TWI586769B - And a composition for forming an organic-inorganic complex - Google Patents

Description

Organic-inorganic composite forming composition

The present invention relates to a composition for forming an organic-inorganic composite in which an organic component and an inorganic component are contained in one layer and the surface side is inorganicized.

The present application claims priority to Japanese Patent Application No. 2015-089382, filed on Apr. 24, 2015, the content of which is incorporated herein.

At present, as a raw material of a commercially available decane-based coating agent, a trifunctional decane is mainly used, and a polyfunctional siloxane having a moderate hardness and flexibility is formed by the trifunctional decane. However, the trifunctional decane film is not sufficiently hard-coating, and it is easy to compensate for this defect by mixing tetrafunctional decane or colloidal cerium oxide in trifunctional decane. However, if the film is hardened, it becomes easy. Cracking, which makes the adhesion worse. For example, a composition for forming an antifouling film containing a trifunctional alkoxydecane compound having an epoxy group is proposed as a coating agent for a decane-based coating (see, for example, Patent Document 1).

Heretofore, the present inventors have provided a method of irradiating an organic ruthenium compound with ultraviolet rays in the presence of a photosensitive compound to have a surface having a very high hardness and having an appropriate hardness on the inner and back sides, and a substrate. The organic-inorganic composite having excellent adhesion (Patent Document 2) further provides an acrylate-based resin which is an ultraviolet curable resin in a polysiloxane-based organic-inorganic composite, and has a very excellent surface. An organic-inorganic composite which is high in hardness and excellent in adhesion to a substrate and moisture resistance (Patent Document 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-195417

[Patent Document 2] WO2006/088079

[Patent Document 3] WO2008/069217 Specification

However, since the conventional organic-inorganic composite contains a metal compound or an acid or the like as a decyl alcohol condensation catalyst, there is a problem that the formed organic-inorganic composite produces yellow coloration derived from a metal compound. An object of the present invention is to provide a composition for forming an organic-inorganic composite which can form an organic-inorganic composite which maintains surface hardness and which has less yellow coloration than before.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that when a benzyl methyl ketal photopolymerization initiator is used as a photopolymerization initiator, no cause and effect are caused. The deterioration caused by the formation of the complex compound of the metal compound of the condensation catalyst can reduce the yellow coloration when the film is formed, thereby completing the present invention.

That is, the present invention relates to:

(1) A composition for forming an organic-inorganic composite, comprising: a) Formula (I) R _n SiX _4-n ‧‧‧(I)

(In the formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in the formula (I), 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, when (4-n) is 2 or more, each X may be the same or different), and i) contains the dissolution parameter of R in formula (I) by Fedors' push algorithm. (SP1) at least one organic ruthenium compound of the organic ruthenium compound (Si1) having a dissolution parameter (SP2) of 1.6 or more, which is determined by the Fedors' push algorithm, and/or its shrinkage Or ii) a dissolution parameter (SP1) obtained by the Fedors method of R in the formula (I), and a dissolution parameter obtained by a Fedors algorithm of the electromagnet-curable compound ( SP2) at least one of the organic ruthenium compound (Si1) having a size of 1.6 or more, and the dissolution parameter (SP1) obtained by the Fedors algorithm of R in the formula (I) is smaller than the above dissolution parameter (SP2). At least one of the organic cerium compound (Si2) having a solubility parameter (SP2) of 1.6 or more, and the molar ratio of the organic cerium compound (Si1) to the organic cerium compound (Si2) of Si1:Si2 is 5: 5~10:0 organic hydrazine compound and/or its condensate; b) selected from metal complexes, metal organic acid salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolyzates thereof, Photosensitive compound of at least one of the group consisting of condensates thereof and the like for light having a wavelength of 350 nm or less; c) a biphenyl condensed dimethanol photopolymerization initiator; and d) electromagnetic wire hardening (2) The composition for forming an organic-inorganic composite according to (1), wherein the metal of the photosensitive compound is T (3) The composition for forming an organic-inorganic composite according to (1) or (2), wherein the biphenyl quinone dimethanol photopolymerization initiator is 2, 2' The composition for forming an organic-inorganic composite according to the above aspect (1) or (2), wherein the electromagnet curable compound is (Meth) acrylate compound.

Furthermore, the present invention relates to a (5) laminated body obtained by coating the composition for organic-inorganic composite formation according to any one of (1) to (4).

According to the present invention, it is possible to provide an organic-inorganic composite which is excellent in adhesion to a substrate, heat-resistant yellowing, and yellowing resistance, and has high surface hardness and transparency.

(1) Organic hydrazine compound and/or its condensate

The organic ruthenium compound of the present invention contains at least one organic ruthenium compound of the organic ruthenium compound represented by the following formula (I). Further, the condensate of the organic hydrazine compound of the present invention means a dimer obtained by hydrolyzing and condensing an organic hydrazine compound to form a decane bond.

R _n SiX _4-n ‧‧‧(I)

In the formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in the formula (I), and X represents a hydroxyl group or a hydrolyzable group, respectively. 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" include a "hydrocarbon group which may be substituted" or a "hydrocarbon group containing a polymer moiety".

The hydrocarbon group of the above-mentioned "hydrocarbon group which may be substituted" is usually a hydrocarbon group having 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkylalkyl group, and an aromatic group. Alkyl, arylalkyl, arylalkenyl, and the like.

