WO2016170771A1 - Composition for forming organic-inorganic composite - Google Patents

Composition for forming organic-inorganic composite Download PDF

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Publication number
WO2016170771A1
WO2016170771A1 PCT/JP2016/002072 JP2016002072W WO2016170771A1 WO 2016170771 A1 WO2016170771 A1 WO 2016170771A1 JP 2016002072 W JP2016002072 W JP 2016002072W WO 2016170771 A1 WO2016170771 A1 WO 2016170771A1
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group
compound
organic
inorganic composite
composition
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PCT/JP2016/002072
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French (fr)
Japanese (ja)
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淳司 岩佐
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日本曹達株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to a composition for forming an organic-inorganic composite containing an organic component and an inorganic component in one layer and having a mineralized surface side.
  • trifunctional silanes are mainly used as raw materials for commercially available silane-based coating agents, and polysiloxanes having appropriate hardness and flexibility are formed by such trifunctional silanes.
  • the film of trifunctional silane still lacks hard coat properties. To compensate for this, it is compensated by mixing tetrafunctional silane or colloidal silica with trifunctional silane, but the film is hardened. In this case, there is a problem that cracking is likely to occur and adhesion is deteriorated.
  • an antifouling film-forming composition containing a trifunctional alkoxysilane compound having an epoxy group has been proposed (see, for example, Patent Document 1).
  • the present inventors have so far irradiated the organic silicon compound with ultraviolet light in the presence of the photosensitive compound, so that the surface has a very high hardness, and the inside and the back side have an appropriate hardness,
  • an organic-inorganic composite having excellent adhesion to the base material is provided (Patent Document 2), and further, the surface of the polysiloxane-based organic-inorganic composite is blended with an acrylate-based resin that is an ultraviolet curable resin.
  • Patent Document 3 an organic-inorganic composite having a very high hardness and excellent adhesion to a substrate and moisture resistance
  • An object of this invention is to provide the composition for organic-inorganic composite formation which can form the organic-inorganic composite with less yellow coloring than before, maintaining surface hardness.
  • the present inventor has found that, when a benzylmethyl ketal photopolymerization initiator is used as a photopolymerization initiator, alteration due to complex formation with a metal compound that is a silanol condensation catalyst may occur. It has been found that yellowing can be reduced when a thin film is formed, and the present invention has been completed.
  • the present invention (1) a) Formula (I) R n SiX 4-n (I) (In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in formula (I), X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n represents And when R 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.
  • the solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound.
  • An organosilicon compound comprising at least one of small organosilicon compounds (Si1) and / or a condensate thereof, or ii)
  • the solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound.
  • An organosilicon compound in which the solubility parameter (SP1) obtained by the estimation method of R Fedors in formula (I) is less than 1.6 or less than or equal to the solubility parameter (SP2).
  • a light-sensitive compound that is sensitive to light c) a composition for forming an organic-inorganic composite containing a benzylmethyl ketal photopolymerization initiator, and d) an electromagnetic radiation curable compound; (2) The composition for forming an organic-inorganic composite according to (1), wherein the metal of the photosensitive compound is Ti, Al, Zr, or Sn; (3) The composition for forming an organic-inorganic complex according to (1) or (2), wherein the benzylmethyl ketal photopolymerization initiator is 2,2′-dimethoxy-1,2-diphenylethane-1-one ; (4) The composition for forming an organic-inorganic composite according to (1) or (2), wherein the electromagnetic radiation curable compound is a (meth) acrylate compound.
  • an organic-inorganic composite having excellent adhesion to a substrate, heat yellowing resistance, and light yellowing resistance and having high surface hardness and transparency can be provided.
  • Organosilicon compound and / or condensate thereof is an organosilicon compound comprising at least one of the organosilicon compounds represented by the following formula (I).
  • the condensate of the organosilicon compound of the present invention is a dimer or the like in which organosilicon compounds are hydrolyzed and condensed to form a siloxane bond.
  • 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.
  • examples of the “organic group in which a carbon atom is directly bonded to Si” represented by R include “an optionally substituted hydrocarbon group” or “a hydrocarbon group including a polymer portion”.
  • 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, an alkenyl group, a cycloalkenyl group, an alkynyl group. Group, cycloalkylalkyl group, aryl group, arylalkyl group, arylalkenyl group and the like.
  • it is 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, or an alkynyl group having 2 to 10 carbon atoms. is there.
  • the “hydrocarbon group” may contain an oxygen atom, a nitrogen atom, or a silicon atom.
  • alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, Examples include isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group and the like.
  • cycloalkyl group having 3 to 8 carbon atoms examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like.
  • alkenyl group having 2 to 10 carbon atoms include a vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, 1-buten-1-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1-buten-2-yl group, 3-buten-2-yl group, 1-pentene-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-hexene-1- Yl group, 5-hexen-1-yl group, 1-hepten-1-yl group, 6-hepten-1-yl group, 1-octen-1-yl group, 7-octen-1-yl group, etc. It is done.
  • C3-C8 cycloalkenyl group examples include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, and 2-cyclohexene- Examples thereof include a 1-yl group and a 3-cyclohexen-1-yl group.
  • alkynyl group having 2 to 10 carbon atoms include 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.
  • cycloalkylalkyl group examples include 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.
  • aryl group means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, a group having a partially saturated ring in addition to a fully unsaturated ring is also included. Specific examples include a phenyl group, a naphthyl group, 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.
  • arylalkyl group examples include 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.
  • arylalkenyl group examples include 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.
  • hydrocarbon group having an oxygen atom examples include an alkoxyalkyl group; a group having an oxirane ring (epoxy group) such as an epoxy group, an epoxyalkyl group, and a glycidyloxyalkyl group; an acryloxymethyl group, a methacryloxymethyl group, and the like. Can be mentioned.
  • examples of the “alkoxyalkyl group” include 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. Specific examples include a methoxymethyl group, a methoxypropyl group, an ethoxyethyl group, and an ethoxybutyl group.
  • the “epoxyalkyl group” is preferably an epoxyalkyl group having 3 to 10 carbon atoms, specifically, a glycidyl group, a glycidylmethyl group, a 2-glycidylethyl group, a 3-glycidylpropyl group, a 4-glycidylbutyl group, Linear alkyl group containing an epoxy group such as 3,4-epoxybutyl group, 4,5-epoxypentyl group, 5,6-epoxyhexyl group; ⁇ -methylglycidyl group, ⁇ -ethylglycidyl group, ⁇ - 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-eth
  • hydrocarbon group having a nitrogen atom As the “hydrocarbon group having a nitrogen atom”, —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 —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).
  • 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.
  • hydrocarbon group having —NR ′ 2 examples include an aminomethyl group, a 1-aminoethyl group, and an N-methylaminomethyl group.
  • substituents examples include a halogeno group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an epoxy group, a glycidyloxy group, an acryloxy group, 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 as or different from each other).
  • the substituent of the above “optionally substituted” includes a halogeno 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 groups, epoxy groups, glycidyloxy groups, acryloxy groups, methacryloxy groups, groups having —NR ′ 2 (wherein R ′ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms) 10 aryl groups, and each R ′ may be the same as or different from each other.
  • alkyl group, alkenyl group, and aryl group include the same hydrocarbon groups as those in R.
  • C 1-6 alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, and n-pentyloxy.
  • halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • n 1 or 2
  • n is particularly preferably 1.
  • each R may be the same or different.
