Energy) to obtain a SAM-treated substrate [Z-4].

4). Evaluation of liquid repellency The static contact angle of the obtained [Z-4] was measured using a contact angle measuring device (Drop Master 700, manufactured by Kyowa Interface Science). The results are shown in Table 1.

Example 2
Mass conversion of solid content obtained by diluting 7.0 g of coating composition [B-1] produced in Example 1 with a solvent obtained by mixing 623.7 g of methyl ethyl ketone and 69.3 g of 1-methoxy-2-propanol. A SAM-treated substrate [Z-5] was obtained in the same manner as in Example 1 except that the coating composition [X-5] having a concentration of 0.2% was used.

Example 3
Implemented except that 7.0 g of composition [B-1] was diluted with 693.0 g of diisopropyl ether, and coating composition [X-6] having a solid content concentration of 0.2% was used. In the same manner as in Example 1, a SAM-treated substrate [Z-6] was obtained.

Comparative Example 1
The surface of the electrolytically plated nickel substrate (25 mm × 25 mm) ultrasonically cleaned with acetone was treated with UV ozone cleaning (about 12000 mJ / cm ² ) for 10 minutes to obtain a SAM forming solution (SAMLAY (registered trademark), manufactured by Nippon Soda). Then, the surface was ultrasonically cleaned in a hydrocarbon-based cleaning agent (NS Clean 100, manufactured by JX Nippon Oil & Energy Corporation) to obtain a SAM-treated substrate [Z-0].

Claims (3)

In the laminate formed in the order of the first layer and the second layer on the substrate,
The first layer is of 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 in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n is 2. , R may be the same or different, and when (4-n) is 2 or more, X may be the same or different.) From the group consisting of chelated or coordinated metal compounds, organic acid metal salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, their hydrolysates, and their condensates as the main component A laminate comprising an organic-inorganic composite thin film containing at least one selected compound and / or a compound derived therefrom, wherein the second layer is a layer containing a hydrolytic condensate of a metal surfactant. The metal surfactant is represented by the formula (II)
^{_{R 11 S M 11 X 11 t}} -s (II)
[Wherein, R ¹¹ 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 ¹¹ 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 ¹¹ represents a hydroxyl group or a hydrolyzable group, and t represents the valence of M. s represents any positive integer from 1 to (t−1), and when s is 2 or more, R ¹¹ may be the same as or different from each other. When (ts) is 2 or more, X ¹¹ may be the same or different, but at least one of X ¹¹ is a hydrolyzable group. The laminate according to claim 1, which is a compound represented by the formula: (A) On the substrate, the 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 when the number of (4-n) is 2 or more, each X may be the same or different.) And / or a condensate thereof, and chelated or coordinated Solid content containing at least one compound selected from the group consisting of metal compounds, organic acid metal salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof An organic-inorganic composite thin film was prepared by applying a composition for forming an organic-inorganic composite thin film having a mass of 0.01-20.0% by mass,
(B) The manufacturing method of the laminated body which produces the layer which is the hydrolysis-condensation product of a metal surfactant, after giving the said organic-inorganic composite thin film plasma treatment or UV ozone treatment.