Preferred are an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, and an alkynyl group having 2 to 10 carbon atoms.

Further, the above "hydrocarbon group" may contain an oxygen atom, a nitrogen atom or a ruthenium atom.

Specific examples of the "alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a n-pentyl group. Isoamyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-decyl, isodecyl, n-decyl and the like.

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

Specific examples of the "alkenyl group having 2 to 10 carbon atoms" include a vinyl group, a 1-propen-1-yl group, a 2-propen-1-yl group, a 1-propen-2-yl group, and a 1-butene group. -1-yl, 2-buten-1-yl, 3-buten-1-yl, 1-buten-2-yl, 3-but-2-yl, 1-penten-1-yl, 4-penten-1-yl, 1-penten-2-yl, 4-penten-2-yl, 3-methyl-1-buten-1-yl, 1-hexen-1-yl, 5-hexen-1-yl, 1-hepten-1-yl, 6-hepten-1-yl, 1-octen-1-yl, 7-octene-1-yl and the like.

Specific examples of the "cycloalkenyl group having 3 to 8 carbon atoms" include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, and 1-cyclohexen-1-yl group. 2-cyclohexen-1-yl, 3-cyclohexen-1-yl and the like.

Specific examples of the "alkynyl group having 2 to 10 carbon atoms" include an ethynyl group, a 1-propyn-1-yl group, a 2-propyn-1-yl group, a 1-butyn-1-yl group, and 3 -butyn-1-yl, 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyne-1 -yl, 1-octyn-1-yl, 7-octyn-1-yl and the like.

Examples of the "cycloalkylalkyl group" include a group in which a cycloalkyl group having 3 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms.

"Aryl" means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to a fully unsaturated ring, a group having a partially saturated ring. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a dihydroindenyl group, and a tetrahydronaphthyl group, and an aryl group having 6 to 10 carbon atoms is preferable.

Examples of the "arylalkyl group" include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms.

Examples of the "arylalkenyl group" include a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkenyl group having 2 to 10 carbon atoms.

Examples of the "hydrocarbon group having an oxygen atom" include an alkoxyalkyl group; a group having an oxirane ring (epoxy group) such as an epoxy group, an alkylene oxide group or a glycidoxyalkyl group; and an acrylonitrile group; Oxymethyl group, methacryloxymethyl group, and the like.

Here, examples of the "alkoxyalkyl group" include alkoxy groups having 1 to 6 carbon atoms and carbon number 1. The alkyl group of ~6 is bonded to the base. Specific examples thereof include a methoxymethyl group, a methoxypropyl group, an ethoxyethyl group, and an ethoxybutyl group.

The "alkylene oxide group" is preferably an alkylene oxide group having 3 to 10 carbon atoms, and specific examples thereof include glycidyl group, glycidylmethyl group, 2-glycidylethyl group, and 3-condensed water. a linear alkyl group containing an epoxy group such as glycerylpropyl group, 4-glycidylbutyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group, 5,6-epoxyhexyl group or the like ; β-methyl glycidyl, β-ethyl glycidyl, β-propyl glycidyl, 2-glycidylpropyl, 2-glycidylbutyl, 3-glycidylbutyl, 2 -methyl-3-glycidylpropyl, 3-methyl-2-glycidylpropyl, 3-methyl-3,4-epoxybutyl, 3-ethyl-3,4-epoxy A branched alkyl group containing an epoxy group, such as a butyl group, a 4-methyl-4,5-epoxypentyl group or a 5-methyl-5,6-epoxyhexyl group.

Specific examples of the glycidoxyalkyl group include a glycidoxymethyl group and a glycidoxypropyl group.

The "hydrocarbon group having a nitrogen atom" may be a hydrocarbon group having -NR' ₂ (wherein R' represents a hydrogen atom, an alkyl group or an aryl group, and each R' may be the same or different), or has -N =CR" ₂ (wherein R" represents a hydrogen atom, an alkyl group, or an aryl group, and each R" may be the same or different).

For example, examples of the hydrocarbon group having -NR' ₂ include an aminomethyl group, a 1-aminoethyl group, and an N-methylaminomethyl group. Specific examples of the group having -N=CR" ₂ include -CH ₂ N=CHCH ₃ group, -CH ₂ N=C(CH ₃ ) ₂ group, and -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 substituent which may be substituted include a halogen group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an epoxy group, a glycidoxy group, an acryloxy group, and a methacryloxy group. And 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 or different) or the like.

Specifically, examples of the substituent which may be substituted include a halogen group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon number. 1 to 6 alkoxy group, epoxy group, glycidoxy group, acryloxy group, methacryloxy group, and group having -NR' ₂ (wherein R' represents a hydrogen atom, a carbon number of 1~ 10 alkyl or carbon 6 to 10 aryl, each R' may be the same or different) and the like. Examples of the alkyl group, the alkenyl group and the aryl group include the same hydrocarbon groups as those of R.

Specific examples of the "alkoxy group having 1 to 6 carbon atoms" include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third group. Butoxy, n-pentyloxy, isopentyloxy, neopentyloxy, n-hexyloxy, isohexyloxy and the like.