  • X represents a hydroxyl group or a hydrolyzable group.
  • (4-n) in formula (I) is 2 or more, each X may be the same or different.
  • the hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of non-catalyst and excess water.
  • Meaning includes an alkoxy group, an acyloxy group, a halogeno group, an isocyanate group, an amino group, or a substituted amino group, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms is preferable.
  • C 1-4 alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group and the like.
  • acyloxy group having 1 to 6 carbon atoms examples include an acetoxy group and a benzoyloxy group.
  • halogeno group examples include a fluoro group, a chloro group, a bromo group, and an iodo group.
  • organosilicon compound represented by the formula (I) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyl Tributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxy Silane, diphenyldimethoxysilane, dibutyldimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloxy-n-propyltrime
  • the organosilicon compound in which R is a hydrocarbon group containing a polymer moiety is obtained by copolymerizing an organosilicon compound having a polymerizable functional group with a monomer having another polymerizable functional group as necessary.
  • the polymer include 3-methacryloxypropyltrimethoxysilane and methacrylic acid esters such as methyl methacrylate and butyl methacrylate, or polymers obtained by copolymerization with methacrylic acid and the like.
  • Another example of an organosilicon compound in which R is a hydrocarbon group containing a polymer moiety is a polymer obtained by introducing an organosilicon moiety by a polymer reaction.
  • Examples include polymers in which glycidyloxypropyltrimethoxysilane is reacted to introduce alkoxysilane moieties in the side chains, and polymers in which silyl groups are introduced into 1,2-polybutadiene side chain double bonds by hydrosilylation with trimethoxyhydrosilane or the like. It is done.
  • 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.
  • (Meth) acrylic acid esters such as 2-ethylhexyl and cyclohexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride; glycidyl (meth) acrylate and the like Epoxy compounds; amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether; (meth) acrylamide, itaconic acid diamide, ⁇ -ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) Amide compounds such as acrylamide; Rironitoriru, styrene, alpha-methyl styrene, vinyl chloride, vinyl acetate, vinyl propionate, bisphenol A type epoxy resins, phenol novolak type epoxy resin, triglycidyl isocyanurate.
  • the compounding amount of the organosilicon compound and / or its condensate is 2 to 2 with respect to the total solid content of the organosilicon compound and / or its condensate, photosensitive compound, photopolymerization initiator, and electromagnetic radiation curable compound. It is 98% by mass, preferably 5 to 50% by mass, more preferably 5 to 30% by mass.
  • the average particle size of the condensate of the organosilicon compound is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. When the average particle size is larger than 100 nm, the forming composition itself becomes unstable and easily gels, and the obtained organic-inorganic composite becomes cloudy. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.
  • the photosensitive compound of the present invention comprises a metal complex, a metal organic acid salt, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensate thereof.
  • the photosensitive compound of the present invention catalyzes silanol condensation and contributes to the condensation of the organosilicon compound.
  • Light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less as a component, preferably using a light source having light of any wavelength of 350 nm or less as a main component Light, that is, light using a light source having a wavelength of 350 nm or less with the largest amount of component.
  • the metal complex 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.
  • having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.
  • the metal complex is preferably a compound in which a ⁇ -ketocarbonyl compound, ⁇ -ketoester compound, and ⁇ -hydroxyester compound are coordinated.
  • methyl acetoacetate, n-propyl acetoacetate, acetoacetic acid ⁇ -ketoesters such as isopropyl, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5 - ⁇ -diketones such as dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid Compound.
  • ⁇ -ketoesters such as isopropyl, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate
  • acetylacetone hexane-2
  • the metal organic acid salt is a salt obtained from a metal ion and an organic acid.
  • 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; Organic compounds exhibiting acidity such as phenol compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides;
  • the metal compound having two or more hydroxyl groups or hydrolyzable groups is other than the metal complex and the metal organic acid salt, and examples thereof include metal hydroxide, metal n-propoxide, metal isopropoxy. And metal alcoholates such as metal n-butoxide.
  • hydrolyzable group in the metal complex, the metal organic acid salt, or the metal compound having two or more hydroxyl groups or hydrolyzable groups examples include an alkoxy group, an acyloxy group, a halogeno group, and an isocyanate group.
  • An alkoxy group having 1 to 4 carbon atoms and an acyloxy group having 1 to 4 carbon atoms are preferable.
  • having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.
  • 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 hydrolyzed using water, more preferably hydrolyzed using 0.5 to 2 mol of water.
  • the hydrolyzate and / or condensate of the metal complex is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal complex. More preferably, it is hydrolyzed by use.
  • the hydrolyzate and / or condensate of the metal organic acid salt is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt. More preferably, it is hydrolyzed with molar water.
  • Examples of the metal in these metal complexes, metal organic acid salts, or metal compounds having two or more hydroxyl groups or hydrolyzable groups include titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), Examples include germanium (Ge), indium (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), etc.
  • titanium (Ti), aluminum (Al ), Zirconium (Zr), and tin (Sn) are preferable, and titanium (Ti) is particularly preferable. These may be used alone or in combination of two or more.
  • the light-sensitive compound used in the present invention is preferably a hydrolyzate and / or a condensate, in particular, a hydrolyzate and / or a condensate of a metal complex, and its average particle size is 20 nm or less. It is preferable that the thickness is 10 nm or less. Thereby, the transparency of the organic-inorganic composite can be improved.
  • the content of the photosensitive compound depends on its type, but generally 0.01 to 0.5 molar equivalent of metal atoms in the photosensitive compound with respect to Si in the organosilicon compound, It is preferably 0.05 to 0.2 molar equivalent.
  • the benzylmethyl ketal photopolymerization initiator used in the present invention is a photopolymerization initiator having a small extinction coefficient with respect to energy rays containing light having a wavelength of 375 nm to 420 nm, Examples thereof include 2,2′-dimethoxy-1,2-diphenylethane-1-one (“Irgacure (registered trademark) 651” manufactured by BASF).
  • the blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the electromagnetic radiation curable compound.
  • a sensitizer can be added as necessary.
  • trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p- Isoamyl dimethylaminobenzoate, N, N-dimethylbenzylamine, 4,4′-bis (diethylamino) benzophenone, and the like can be used.
  • the electromagnetic radiation curable compound of the present invention is a compound or resin having a functional group that undergoes a polymerization reaction upon irradiation with electromagnetic radiation in the presence of the photopolymerization initiator.
  • electromagnetic radiation ultraviolet rays, X-rays, radiation, ionizing radiation, ionizing radiation ( ⁇ rays, ⁇ rays, ⁇ rays, neutron rays, electron beams) can be used, and light having a wavelength of 350 nm or less is preferable.
  • Irradiation of electromagnetic radiation can be performed using a known apparatus such as an ultra-high 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.
  • a light source including light of any wavelength in the range of 150 to 350 nm and more preferably a light source including light of any wavelength in the range of 250 to 310 nm.
  • the amount of light irradiated to sufficiently cure the organic-inorganic composite-forming composition is about 0.1 to 100 J / cm 2
  • the curing efficiency of the composition irradiation energy and curing of the composition
  • it is preferably about 0.4 to 10 J / cm 2 , and more preferably about 0.4 to 5 J / cm 2 .
  • the electromagnetic radiation curable compound examples include a vinyl compound containing a (meth) acrylate compound, an epoxy resin, and the like.
  • the number of functional groups that cause a polymerization reaction upon irradiation with electromagnetic radiation is not particularly limited as long as it is one or more.
  • the (meth) acrylate compound examples include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, Polycarbonate diacrylate, tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) Examples thereof include siloxane polymers having an acryloyloxy group, preferably polyester (meth) acrylate and polyurethane (meth) acrylic. Over DOO, an epoxy poly (meth) acrylate, more preferably a polyurethane (meth) acrylate.
  • Epoxy (meth) acrylate can be obtained by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin and acrylic acid.
  • the polyester (meth) acrylate is obtained by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with acrylic acid. It can also be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.
  • Urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol, polyether polyol, polycarbonate diol, and the like. It is done.
  • Examples of vinyl compounds other than acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester.
  • Epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxy (Cyclohexylmethyl) adipate and the like.
  • the molecular weight of the electromagnetic radiation curable compound is not limited as long as it dissolves in the composition for forming an organic-inorganic composite, but is usually 500 to 50,000, preferably 1,000 to 10,000 as a weight average molecular weight. .
  • the blending amount of the electromagnetic radiation curable compound used in the present invention is 2 with respect to the total solid content of the organosilicon compound and / or the condensate thereof, the photosensitive compound, the photopolymerization initiator, and the electromagnetic radiation curable compound. It is ⁇ 98% by mass, preferably 5 to 95% by mass.
  • the organosilicon compound used in the present invention is determined by R's Fedors estimation method in formula (I).
  • the solubility parameter (SP1) is preferably an organosilicon compound (Si1) smaller than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound.
  • the difference between SP1 and SP2 is preferably 1.6 to 8.5, and more preferably 1.6 to 7.2.
  • the organosilicon compound used in the present invention may further contain an organosilicon compound in which SP1 is less than 1.6 less than SP2, or an organosilicon compound (Si2) in which SP1 is greater than SP2, and the ratio between Si1 and Si2 (Si1: Si2) is 5: 5 to 10: 0, and preferably 9: 1 to 10: 0.
  • the organic-inorganic composite-forming composition of the present invention contains the photosensitive compound, the benzyl methyl ketal photopolymerization initiator, and the electromagnetic radiation curable compound in addition to the organosilicon compound.
  • the organosilicon compound differs depending on the type of electromagnetic radiation curable compound. Since the solubility parameter (SP value) of the organosilicon compound and the electromagnetic radiation curable compound can be calculated based on the Fedors' estimation method, the organosilicon compound and the electromagnetic radiation curable compound can be calculated based on the precalculated SP value. A combination can be determined. In the formula (I), when n is 2 and R is different, the SP value having the larger numerical value is set as the SP1, and the combination with the electromagnetic radiation curable compound is determined.
  • organosilicon compounds that can be used in the present invention are listed in Table 1 below together with SP values.
  • SP values of typical electromagnetic radiation curable compounds that can be used in the present invention are listed in Table 2.
  • acrylates such as polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy poly (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, etc.
  • the SP value is in the range of 9 to 11 depending on the type of functional group contained.
  • the combination of the organosilicon compound (Si1) and (Si2) includes vinyltrimethoxysilane and 3-methacryloxy-n-propyltri A combination of methoxysilane and a combination of vinyltrimethoxysilane and 3-glycidyloxy-n-propyltrimethoxysilane are preferred.
  • the solvent 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; cyclohexane, Cycloaliphatic hydrocarbons such as cyclopentane; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; N, N-dimethylformamide, N, N— Amides such as dimethylacetamide; Sulfoxides such as dimethyl sulfoxide; Alcohols such as methanol and ethanol; Polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; These solvents can be used alone or in combination of two or more.
  • aromatic hydrocarbons such as
  • 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 those described above, and titanium couplings.
  • dehydrating agents such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, various surfactants, silane coupling agents other than those described above, and titanium couplings.
  • Additives such as agents, dyes, dispersants, thickeners, and leveling agents can also be added.
  • the solid content (organosilicon compound and / or condensate thereof, photosensitive compound, photopolymerization initiator, and electromagnetic radiation curable compound) in the composition for forming an organic-inorganic composite of the present invention is 1 to 75 masses. %, Preferably 10 to 60% by mass.
  • composition for forming organic / inorganic composite of the present invention is added with water and / or a solvent, if necessary, to form an organosilicon compound, a photosensitive compound, and a photopolymerization. It can be prepared by mixing an initiator and an electromagnetic radiation curable compound.
  • a photosensitive compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added (partial) to cause hydrolysis.
  • an electromagnetic radiation curable compound is dissolved in a solvent, a photopolymerization initiator is added, and then both solutions are mixed.
  • an organosilicon compound and a photosensitive compound are added to a solvent and stirred, and then a predetermined amount of water is added to perform (partial) hydrolysis, and then an electromagnetic radiation curable compound and a photopolymerization initiator are added to the solvent. You may mix with the added solution.
  • the method of mixing the organosilicon compound and the photosensitive compound after mixing the organosilicon compound and the photosensitive compound, water is added (partial) hydrolysis. And a method of separately (partially) hydrolyzing an organosilicon compound and a photosensitive compound. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water.
  • the amount of the predetermined amount of water depends on the type of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 1 mol of the metal compound. It is preferable to use 0.5 mol or more of water, more preferably 0.5 to 2 mol of water. In the case where the photosensitive compound is a metal complex or an organic acid metal salt compound, 5 to 100 mol of water is preferably used with respect to 1 mol of the metal complex or metal organic acid salt compound. It is more preferable to use
  • the condensate of the organosilicon compound of the present invention a product obtained by (partially) hydrolyzing an organosilicon compound using a known silanol condensation catalyst may be used.
  • the average particle size of the condensate is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. When the average particle size is larger than 100 nm, the composition becomes cloudy, the composition becomes unstable and is easily gelled. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.
  • the organic-inorganic composite of the present invention is, for example, an organic-inorganic composite thin film obtained by applying the organic-inorganic composite-forming composition on a substrate.
  • the substrate on which the organic-inorganic composite of the present invention can be formed include metals, ceramics, glass, and plastics.
  • plastic is preferably used, and specifically, a plastic substrate for a touch panel can be used.
  • 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 polyethersulfone substrate.
  • a coating method of the composition for forming an organic / inorganic composite a known coating method can be used.
  • a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, A gravure printing method, a silk screen method, an inkjet method, etc. can be mentioned.
  • the thickness of the thin film to be formed is not particularly limited, and is, for example, about 0.05 to 200 ⁇ m.
  • the thin film formed by applying the organic-inorganic composite-forming composition is preferably dried, for example, at 40 to 200 ° C. for about 1 to 120 minutes, and at 60 to 120 ° C. for about 10 to 60 minutes. More preferably.
  • Examples of the method for curing the organic-inorganic composite of the present invention include a method in which the organic-inorganic composite-forming composition is irradiated with light having a wavelength of 350 nm or less.
  • Irradiation with light having a wavelength of 350 nm or less can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp.
  • the irradiation light is in the range of 150 to 350 nm. It is preferable that the light contains light having any one of the above wavelengths, and it is more preferable that the light contains light having any wavelength in the range of 250 to 310 nm. As long as it is sensitive to wavelengths in this range and does not react to light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight.
  • the irradiation light quantity of the light to be irradiated is, for example, about 0.1 to 100 J / cm 2, and considering the curing efficiency (relation between irradiation energy and film curing degree), 0.2 to 20 J / cm 2. Is preferably about 0.5 to 10 J / cm 2 .