Specific examples of the "halogen group" include a fluorine group, a chlorine group, a bromine group, and an iodine group.

In the above, from the viewpoint of the inorganication of the surface of the organic-inorganic composite, a vinyl group, a group having an oxirane ring (epoxy group), a group having -NR' ₂ or having -N=CR" ₂ is a preferred group of the group.

Further, in the formula (I), n represents 1 or 2, and particularly preferably n is 1. When n is 2, each R may be the same or different.

In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) of the formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group means, for example, a base which can be hydrolyzed to form a stanol group or a base of a siloxane condensate by heating at 25 to 100 ° C in the coexistence of no catalyst or excess water. The alkoxy group, the decyloxy group, the halogen group, the isocyanate group, the amine group or the substituted amine group may, for example, be preferably an alkoxy group having 1 to 4 carbon atoms or a decyloxy group having 1 to 6 carbon atoms.

Specific examples of the "alkoxy group having 1 to 4 carbon atoms" include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third group. Butoxy and the like.

Specific examples of the "oxyl group having 1 to 6 carbon atoms" (wherein the carbon number does not include a carbonyl group) include an ethoxycarbonyl group and a benzamidine group.

Specific examples of the "halogen group" include a fluorine group, a chlorine group, a bromine group, and an iodine group.

Specific examples of the organic phosphonium compound represented by the formula (1) include methyltrichlorodecane, methyltrimethoxydecane, methyltriethoxydecane, methyltributoxydecane, and ethyl. Trimethoxy decane, ethyl triisopropoxy decane, ethyl tributoxy decane, butyl trimethoxy decane, pentafluorophenyl trimethoxy decane, phenyl trimethoxy decane, nonafluorobutyl B Dimethoxy decane, trifluoromethyl trimethoxy decane, dimethyl diamino decane, dimethyl dichloro decane, dimethyl diethoxy decane, dimethyl dimethoxy decane, Diphenyldimethoxydecane, dibutyldimethoxydecane, vinyltrimethoxydecane, 3-(methyl)propenyloxyn-propyltrimethoxydecane, 3-(3-methyl 3-oxetanyl methoxy)-n-propyltrimethoxydecane, 4-oxecyclohexyltrimethoxydecane, methyltris[(methyl)propenyloxy]decane, methyltri [ 2-(Methyl)acryloxyethoxyethoxy]decane, methyl-triglycidoxydecane, methyltris(3-methyl-3-oxetanemethoxy)decane, vinyl Trichlorodecane, B Triethoxy decane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxy-n-propyltrimethoxydecane, 3-glycidoxy-propyl-propyl Diethoxy decane, 3-glycidoxy n-propyl triethoxy decane, p-styryl trimethoxy decane, 3-methyl propylene methoxy propyl methyl dimethoxy decane, 3 -Methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, N-(2-aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxy Baseline, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl-butylene)propane Alkylamine, 3-anilinopropyltrimethoxydecane, and the like.

The organic ruthenium compound in which R is a hydrocarbon group containing a polymer moiety is a polymer obtained by copolymerizing an organic ruthenium compound having a polymerizable functional group with another monomer having a polymerizable functional group, and examples thereof include: A polymer obtained by copolymerizing 3-methacryloxypropyltrimethoxydecane with a methacrylate such as methyl methacrylate or butyl methacrylate or methacrylic acid or the like.

Further, another example of the organic ruthenium compound in which R is a hydrocarbon group containing a polymer moiety is a polymer obtained by introducing an organic oxime moiety by a polymer reaction, and examples thereof include polymethacrylic acid and 3-glycidoxy group. a polymer obtained by reacting propyltrimethoxydecane with alkoxy decane in a side chain, and introducing a 1,2-polybutadiene side chain double bond by hydrogenation using trimethylhydrohydrohalane or the like a polymer of a decyl group or the like.

Specific examples of the monomer capable of polymerizing the organic ruthenium compound having a polymerizable functional group include methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. (meth) acrylate such as 2-ethylhexyl acrylate or cyclohexyl (meth) acrylate; carboxylic acid and maleic anhydride such as (meth)acrylic acid, itaconic acid, and fumaric acid An acid anhydride; an epoxy compound such as glycidyl (meth)acrylate; an amine compound such as diethylaminoethyl (meth)acrylate or aminoethyl vinyl ether; (meth) acrylamide, Ikon Diamine, α-ethyl acrylamide, crotonamide, diammonium methacrylate, diammonium maleate, N-butoxymethyl (meth) acrylamide, etc. Indoleamine compound; acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, bisphenol A epoxy resin, phenolic novolac epoxy resin, isocyanuric acid Glycidyl ester and the like.

In addition, examples of the polymer which can be introduced into the organic oxime portion by a polymer reaction include poly(meth)acrylic acid, p-hydroxystyrene, and polybutadiene.

The amount of the organic ruthenium compound and/or the condensate thereof is 2% to the total solid content of the organic ruthenium compound and/or its condensate, the photosensitive compound, the photopolymerization initiator, and the electromagnet curable compound. 98% by mass, preferably 5 to 50% by mass, more preferably 5 to 30% by mass.