  • irradiation with light having a wavelength of 350 nm or less is irradiation using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. The irradiation used.
  • the organic-inorganic composite of the present invention is a) Formula (I) R n SiX 4-n (I) (In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in formula (I), X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n represents And when R 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.
  • the solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound.
  • the solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound.
  • An organosilicon compound in which the solubility parameter (SP1) obtained by the estimation method of R Fedors in formula (I) is less than 1.6 or less than or equal to the solubility parameter (SP2).
  • a light-sensitive compound and / or a derivative thereof sensitive to light c) a benzyl methyl ketal photopolymerization initiator, and d) a cured product of an electromagnetic radiation curable compound.
  • the organosilicon compound or the condensate thereof and the electromagnetic curable compound in the organic-inorganic composite-forming composition as the raw material are the condensate of the organosilicon compound and the electromagnetic curable compound, respectively. It becomes a cured product.
  • the photo-sensitive compound contained in the organic-inorganic composite is a photo-sensitive compound and / or derivative thereof dispersed in a non-bonded state in a condensate of an organosilicon compound, or a photo-sensitive compound in a condensate of an organosilicon compound. Or a derivative thereof (for example, a compound having a Si—OM bond (M represents a metal atom in a photosensitive compound)) or a mixture thereof. Is included.
  • the blending ratio of each component is the same as the blending ratio of each component in the solid content of the composition for forming an organic-inorganic composite.
  • a condensate of an organic silicon compound, which is an inorganic component is segregated on the surface portion in the formation process.
  • the electromagnetic radiation curable compound, which is a relatively organic component decreases at the surface portion. Therefore, the carbon concentration of the surface portion is lower than that of the inside, and the silicon concentration is higher. That is, the surface side becomes mineralized more than the inside, and the surface side has high hardness. Therefore, the laminated body which the surface side has high hardness is obtained by apply
  • Example 1 (Preparation of composition for forming organic-inorganic composite) 5.95 g of vinyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.) and 4.07 g of 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) To the mixed solution, 10.63 g of industrial ethanol (manufactured by Nippon Alcohol Sales, “Solmix (registered trademark) AP-7”) and diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., “T- 50 ”, titanium oxide equivalent solid content: 16.5 mass%) 2.78 g was added and stirred for 30 minutes.
  • Solmix registered trademark
  • T- 50 titanium oxide equivalent solid content: 16.5 mass
  • Example 2 (Preparation of organic / inorganic composite substrate)
  • the organic-inorganic composite-forming composition [C-1] obtained in Example 1 was bar-coated on a white acrylic substrate so as to have a thickness of about 6 ⁇ m, and 3 ° C. at 80 ° C. with a hot air circulating dryer.
  • a condensing type high-pressure mercury lamp (UV light mainly composed of light having wavelengths of 365 nm, 313 nm, and 254 nm, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height of 9.8 cm
  • the organic-inorganic composite-formed substrate [D-1] was obtained by irradiating with ultraviolet rays so that the integrated irradiation amount was 400 mJ / cm 2 at a conveyor speed of 4.6 m / min.
  • the substrate [D-1] and the substrate [RD-1], Example 2 and the total irradiation amount is respectively 500 mJ / cm 2 under the same conditions, 1500mJ / cm 2, 3000mJ / cm 2, 5000mJ / cm 2 become as After irradiating with ultraviolet rays, it was cooled at room temperature for 5 minutes, and b * values before and after irradiation were measured using a color turbidity measuring device. The results are shown in Table 5. It has been found that the substrate [D-1] of the present invention has less color change due to ultraviolet irradiation and is excellent in light yellowing resistance compared to the substrate [RD-1].

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Abstract

The objective of the present invention is to provide a composition for forming an organic-inorganic composite, which forms an organic-inorganic composite that has excellent adhesion to a base, excellent yellowing resistance against heat and excellent yellowing resistance against light, while having high surface hardness and high transparency. A composition for forming an organic-inorganic composite according to the present invention contains the following components: (a) an organosilicon compound represented by formula (I) RnSiX4-n and/or a condensation product thereof; (b) at least one photosensitive compound which is selected from the group consisting of metal complexes, organic acid salts of metals, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysis products of these compounds and condensation products of these compounds, and which is sensitive to light having a wavelength of 350 nm or less; (c) a benzyl methyl ketal-based photopolymerization initiator; and (d) an electromagnetic radiation curable compound.

Description

有機無機複合体形成用組成物Composition for forming organic-inorganic composite
　本発明は、有機成分と無機成分を１層中に含有し、かつ、表面側が無機化した有機無機複合体の形成用組成物に関する。
　本願は、２０１５年４月２４日に出願された日本国特許出願第２０１５－０８９３８２号に対し優先権を主張し、その内容をここに援用する。 The present invention relates to a composition for forming an organic-inorganic composite containing an organic component and an inorganic component in one layer and having a mineralized surface side.
This application claims priority to Japanese Patent Application No. 2015-089382 filed on April 24, 2015, the contents of which are incorporated herein by reference.
　現在、市販品のシラン系コート剤の原料としては、主として３官能のシランが用いられており、かかる３官能シランにより、適度な硬さと柔軟性を持つポリシロキサンが形成される。しかしながら、３官能シランの膜では、まだハードコート性が不足しており、それを補うために、３官能シランに、４官能シランやコロイダルシリカを混合することにより補っているが、膜を硬くすれば、ヒビ割れやすくなり、密着性が悪くなるという問題がある。例えば、シラン系のコート剤としては、エポキシ基を有する３官能アルコキシシラン化合物を含有する防汚膜形成用組成物が提案されている（例えば、特許文献１参照）。  Currently, trifunctional silanes are mainly used as raw materials for commercially available silane-based coating agents, and polysiloxanes having appropriate hardness and flexibility are formed by such trifunctional silanes. However, the film of trifunctional silane still lacks hard coat properties. To compensate for this, it is compensated by mixing tetrafunctional silane or colloidal silica with trifunctional silane, but the film is hardened. In this case, there is a problem that cracking is likely to occur and adhesion is deteriorated. For example, as a silane-based coating agent, an antifouling film-forming composition containing a trifunctional alkoxysilane compound having an epoxy group has been proposed (see, for example, Patent Document 1).
　本発明者らはこれまでに、光感応性化合物の存在下で有機ケイ素化合物に紫外線を照射することにより、表面が非常に高い硬度を有すると共に、内部及び裏面側が適当な硬度を有しつつ、かつ基材との密着性に優れた有機無機複合体を提供し（特許文献２）、さらに、ポリシロキサン系の有機無機複合体に紫外線硬化性樹脂であるアクリレート系樹脂を配合することにより、表面が非常に高い硬度を有すると共に、基材との密着性及び耐湿性に優れた有機無機複合体を提供してきた（特許文献３）。 The present inventors have so far irradiated the organic silicon compound with ultraviolet light in the presence of the photosensitive compound, so that the surface has a very high hardness, and the inside and the back side have an appropriate hardness, In addition, an organic-inorganic composite having excellent adhesion to the base material is provided (Patent Document 2), and further, the surface of the polysiloxane-based organic-inorganic composite is blended with an acrylate-based resin that is an ultraviolet curable resin. Has provided an organic-inorganic composite having a very high hardness and excellent adhesion to a substrate and moisture resistance (Patent Document 3).
特開平１０－１９５４１７号公報Japanese Patent Laid-Open No. 10-195417 ＷＯ２００６／０８８０７９号パンフレットWO 2006/088079 pamphlet ＷＯ２００８／０６９２１７号パンフレットWO2008 / 069217 pamphlet
　しかしながら、従来の有機無機複合体は、シラノール縮合触媒である金属化合物や酸等を含むため、形成された有機無機複合体には金属化合物由来の黄着色が生じるという問題があった。本発明は、表面硬度を保ちつつ、従来よりも黄着色の少ない有機無機複合体を形成できる有機無機複合体形成用組成物を提供することを目的とする。 However, since the conventional organic-inorganic composite contains a metal compound or an acid that is a silanol condensation catalyst, the formed organic-inorganic composite has a problem that yellow coloring derived from the metal compound occurs. An object of this invention is to provide the composition for organic-inorganic composite formation which can form the organic-inorganic composite with less yellow coloring than before, maintaining surface hardness.
　本発明者は、上記課題を解決するために鋭意検討を行った結果、光重合開始剤としてベンジルメチルケタール系光重合開始剤を用いると、シラノール縮合触媒である金属化合物との錯体形成による変質が起こらず、薄膜を形成した際に黄着色を低減できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that, when a benzylmethyl ketal photopolymerization initiator is used as a photopolymerization initiator, alteration due to complex formation with a metal compound that is a silanol condensation catalyst may occur. It has been found that yellowing can be reduced when a thin film is formed, and the present invention has been completed.
　すなわち、本発明は、
（１）
ａ）式（Ｉ）
ＲｎＳｉＸ４－ｎ・・・（Ｉ）
（式（Ｉ）中、Ｒは式（Ｉ）中のＳｉに炭素原子が直接結合する有機基を表し、Ｘは夫々水酸基又は加水分解性基を表す。ｎは１又は２を表し、ｎが２のとき各Ｒは同一でも異なっていてもよく、（４－ｎ）が２以上のとき各Ｘは同一でも異なっていてもよい。）で表され、かつ、
ｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種からなる有機ケイ素化合物及び／又はその縮合物、又は、
ｉｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種と、
式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、前記溶解パラメータ（ＳＰ２）より１．６未満小さい又は前記溶解パラメータ（ＳＰ２）と等しいか大きい有機ケイ素化合物（Ｓｉ２）の少なくとも１種とからなり、
前記有機ケイ素化合物（Ｓｉ１）と前記有機ケイ素化合物（Ｓｉ２）のモル比Ｓｉ１：Ｓｉ２が５：５～１０：０である有機ケイ素化合物及び／又はその縮合物、
ｂ）金属錯体、金属有機酸塩、２以上の水酸基若しくは加水分解性基を有する金属化合物、それらの加水分解物、及びそれらの縮合物からなる群より選ばれる少なくとも１種の３５０ｎｍ以下の波長の光に感応する光感応性化合物、
ｃ）ベンジルメチルケタール系光重合開始剤、及び
ｄ）電磁線硬化性化合物
を含有する有機無機複合体形成用組成物；
（２）光感応性化合物の金属がＴｉ、Ａｌ、Ｚｒ、又はＳｎである、（１）に記載の有機無機複合体形成用組成物；
（３）ベンジルメチルケタール系光重合開始剤が２，２’－ジメトキシ－１，２－ジフェニルエタン－１－オンである、（１）又は（２）に記載の有機無機複合体形成用組成物；
（４）電磁線硬化性化合物が（メタ）アクリレート系化合物である、（１）又は（２）に記載の有機無機複合体形成用組成物；に関する。 That is, the present invention
(1)
a) Formula (I)
R n SiX 4-n (I)
(In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in formula (I), X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n represents And when R 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.
i) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. An organosilicon compound comprising at least one of small organosilicon compounds (Si1) and / or a condensate thereof, or
ii) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. At least one small organosilicon compound (Si1);
An organosilicon compound in which the solubility parameter (SP1) obtained by the estimation method of R Fedors in formula (I) is less than 1.6 or less than or equal to the solubility parameter (SP2). Consisting of at least one of Si2),
An organosilicon compound in which the molar ratio Si1: Si2 of the organosilicon compound (Si1) and the organosilicon compound (Si2) is 5: 5 to 10: 0 and / or a condensate thereof,
b) At least one wavelength of 350 nm or less selected from the group consisting of metal complexes, metal organic acid salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light,
c) a composition for forming an organic-inorganic composite containing a benzylmethyl ketal photopolymerization initiator, and d) an electromagnetic radiation curable compound;
(2) The composition for forming an organic-inorganic composite according to (1), wherein the metal of the photosensitive compound is Ti, Al, Zr, or Sn;
(3) The composition for forming an organic-inorganic complex according to (1) or (2), wherein the benzylmethyl ketal photopolymerization initiator is 2,2′-dimethoxy-1,2-diphenylethane-1-one ;
(4) The composition for forming an organic-inorganic composite according to (1) or (2), wherein the electromagnetic radiation curable compound is a (meth) acrylate compound.
　さらに、
（５）基材に（１）～（４）のいずれかに記載の有機無機複合体形成用組成物を塗布して得られる積層体；に関する。 further,
(5) A laminate obtained by applying the organic-inorganic composite-forming composition according to any one of (1) to (4) to a substrate.
　本発明によれば、基材との密着性、耐熱黄変性、及び耐光黄変性に優れ、かつ高い表面硬度と透明性を有する有機無機複合体を提供することができる。 According to the present invention, an organic-inorganic composite having excellent adhesion to a substrate, heat yellowing resistance, and light yellowing resistance and having high surface hardness and transparency can be provided.
（１）有機ケイ素化合物及び／又はその縮合物
　本発明の有機ケイ素化合物は、以下の式（Ｉ）で表される有機ケイ素化合物の少なくとも１種以上からなる有機ケイ素化合物である。また、本発明の有機ケイ素化合物の縮合物とは、有機ケイ素化合物同士が加水分解縮合してシロキサン結合を形成した２量体等である。 (1) Organosilicon compound and / or condensate thereof The organosilicon compound of the present invention is an organosilicon compound comprising at least one of the organosilicon compounds represented by the following formula (I). The condensate of the organosilicon compound of the present invention is a dimer or the like in which organosilicon compounds are hydrolyzed and condensed to form a siloxane bond.
ＲｎＳｉＸ４－ｎ・・・（Ｉ） R n SiX 4-n (I)
　式（Ｉ）中、Ｒは式（Ｉ）中のＳｉに炭素原子が直接結合する有機基を表し、Ｘは夫々水酸基又は加水分解性基を表す。ｎは１又は２を表し、ｎが２のとき各Ｒは同一でも異なっていてもよく、（４－ｎ）が２以上のとき各Ｘは同一でも異なっていてもよい。 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.
　ここで、Ｒで表される「Ｓｉに炭素原子が直接結合する有機基」としては、「置換されていてもよい炭化水素基」又は「ポリマー部分を含む炭化水素基」を挙げることができる。　
　上記「置換されていてもよい炭化水素基」の炭化水素基としては、通常、炭素数１～３０の炭化水素基であり、例えば、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキルアルキル基、アリール基、アリールアルキル基、アリールアルケニル基等が挙げられる。
　好ましくは、炭素数１～１０のアルキル基、炭素数３～８のシクロアルキル基、炭素数２～１０のアルケニル基、炭素数３～８のシクロアルケニル基、炭素数２～１０のアルキニル基である。 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” or “a hydrocarbon group including a polymer portion”.