Further, the average particle diameter of the condensate of the organic cerium compound is preferably from 2 nm to 100 nm, more preferably from 5 nm to 30 nm. When the average particle diameter is more than 100 nm, the composition for formation itself becomes unstable and becomes easy to gel, and the obtained organic-inorganic composite is cloudy. When the average particle diameter is less than 2 nm, there is a case where the film properties are adversely affected.

(2) Photosensitive compounds

The photosensitive compound of the present invention is selected from the group consisting of a metal complex, a metal organic acid salt, a metal compound having two or more hydroxyl groups or a hydrolyzable group, a hydrolyzate thereof, and the like, and the like. At least one photosensitive compound that induces light at a wavelength of 350 nm or less.

The photosensitive compound of the present invention catalyzes the condensation of stanol to contribute to the condensation of the organic hydrazine compound.

The light having a wavelength of 350 nm or less is light using a light source having a wavelength of 350 nm or less as a component, and is preferably a light source using light having a wavelength of 350 nm or less as a main component. Light, that is, light obtained by using a light source having a wavelength of 350 nm or less.

The metal complex compound is preferably a metal complex having a hydroxyl group or a hydrolyzable group, and more preferably a metal complex having two or more hydroxyl groups or hydrolyzable groups. In addition, the term "having two or more hydroxyl groups or a hydrolyzable group" means that the total of the hydrolyzable group and the hydroxyl group is two or more. Further, the metal complex is preferably a compound in which a β-ketocarbonyl compound, a β-ketoester compound, and an α-hydroxyester compound are coordinated, and specific examples thereof include methyl ethyl acetate. Β-ketoesters such as n-propyl acetate, isopropyl acetate, n-butyl acetate, second butyl acetate, and tert-butyl acetate; acetonitrile, hexane- 2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, decane-2,4-dione, 5-A A β-diketone such as a hexane-hexane-2,4-dione; a compound obtained by coordination of a hydroxycarboxylic acid such as glycolic acid or lactic acid.

The metal organic acid salt is a salt obtained from a metal ion and an organic acid, and examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfur-containing organic acids such as sulfonic acid and sulfinic acid; and phenolic compounds; An enol compound; an anthracene compound; a quinone imine compound; an aromatic sulfonamide or the like which exhibits an acidic organic compound.

Further, the metal compound having two or more hydroxyl groups or hydrolyzable groups is, in addition to the metal complex and the metal organic acid salt, for example, metal hydroxide a metal alkoxide such as metal n-propoxide, metal isopropoxide or metal n-butoxide.

Examples of the hydrolyzable group in the metal complex, the metal organic acid salt, or the metal compound having two or more hydroxyl groups or hydrolyzable groups include alkoxy groups, decyloxy groups, halogen groups, and isocyanates. The group is preferably an alkoxy group having 1 to 4 carbon atoms and a decyloxy group having 1 to 4 carbon atoms. In addition, the term "having two or more hydroxyl groups or a hydrolyzable group" means that the total of the hydrolyzable group and the hydroxyl group is two or more.

The hydrolyzate and/or condensate of the metal compound having two or more hydroxyl groups or hydrolyzable groups is preferably 0.5 mol or more with respect to the metal compound 1 mol having two or more hydroxyl groups or hydrolyzable groups. The water is hydrolyzed, and it is more preferably hydrolyzed using 0.5 to 2 moles of water.

Further, the hydrolyzate and/or condensate of the metal complex is preferably hydrolyzed with 5 to 100 moles of water per mole of the metal complex 1 mol, more preferably 5 to 20 The water of Moer is hydrolyzed.

Further, the hydrolyzate and/or condensate of the metal organic acid salt is preferably hydrolyzed with 5 to 100 moles of water relative to the metal organic acid salt 1 mol, more preferably 5 to 20 The water of Moer is hydrolyzed.

Further, examples of the metal in the metal complex, the metal organic acid salt, or the metal compound having two or more hydroxyl groups or hydrolyzable groups include titanium (Ti), zirconium (Zr), and aluminum (Al). , bismuth (Si), germanium (Ge), indium (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), etc., among which titanium is preferred. (Ti), aluminum (Al), zirconium (Zr), tin (Sn), and more preferably titanium (Ti). These may be used alone or in combination of two or more.

The photosensitive compound used in the present invention is preferably a hydrolyzate and/or a condensate, and particularly preferably a hydrolyzate and/or a condensate of a metal complex, and the average particle diameter thereof is preferably 20 nm or less, more preferably It is 10 nm or less. Thereby, the transparency of the organic-inorganic composite can be improved.

The content of the photosensitive compound depends on the kind thereof, and it is usually preferred to be relatively In the Si in the organic cerium compound, the metal atom in the photosensitive compound is 0.01 to 0.5 mol equivalent, preferably 0.05 to 0.2 mol equivalent.

(3) Biphenyl condensate dimethanol photopolymerization initiator

The biphenyl fluorene dimethanol photopolymerization initiator used in the present invention is a photopolymerization initiator having a small absorption coefficient with respect to an energy line containing light having a wavelength of 375 nm to 420 nm, and examples thereof include 2, 2'. -Dimethoxy-1,2-diphenylethane-1-one ("Irgacure (registered trademark) 651" manufactured by BASF).

The amount of the photopolymerization initiator to be used in the present invention is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass based on the amount of the electromagnet curable compound.