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, an alkenyl group, a cycloalkenyl group, an alkynyl group. Group, cycloalkylalkyl group, aryl group, arylalkyl group, arylalkenyl group and the like.
Preferably, it is 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, or an alkynyl group having 2 to 10 carbon atoms. is there.
　また、上記「炭化水素基」は、酸素原子、窒素原子、又はケイ素原子を含んでいてもよい。 The “hydrocarbon group” may contain an oxygen atom, a nitrogen atom, or a silicon atom.
　「炭素数１～１０のアルキル基」としては、具体的には、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ネオペンチル基、ｎ－ヘキシル基、イソヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、イソノニル基、ｎ－デシル基等が挙げられる。 Specific examples of the “alkyl group having 1 to 10 carbon atoms” include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, Examples include isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group and the like.
　「炭素数３～８のシクロアルキル基」としては、具体的には、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。 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, a cyclooctyl group, and the like.
　「炭素数２～１０のアルケニル基」としては、具体的には、ビニル基、１－プロペン－１－イル基、２－プロぺン－１－イル基、１－プロペン－２－イル基、１－ブテン－１－イル基、２－ブテン－１－イル基、３－ブテン－１－イル基、１－ブテン－２－イル基、３－ブテン－２－イル基、１－ペンテン－１－イル基、４－ペンテン－１－イル基、１－ペンテン－２－イル基、４－ペンテン－２－イル基、３－メチル－１－ブテン－１－イル基、１－ヘキセン－１－イル基、５－ヘキセン－１－イル基、１－ヘプテン－１－イル基、６－ヘプテン－１－イル基、１－オクテン－１－イル基、７－オクテン－１－イル基等が挙げられる。 Specific examples of the “alkenyl group having 2 to 10 carbon atoms” include a vinyl group, 1-propen-1-yl group, 2-propen-1-yl group, 1-propen-2-yl group, 1-buten-1-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1-buten-2-yl group, 3-buten-2-yl group, 1-pentene-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-hexene-1- Yl group, 5-hexen-1-yl group, 1-hepten-1-yl group, 6-hepten-1-yl group, 1-octen-1-yl group, 7-octen-1-yl group, etc. It is done.
　「炭素数３～８のシクロアルケニル基」としては、具体的には、１－シクロペンテン－１－イル基、２－シクロペンテン－１－イル基、１－シクロヘキセン－１－イル基、２－シクロヘキセン－１－イル基、３－シクロヘキセン－１－イル基等が挙げられる。 Specific examples of the “C3-C8 cycloalkenyl group” include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, and 2-cyclohexene- Examples thereof include a 1-yl group and a 3-cyclohexen-1-yl group.
　「炭素数２～１０のアルキニル基」としては、具体的には、エチニル基、１－プロピン－１－イル基、２－プロピン－１－イル基、１－ブチン－１－イル基、３－ブチン－１－イル基、１－ペンチン－１－イル基、4－ペンチン－１－イル基、１－ヘキシン－１－イル基、５－ヘキシン－１－イル基、１－ヘプチン－１－イル基、１－オクチン－１－イル基、７－オクチン－１－イル基等が挙げられる。 Specific examples of the “alkynyl group having 2 to 10 carbon atoms” include 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.
　「シクロアルキルアルキル基」としては、炭素数３～１０のシクロアルキル基と炭素数１～１０のアルキル基の結合した基が挙げられる。
　「アリール基」は、単環又は多環のアリール基を意味し、多環アリール基の場合は、完全不飽和環に加え、部分飽和環を有する基も包含する。具体的には、フェニル基、ナフチル基、アズレニル基、インデニル基、インダニル基、テトラリニル基等が挙げられ、炭素数６～１０のアリール基が好ましい。
　「アリールアルキル基」としては、炭素数６～１０のアリール基と炭素数１～１０のアルキル基が結合した基が挙げられる。
　「アリールアルケニル基」としては、炭素数６～１０のアリール基と炭素数２～１０のアルケニル基が結合した基が挙げられる。 Examples of the “cycloalkylalkyl group” include 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.
The “aryl group” means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, a group having a partially saturated ring in addition to a fully unsaturated ring is also included. Specific examples include a phenyl group, a naphthyl group, 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.
Examples of the “arylalkyl group” include a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded.
Examples of the “arylalkenyl group” include a group in which an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are bonded.
　「酸素原子を有する炭化水素基」としては、アルコキシアルキル基；エポキシ基、エポキシアルキル基、グリシジルオキシアルキル基等のオキシラン環（エポキシ基）を有する基；アクリロキシメチル基、メタクリロキシメチル基等が挙げられる。 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 epoxyalkyl group, and a glycidyloxyalkyl group; an acryloxymethyl group, a methacryloxymethyl group, and the like. Can be mentioned.
　ここで、「アルコキシアルキル基」としては、炭素数１～６のアルコキシ基と炭素数１～６のアルキル基が結合した基が挙げられる。具体的には、メトキシメチル基、メトキシプロピル基、エトキシエチル基、エトキシブチル基等が挙げられる。
　「エポキシアルキル基」としては、炭素数３～１０のエポキシアルキル基が好ましく、具体的には、グリシジル基、グリシジルメチル基、２－グリシジルエチル基、３－グリシジルプロピル基、４－グリシジルブチル基、３，４－エポキシブチル基、４，５－エポキシペンチル基、５，６－エポキシヘキシル基等のエポキシ基を含む直鎖状のアルキル基；β－メチルグリシジル基、β－エチルグリシジル基、β－プロピルグリシジル基、２－グリシジルプロピル基、２－グリシジルブチル基、３－グリシジルブチル基、２－メチル－３－グリシジルプロピル基、３－メチル－２－グリシジルプロピル基、３－メチル－３，４－エポキシブチル基、３－エチル－３，４－エポキシブチル基、４－メチル－４，５－エポキシペンチル基、５－メチル－５，６－エポキシヘキシル基等のエポキシ基を含む分岐鎖状のアルキル基等が挙げられる。
　グリシジルオキシアルキル基としては、具体的には、グリシジルオキシメチル基、グリシジルオキシプロピル基等が挙げられる。 Here, examples of the “alkoxyalkyl group” include 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. Specific examples include a methoxymethyl group, a methoxypropyl group, an ethoxyethyl group, and an ethoxybutyl group.
The “epoxyalkyl group” is preferably an epoxyalkyl group having 3 to 10 carbon atoms, specifically, a glycidyl group, a glycidylmethyl group, a 2-glycidylethyl group, a 3-glycidylpropyl group, a 4-glycidylbutyl group, Linear alkyl group containing an epoxy group 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-methyl Like branched-chain alkyl group containing an epoxy group such as 5,6-epoxy hexyl group.
Specific examples of the glycidyloxyalkyl group include a glycidyloxymethyl group and a glycidyloxypropyl group.
　「窒素原子を有する炭化水素基」としては、－ＮＲ’２（式中、Ｒ’は水素原子、アルキル基又はアリール基を表し、各Ｒ’は互いに同一でも相異なっていてもよい。）を有する炭化水素基、又は－Ｎ＝ＣＲ’’２（式中、Ｒ’’は水素原子、アルキル基、又はアリール基を表し、各Ｒ’’は互いに同一でも相異なっていてもよい。）を有する炭化水素基が挙げられる。 As the “hydrocarbon group having a nitrogen atom”, —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 —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). The hydrocarbon group which has is mentioned.
　例えば、－ＮＲ’２を有する炭化水素基としては、具体的には、アミノメチル基、１－アミノエチル基、Ｎ－メチルアミノメチル基等が挙げられる。－Ｎ＝ＣＲ’’２を有する基としては、具体的には、－ＣＨ２Ｎ＝ＣＨＣＨ３基、－ＣＨ２Ｎ＝Ｃ（ＣＨ３）２基、－ＣＨ２ＣＨ２Ｎ＝ＣＨＣＨ３基、－ＣＨ２Ｎ＝ＣＨＰｈ基、－ＣＨ２Ｎ＝Ｃ（Ｐｈ）ＣＨ３基等が挙げられる。 For example, specific examples of the hydrocarbon group having —NR ′ 2 include an aminomethyl group, a 1-aminoethyl group, and an N-methylaminomethyl group. Examples of the group having a -N = CR '' 2, specifically, -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.
　上記「置換されていてもよい」の置換基としては、ハロゲノ基、アルキル基、アルケニル基、アリール基、アルコキシ基、エポキシ基、グリシジルオキシ基、アクリロキシ基、メタクリロキシ基、－ＮＲ’２を有する基（式中、Ｒ’は水素原子、アルキル基又はアリール基を表し、各Ｒ’は互いに同一でも相異なっていてもよい。）等を挙げることができる。 Examples of the substituent that may be substituted include a halogeno group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an epoxy group, a glycidyloxy group, an acryloxy group, 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 as or different from each other).
　詳しくは、上記「置換されていてもよい」の置換基としては、ハロゲノ基、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数６～１０のアリール基、炭素数１～６のアルコキシ基、エポキシ基、グリシジルオキシ基、アクリロキシ基、メタクリロキシ基、－ＮＲ’２を有する基（式中、Ｒ’は水素原子、炭素数１～１０のアルキル基又は炭素数６～１０のアリール基を表し、各Ｒ’は互いに同一でも相異なっていてもよい。）等を挙げることができる。アルキル基、アルケニル基、アリール基としては、Ｒにおけるものと同じ炭化水素基が挙げられる。
　「炭素数１～６のアルコキシ基」としては、具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｔ－ブトキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、ｎ－ヘキシルオキシ基、イソヘキシルオキシ基等が挙げられる。
　「ハロゲノ基」としては、具体的には、フルオロ基、クロロ基、ブロモ基、イオド基等が挙げられる。 Specifically, the substituent of the above “optionally substituted” includes a halogeno 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 groups, epoxy groups, glycidyloxy groups, acryloxy groups, methacryloxy groups, groups having —NR ′ 2 (wherein R ′ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms) 10 aryl groups, and each R ′ may be the same as or different from each other. Examples of the alkyl group, alkenyl group, and aryl group include the same hydrocarbon groups as those in R.
Specific examples of the “C 1-6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, and n-pentyloxy. Group, isopentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group and the like.
Specific examples of the “halogeno group” include a fluoro group, a chloro group, a bromo group, and an iodo group.
　上記のうち、ビニル基、オキシラン環（エポキシ基）を有する基、－ＮＲ’２を有する基、又は－Ｎ＝ＣＲ’’２を有する基は、有機無機複合体の表面の無機化の観点からは、好ましい基である。 Among the above, vinyl group, a group having an oxirane ring (epoxy group), -NR 'group having 2 or -N = CR' groups with '2, from the viewpoint of mineralization of the surface of the organic-inorganic composite Is a preferred group.
　また、式（Ｉ）中、ｎは、１又は２を表し、ｎが１のものが特に好ましい。ｎが２のとき、各Ｒは同一でも相異なっていてもよい。 In formula (I), n represents 1 or 2, and n is particularly preferably 1. When n is 2, each R may be the same or different.
　式（Ｉ）において、Ｘは、水酸基又は加水分解性基を表す。式（Ｉ）の（４－ｎ）が２以上のとき、各Ｘは同一でも相異なっていてもよい。加水分解性基とは、例えば、無触媒、過剰の水の共存下、２５℃～１００℃で加熱することにより、加水分解されてシラノール基を生成できる基や、シロキサン縮合物を形成できる基を意味し、アルコキシ基、アシルオキシ基、ハロゲノ基、イソシアネート基、アミノ基若しくは置換アミノ基等を挙げることができ、炭素数１～４のアルコキシ基又は炭素数１～６のアシルオキシ基が好ましい。 In the formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) in formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a group that can form a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of non-catalyst and excess water. Meaning includes an alkoxy group, an acyloxy group, a halogeno group, an isocyanate group, an amino group, or a substituted amino group, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 6 carbon atoms is preferable.
　「炭素数１～４のアルコキシ基」としては、具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｔ－ブトキシ基等が挙げられる。
　「炭素数１～６のアシルオキシ基」（ただし、炭素数にはカルボニル基の炭素を含まない）としては、具体的には、アセトキシ基、ベンゾイルオキシ基等が挙げられる。
　「ハロゲノ基」としては、具体的には、フルオロ基、クロロ基、ブロモ基、イオド基等が挙げられる。 Specific examples of the “C 1-4 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group and the like.
Specific examples of the “acyloxy group having 1 to 6 carbon atoms” (however, the carbon number does not include carbon of the carbonyl group) include an acetoxy group and a benzoyloxy group.
Specific examples of the “halogeno group” include a fluoro group, a chloro group, a bromo group, and an iodo group.
　式（Ｉ）で表される有機ケイ素化合物としては、具体的には、メチルトリクロロシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリイソプロポキシシラン、エチルトリブトキシシラン、ブチルトリメトキシシラン、ペンタフルオロフェニルトリメトキシシラン、フェニルトリメトキシシラン、ノナフルオロブチルエチルジメトキシシラン、トリフルオロメチルトリメトキシシラン、ジメチルジアミノシラン、ジメチルジクロロシラン、ジメチルジアセトキシシラン、ジメチルジメトキシシラン、ジフェニルジメトキシシラン、ジブチルジメトキシシラン、ビニルトリメトキシシラン、３－（メタ）アクリロキシ－ｎ－プロピルトリメトキシシラン、３－（３－メチル－３－オキセタンメトキシ）－ｎ－プロピルトリメトキシシラン、４－オキサシクロヘキシルトリメトキシシラン、メチルトリス[（メタ）アクリロキシ]シラン、メチルトリス［２－（メタ）アクリロキシエトキシ］シラン、メチル－トリグリシジルオキシシラン、メチルトリス（３－メチル－３－オキセタンメトキシ）シラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシジルオキシ－ｎ－プロピルトリメトキシシラン、３－グリシジルオキシ－ｎ－プロピルメチルジエトキシシラン、３－グリシジルオキシ－ｎ－プロピルトリエトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、３－アニリノプロピルトリメトキシシラン等が挙げられる。 Specific examples of the organosilicon compound represented by the formula (I) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyl Tributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyldimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxy Silane, diphenyldimethoxysilane, dibutyldimethoxysilane, vinyltrimethoxysilane, 3- (meth) acryloxy-n-propyltrimethoxysilane, 3- ( -Methyl-3-oxetanemethoxy) -n-propyltrimethoxysilane, 4-oxacyclohexyltrimethoxysilane, methyltris [(meth) acryloxy] silane, methyltris [2- (meth) acryloxyethoxy] silane, methyl-triglycidyl Oxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane, vinyltrichlorosilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxy-n-propyltrimethoxy Silane, 3-glycidyloxy-n-propylmethyldiethoxysilane, 3-glycidyloxy-n-propyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl -Butylidene) propylamine, 3-anilinopropyltrimethoxysilane and the like.