Further, in the present invention, a sensitizer may be added as needed, and for example, trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, p-dimethylaminobenzene may be used. Ethyl formate, p-amyldimethylammonium benzoate, N,N-dimethylbenzylamine, and 4,4'-bis(diethylamino)benzophenone.

(4) Electromagnetic wire hardening compound

The electromagnet curable compound of the present invention is a compound or resin having a functional group which causes polymerization reaction by irradiation of a magnet wire in the presence of the photopolymerization initiator.

As the electromagnetic wire, ultraviolet rays, X-rays, radiation, ionized radiation, free radiation (α-ray, β-ray, γ-ray, neutron beam, or electron beam) can be used, and light having a wavelength of 350 nm or less is preferable.

In the irradiation of the electromagnetic wire, a known device such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp, or a xenon arc lamp can be used as the light source for illumination, preferably A light source comprising light of any one of wavelengths in the range of 150 to 350 nm is more preferably a light source containing light of any one of wavelengths in the range of 250 to 310 nm.

In addition, the amount of light to be irradiated in order to sufficiently cure the composition for forming an organic-inorganic composite is about 0.1 to 100 J/cm ² , and the curing efficiency of the composition (the relationship between the irradiation energy and the degree of hardening of the composition) is considered. It is preferably about 0.4 to 10 J/cm ² , more preferably about 0.4 to 5 J/cm ² .

Specific examples of the electromagnet curable compound include a vinyl compound containing a (meth) acrylate compound, an epoxy resin, and the like. The number of the functional groups which cause the polymerization reaction by the irradiation of the electromagnetic wires is not particularly limited as long as it is one or more.

Specific examples of the (meth) acrylate-based compound include poly(meth)acrylic acid urethane, polyester (meth) acrylate, epoxy (meth) acrylate, and polydecylamine. (Meth) acrylate, polybutadiene (meth) acrylate, polystyrene (meth) acrylate, polycarbonate diacrylate, tripropylene glycol di(meth) acrylate, hexane diol di ( Methyl)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, helium oxygen with (meth)acryloxyloxy group An alkane polymer or the like, preferably a polyester (meth) acrylate, a poly(meth) acrylate urethane, an epoxy poly(meth) acrylate, more preferably a poly(meth) acrylate amine group. Formate.

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

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

The (meth)acrylic acid urethane is a reaction product of an isocyanate compound obtained by reacting a polyhydric alcohol with a diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyhydric alcohol include polyester polyol and polyether. Polyol, polycarbonate diol, and the like.

In addition, examples of the vinyl compound other than the acrylate compound include N-vinylpyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. , for example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl-5,5 - spiro-3,4-epoxy)cyclohexane Alkane, bis(3,4-epoxycyclohexylmethyl) adipate, and the like.

The molecular weight of the electromagnet curable compound is not particularly limited as long as it is dissolved in the composition for forming an organic-inorganic composite, and is usually 500 to 50,000, preferably 1,000 to 10,000, as the mass average molecular weight.

The amount of the electromagnet curable compound used in the present invention is a total solid content of the organic ruthenium compound and/or its condensate, the photosensitive compound, the photopolymerization initiator, and the electromagnet curable compound. 2 to 98% by mass, preferably 5 to 95% by mass.

(5) Combination of an organic cerium compound and a magnetostatic compound based on the dissolution parameter determined by the Fedors' push algorithm

The organic ruthenium compound used in the present invention is preferably a dissolution parameter (SP1) obtained by the Fedors method of R in the formula (I), which is obtained by the Fedors algorithm of the electromagnetic sclerosing compound. An organic ruthenium compound (Si1) having a dissolution parameter (SP2) of 1.6 or more is obtained. The difference between SP1 and SP2 is preferably 1.6 to 8.5, more preferably 1.6 to 7.2.

The organic ruthenium compound used in the present invention may further comprise an organic ruthenium compound having a SP1 ratio smaller than that of SP2 or an organic ruthenium compound (Si2) having a SP1 ratio larger than SP2, and a ratio of Si1 to Si2 (Si1:Si2) of 5 : 5~10:0, preferably 9:1~10:0.

In other words, the composition for forming an organic-inorganic composite of the present invention contains the photosensitive compound, the biphenyl fluorene dimethanol photopolymerization initiator, and the electromagnet curable compound in addition to the organic ruthenium compound.

The organic ruthenium compound differs depending on the type of the electromagnet curable compound. Since the dissolution parameter (SP value) of the organic ruthenium compound and the electromagnet curable compound can be calculated based on the Fedors' calculation algorithm, the combination of the organic ruthenium compound and the electromagnet curable compound can be determined based on the SP value calculated in advance.

In the above formula (I), when n is 2 and R is different, the SP value is larger As the above SP1, a combination with a magnetostrictive compound is determined.

An example of an organic ruthenium compound which can be used in the present invention is listed together with the SP value in Table 1 below.

Next, the SP values of the representative electromagnet curable compounds usable in the present invention are shown in Table 2.

Poly(meth)acrylic acid urethane, polyester (meth) acrylate, epoxy poly(meth) acrylate, polydecyl (meth) acrylate, polybutadiene other than the above compounds Acrylate-based compounds such as (meth) acrylate, polystyrene (meth) acrylate, and polycarbonate diacrylate, the SP value of which depends on the type of functional group contained, and is in the range of 9 to 11. .

In the case of the present invention, in the case where the electromagnet curable compound is a (meth) acrylate compound, as a combination of the organic ruthenium compound (Si1) and (Si2), vinyltrimethoxydecane and 3- are preferable. A combination of methacryloxyl n-propyltrimethoxydecane, a combination of vinyltrimethoxynonane and 3-glycidoxy-n-propyltrimethoxydecane, and the like.

(6) Other ingredients

The solvent to be used in the present invention is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and octane; and alicyclic rings such as cyclohexane and cyclopentane. Hydrocarbons; ketones such as acetone, methyl ethyl ketone, cyclohexanone; tetrahydrofuran, Ethers such as alkyl ethers; esters such as ethyl acetate and butyl acetate; decylamines such as N,N-dimethylformamide and N,N-dimethylacetamide; Anthraquinones; alcohols such as methanol and ethanol; polyol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents may be used alone or in combination of two or more.

In the composition for forming an organic-inorganic composite of the present invention, a known dehydrating agent such as methyl orthoformate, methyl orthoacetate or tetraethoxysilane may be added, various surfactants, and a decane coupling agent other than the above. Additives such as titanium coupling agents, dyes, dispersants, tackifiers, leveling agents, etc.

The solid content component (organoquinone compound and/or condensate thereof, photosensitive compound, photopolymerization initiator, and magnetostrictive compound) in the composition for forming an organic-inorganic composite of the present invention is preferably 1 ~75% by mass, more preferably 10 to 60% by mass.

(7) Method for preparing composition for organic-inorganic composite formation

The composition for forming an organic-inorganic composite of the present invention can be prepared by adding water and/or a solvent, and mixing an organic hydrazine compound, a photosensitive compound, a photopolymerization initiator, and a magneto-hardening compound, as needed.

For example, a photosensitive compound is mixed in a solvent, a specific amount of water is added, (partial) hydrolysis is carried out, and then an organic hydrazine compound is added for (partial) hydrolysis. On the other hand, a method in which a magnetic wire curable compound is dissolved in a solvent and a photopolymerization initiator is added, and then the two solutions are mixed. Further, an organic ruthenium compound and a photosensitive compound may be added to a solvent and stirred, and then a specific amount of water may be added to carry out (partial) hydrolysis, and a solution of a magnetic line-curable compound and a photopolymerization initiator may be added to the solvent. mixing.

These four components may be mixed at the same time, and a method of mixing the organic ruthenium compound and the photosensitive compound may be a method of performing (partial) hydrolysis by mixing an organic ruthenium compound and a photosensitive compound, or by mixing water; or mixing Organic bismuth compound and sensitization The method of separately (partially) hydrolyzing the compound. Water or a solvent is not necessarily added, but it is preferred to add water to prepare a (partial) hydrolyzate. The amount of the specific amount of water depends on the kind of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, it is preferably 1 molar relative to the metal compound. Use more than 0.5 moles of water, more preferably 0.5 to 2 moles of water. Further, in the case where the photosensitive compound is a metal complex or an organic acid metal salt compound, it is preferred to use 5 to 100 moles of water with respect to the metal complex or the metal organic acid salt compound 1 mole. Jia uses 5 to 20 moles of water.

The condensate of the organic hydrazine compound of the present invention may be obtained by (partially) hydrolyzing an organic hydrazine compound using a known decyl alcohol condensation catalyst.

The average particle diameter of the condensate is preferably from 2 nm to 100 nm, more preferably from 5 nm to 30 nm. When the average particle diameter is more than 100 nm, the composition becomes cloudy, and the composition becomes unstable and becomes easily gelled. When the average particle diameter is less than 2 nm, there is a case where the coating property is adversely affected.

(8) Organic-inorganic composite and manufacturing method thereof

The organic-inorganic composite film of the present invention is, for example, an organic-inorganic composite film obtained by coating the composition for forming an organic-inorganic composite described above on a substrate.

Examples of the substrate capable of forming the organic-inorganic composite of the present invention include metals, ceramics, glass, and plastics. In the above, plastics are preferably exemplified, and specific examples thereof include plastic substrates for touch panels. Conventionally, it has been difficult to form a film on a plastic substrate, and it is limited to an inorganic substrate such as glass. However, the film of the present invention can be easily formed even if it is a plastic substrate which is difficult to form, and is also suitable for a plastic optical component. Examples of the plastic substrate include a polycarbonate substrate, an acrylic resin substrate, a polyimide substrate, a polyester substrate, an epoxy resin substrate, a liquid crystal polymer substrate, and a polyether fluorenyl group. material.

Moreover, as a coating method of the composition for forming an organic-inorganic composite, a known coating method can be used, and examples thereof include a dipping method, a spray method, a hard coating method, a roll coating method, and a spinning method. A spin coating method, a curtain coating method, a gravure printing method, a screen printing method, an inkjet method, or the like. Further, the film thickness of the formed film is not particularly limited, and is, for example, about 0.05 to 200 μm.

The drying treatment of the film formed by coating the composition for forming an organic-inorganic composite is preferably carried out at 40 to 200 ° C for about 1 to 120 minutes, more preferably at 60 to 120 ° C for 10 to 60 minutes. about.

The method of curing the organic-inorganic composite of the present invention is a method of irradiating the composition for forming an organic-inorganic composite with light having a wavelength of 350 nm or less.

The irradiation of light having a wavelength of 350 nm or less can be carried out, for example, by using a known apparatus such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, or an excimer lamp, and the irradiated light preferably contains any one of 150 to 350 nm. The light of the wavelength is more preferably light of any wavelength in the range of 250 to 310 nm. If it is inductive to the wavelength of the range and does not react to light exceeding 350 nm, preferably more than 310 nm, it is hardly affected by sunlight. Further, as the irradiation light amount of the irradiated light of, for example, 0.1 ~ 100J / cm ² or so, in view of hardening efficiency (relationship between the energy and degree of film hardening irradiation) is preferably 0.2 ~ 20J / cm ² or so, more Good is about 0.5~10J/cm ² .

In addition, the irradiation of light having a wavelength of 350 nm or less is a light source using a light having a wavelength of 350 nm or less as a component, and it is preferable to use a light source having a wavelength of 350 nm or less as a main component. Irradiation.

The organic-inorganic composite of the present invention contains: a) Formula (I) R _n SiX _4-n ‧‧‧(I)

(In the formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in the formula (I), 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, when (4-n) is 2 or more, each X may be the same or different), and i) contains the dissolution parameter of R in formula (I) by Fedors' push algorithm. (SP1) a condensate of at least one organic ruthenium compound having at least one organic ruthenium compound (Si1) having a dissolution parameter (SP2) of 1.6 or more, which is obtained by a Fedors' push algorithm, or a ii) inclusion formula ( I) The solubility parameter (SP1) obtained by Fedors' algorithm is higher than the dissolution parameter (SP2) of the electromagnet curable compound by the Fedors algorithm. At least one of (Si1) and the dissolution parameter (SP1) determined by Fedors' push algorithm of R in the formula (I) are smaller than the above dissolution parameter (SP2) by 1.6 or equal to or greater than the above dissolution parameter. At least one of the organic cerium compound (Si2) of (SP2), and the organic cerium compound of the organic cerium compound (Si1) and the organic cerium compound (Si2) having a molar ratio of Si1:Si2 of 5:5 to 10:0 a condensate; b) selected from the group consisting of a metal complex, a metal organic acid salt, a metal compound having two or more hydroxyl groups or a hydrolyzable group, a hydrolyzate thereof, and the like At least one photosensitive compound that induces light at a wavelength of 350 nm or less and/or a derivative thereof; c) Dimethyl acetal XI-based photopolymerization initiator; and d) the cured curable compound of magnet wire.

The organic ruthenium compound, the condensate thereof, and the electromagnet curable compound in the composition for forming an organic-inorganic composite as a raw material are each a condensate of an organic ruthenium compound and a cured product of a magneto-hardening compound in the organic-inorganic composite.

The photosensitive compound contained in the organic-inorganic composite includes a photosensitive compound and/or a derivative thereof dispersed in a condensate of an organic ruthenium compound in a non-bonded state, or a photosensitive compound and/or a derivative thereof It is bonded to a condensate of an organic cerium compound (for example, a person having a Si-OM bond (M represents a metal atom in a photosensitive compound)) or a mixed state thereof.

The compounding ratio of each of the above components and the solid form of the composition for forming an organic-inorganic composite The composition ratio of each component in the composition is the same.

The organic-inorganic composite of the present invention is segregated on the surface portion of the condensate of the organic cerium compound as an inorganic component in the formation process. The magnetic wire curable compound which is relatively an organic component is reduced in the surface portion. Therefore, the carbon concentration of the surface portion is lower than that of the interior, and the concentration of rhodium is increased. That is, the surface side is in a state of being mineralized as compared with the inside, and the surface side has a high hardness.

Therefore, the composition for forming an organic-inorganic composite of the present invention is applied to a substrate and cured, whereby a laminate having a high hardness on the surface side can be obtained.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the technical scope of the present invention is not limited to the examples.

[Example 1]

(Preparation of composition for forming an organic-inorganic composite)

Mixed with vinyl trimethoxy decane ("KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.) 5.95g and 3-methacryloxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM-503") 4.07g of liquid was added with industrial ethanol ("Solmix (registered trademark) AP-7" manufactured by Japan Alcohol Trading) 10.63g and titanium diisopropoxy acetonate (Japan Soda "T-50" manufactured by the company (trademark: solid content of 16.5% by mass) of 2.78 g, and stirred for 30 minutes. Thereafter, 3.10 g of ultrapure water was added, and further stirred at room temperature for 2 hours to obtain a polyoxyalkylene solution [A-1].

12.16 g of an urethane urethane oligomer ("UV1700B" manufactured by Nippon Synthetic Chemical Co., Ltd.) was dissolved in 17.88 g of methyl isobutyl ketone. To this solution, 2,2'-dimethoxy-1,2-diphenylethane-1-one ("Irgacure (registered trademark) 651" manufactured by BASF) was added as a photopolymerization initiator 0.446 g. (The concentration of the whole solid component was 3.2% by mass), and the solution [B-1] was obtained.

The ratio of the solid content concentration is [A-1] / [B-1] = 10% by mass / 90% by mass In the manner, [A-1] 4.47 g and [B-1] 30.49 g were mixed to prepare a composition [C-1] (solid content concentration: 39.9 mass%) of the organic-inorganic composite.

[Comparative Example 1]

In the preparation of [B-1] of Example 1, the photopolymerization initiator was changed to 2-methyl-1-(methylthiophenyl)-2-morpholinylpropan-1-one (manufactured by BASF). The composition for forming an organic-inorganic composite [RC-1] was prepared in the same manner as in Example 1 except that "Irgacure (registered trademark) 907") was used.

[Embodiment 2]

(Production of organic-inorganic composite forming substrate)

The organic-inorganic composite-forming composition [C-1] obtained in Example 1 was hard-coated on a white acrylic substrate to have a thickness of about 6 μm, and was dried at 80 ° C by a warm air circulation type dryer. After heating for 3 minutes, a concentrating high-pressure mercury lamp (UV light having a wavelength of 365 nm, 313 nm, and 254 nm as a main component, manufactured by EYE GRAPHICS, 1 lamp type, 120 W/cm, and a lamp height of 9.8 cm) was used. At a speed of 4.6 m/min, ultraviolet rays were irradiated so that the total irradiation amount became 400 mJ/cm ^{2 to} obtain an organic-inorganic composite-forming substrate [D-1].

[Comparative Example 2]

The organic-inorganic composite-forming substrate [RD-1] was obtained in the same manner as in Example 2 except that [RC-1] was used instead of [C-1].

[Evaluation of film]

The following evaluations were performed on the obtained substrates [D-1] and [RD-1].

(evaluation of coloring)

In order to investigate the degree of coloration of the substrate [D-1], the substrate [RD-1], and the untreated substrate, the b* value (yellow tone) was measured using a color turbidity measuring device (COH400, Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 3. It is understood that [D-1] of the present invention has a lower coloration than [RD-1].

(heat resistance evaluation)

The substrate [D-1] and the substrate [RD-1] were respectively subjected to heat treatment for 10 minutes, 30 minutes, 60 minutes, and 120 minutes by a warm air circulation type dryer having a temperature management of 100 ° C, and then at room temperature. After cooling for 5 minutes, the b* value before and after the heat treatment was measured using a color turbidity meter. The results are shown in Table 4. It is understood that the substrate [D-1] of the present invention has less color change before and after heat treatment than the substrate [RD-1], and is excellent in heat yellowing resistance.

(light resistance evaluation)

With respect to the substrate [D-1] and the substrate [RD-1], the cumulative irradiation amount was 500 mJ/cm ² , 1500 mJ/cm ² , 3000 mJ/cm ² , and 5000 mJ/cm ^{2 under} the same conditions as in the second embodiment. After the ultraviolet rays were irradiated, the mixture was cooled at room temperature for 5 minutes, and the b* value before and after the irradiation was measured using a color turbidity measuring instrument. The results are shown in Table 5. It is understood that the substrate [D-1] of the present invention has less color change by ultraviolet irradiation than the substrate [RD-1], and is excellent in light yellowing resistance.

Claims (5)

A composition for forming an organic-inorganic composite, comprising: a) a formula (I) R _n SiX _4-n ‧ ‧ (I) (in the formula (I), R represents a carbon atom directly bonded to the formula (I) In the organic group on 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 or different, and when (4-n) is 2 or more, each X may be the same. Further, the organic ruthenium compound and/or its condensate represented by the above, the organic ruthenium compound is i) the dissolution parameter (SP1) of the R in the formula (I) obtained by the Fedors method. The hardening compound has at least one of the above organic sulfonium compounds (Si1) having a dissolution parameter (SP2) of 1.6 or more, which is obtained by a Fedors' push algorithm; or ii) contains R in the formula (I) by Fedors The dissolution parameter (SP1) obtained by the algorithm is at least one of the above-mentioned organic bismuth compound (Si1) having a dissolution parameter (SP2) smaller than or equal to 1.6 by the Fedors' calculation algorithm. The dissolution parameter (SP1) obtained by the Fedors algorithm of R in the formula (I) is smaller than the above dissolution parameter (SP2) by less than 1.6 or equal to or greater than the above dissolution parameter (SP2). At least one of the cerium compound (Si2), and the organic cerium compound of the above organic cerium compound (Si1) and the above organic cerium compound (Si2) having a molar ratio of Si1:Si2 of 5:5 to 10:0 and/or its condensation And b) at least one selected from the group consisting of a metal complex, a metal organic acid salt, a metal compound having two or more hydroxyl groups or a hydrolyzable group, a hydrolyzate thereof, and the like a photosensitive compound that is photoinduced to a wavelength of 350 nm or less; c) a benzyl methyl ketal photopolymerization initiator; and d) an electromagnet curable compound. The composition for forming an organic-inorganic composite according to claim 1, wherein the metal of the photosensitive compound is Ti, Al, Zr, or Sn. The composition for forming an organic-inorganic composite according to claim 1 or 2, wherein the biphenyl quinone dimethanol photopolymerization initiator is 2,2'-dimethoxy-1,2-diphenylethane- 1-ketone. The composition for forming an organic-inorganic composite according to claim 1 or 2, wherein the electromagnet curable compound is a (meth) acrylate-based compound. A laminate obtained by coating a substrate with an organic-inorganic composite-forming composition according to any one of claims 1 to 4.