　Ｒがポリマー部分を含む炭化水素基である有機ケイ素化合物とは、重合性官能基を有する有機ケイ素化合物を、必要に応じて他の重合性官能基を有する単量体と共重合させて得られるポリマーを表し、３－メタクリロキシプロピルトリメトキシシランと、メチルメタクリレート、ブチルメタクリレート等のメタクリル酸エステル、又はメタクリル酸等と共重合して得られるポリマー等が挙げられる。
　また、Ｒがポリマー部分を含む炭化水素基である有機ケイ素化合物の別な例としては、高分子反応で、有機ケイ素部分を導入して得られるポリマーを示し、ポリメタクリル酸に対して、３－グリシジルオキシプロピルトリメトキシシランを反応させて、側鎖にアルコキシシラン部位を導入したポリマー、１，２－ポリブタジエン側鎖二重結合にトリメトキシヒドロシラン等によるヒドロシリル化によりシリル基を導入したポリマー等が挙げられる。
　重合性官能基を有する有機ケイ素化合物と重合可能な単量体としては、具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２－エチルヘキシル、シクロヘキシル（メタ）アクリレート等の（メタ）アクリル酸エステル；（メタ）アクリル酸、イタコン酸、フマル酸等のカルボン酸および無水マレイン酸等の酸無水物；グリシジル（メタ）アクリレート等のエポキシ化合物；ジエチルアミノエチル（メタ）アクリレート、アミノエチルビニルエーテル等のアミノ化合物；（メタ）アクリルアミド、イタコン酸ジアミド、α－エチルアクリルアミド、クロトンアミド、フマル酸ジアミド、マレイン酸ジアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド等のアミド化合物；アクリロニトリル、スチレン、α－メチルスチレン、塩化ビニル、酢酸ビニル、プロピオン酸ビニル、ビスフェノールＡ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、トリグリシジルイソシアヌレート等が挙げられる。
　また、高分子反応により、有機ケイ素部分を導入することが可能なポリマーとしては、具体的には、ポリ（メタ）アクリル酸、ｐ－ヒドロキシスチレン、ポリブタジエン等が挙げられる。 The organosilicon compound in which R is a hydrocarbon group containing a polymer moiety is obtained by copolymerizing an organosilicon compound having a polymerizable functional group with a monomer having another polymerizable functional group as necessary. Examples of the polymer include 3-methacryloxypropyltrimethoxysilane and methacrylic acid esters such as methyl methacrylate and butyl methacrylate, or polymers obtained by copolymerization with methacrylic acid and the like.
Another example of an organosilicon compound in which R is a hydrocarbon group containing a polymer moiety is a polymer obtained by introducing an organosilicon moiety by a polymer reaction. Examples include polymers in which glycidyloxypropyltrimethoxysilane is reacted to introduce alkoxysilane moieties in the side chains, and polymers in which silyl groups are introduced into 1,2-polybutadiene side chain double bonds by hydrosilylation with trimethoxyhydrosilane or the like. It is done.
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. (Meth) acrylic acid esters such as 2-ethylhexyl and cyclohexyl (meth) acrylate; carboxylic acids such as (meth) acrylic acid, itaconic acid and fumaric acid and acid anhydrides such as maleic anhydride; glycidyl (meth) acrylate and the like Epoxy 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) Amide compounds such as acrylamide; Rironitoriru, styrene, alpha-methyl styrene, vinyl chloride, vinyl acetate, vinyl propionate, bisphenol A type epoxy resins, phenol novolak type epoxy resin, triglycidyl isocyanurate.
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.
　有機ケイ素化合物及び／又はその縮合物の配合量は、有機ケイ素化合物及び／又はその縮合物、光感応性化合物、光重合開始剤、及び電磁線硬化性化合物の全固形分に対して、２～９８質量％、好ましくは５～５０質量％、更に好ましくは５～３０質量％である。
　また、有機ケイ素化合物の縮合物の平均粒子径は２ｎｍ～１００ｎｍが好ましく、５ｎｍ～３０ｎｍであることがより好ましい。平均粒子径が１００ｎｍより大きい場合、形成用組成物自体が不安定となりゲル化し易くなり、また得られる有機無機複合体が白濁する。平均粒子径が２ｎｍより小さい場合は、塗膜性に悪影響が出る場合がある。 The compounding amount of the organosilicon compound and / or its condensate is 2 to 2 with respect to the total solid content of the organosilicon compound and / or its condensate, photosensitive compound, photopolymerization initiator, and electromagnetic radiation curable compound. It is 98% by mass, preferably 5 to 50% by mass, more preferably 5 to 30% by mass.
The average particle size of the condensate of the organosilicon compound is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. When the average particle size is larger than 100 nm, the forming composition itself becomes unstable and easily gels, and the obtained organic-inorganic composite becomes cloudy. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.
（２）光感応性化合物
　本発明の光感応性化合物は、金属錯体、金属有機酸塩、２以上の水酸基若しくは加水分解性基を有する金属化合物、それらの加水分解物、及びそれらの縮合物からなる群より選ばれる少なくとも１種の３５０ｎｍ以下の波長の光に感応する光感応性化合物である。
　本発明の光感応性化合物は、シラノール縮合を触媒し、有機ケイ素化合物の縮合に寄与する。 (2) Photosensitive compound The photosensitive compound of the present invention comprises a metal complex, a metal organic acid salt, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensate thereof. A photosensitive compound sensitive to at least one light having a wavelength of 350 nm or less selected from the group consisting of:
The photosensitive compound of the present invention catalyzes silanol condensation and contributes to the condensation of the organosilicon compound.
　３５０ｎｍ以下の波長の光とは、３５０ｎｍ以下のいずれかの波長の光を成分とする光源を用いてなる光、好ましくは、３５０ｎｍ以下のいずれかの波長の光を主成分とする光源を用いてなる光、すなわち、最も成分量の多い波長が３５０ｎｍ以下の光源を用いてなる光を意味する。 Light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less as a component, preferably using a light source having light of any wavelength of 350 nm or less as a main component Light, that is, light using a light source having a wavelength of 350 nm or less with the largest amount of component.
　上記金属錯体としては、水酸基若しくは加水分解性基を有する金属錯体であることが好ましく、２以上の水酸基若しくは加水分解性基を有する金属錯体であることがより好ましい。なお、２以上の水酸基若しくは加水分解性基を有するとは、加水分解性基及び水酸基の合計が２以上であることを意味する。また、前記金属錯体としては、β－ケトカルボニル化合物、β－ケトエステル化合物、及びα－ヒドロキシエステル化合物が配位した化合物が好ましく、具体的には、アセト酢酸メチル、アセト酢酸ｎ－プロピル、アセト酢酸イソプロピル、アセト酢酸ｎ－ブチル、アセト酢酸ｓｅｃ－ブチル、アセト酢酸ｔ－ブチル等のβ－ケトエステル類；アセチルアセトン、へキサン－２，４－ジオン、ヘプタン－２，４－ジオン、ヘプタン－３，５－ジオン、オクタン－２，４－ジオン、ノナン－２，４－ジオン、５－メチル－へキサン－２，４－ジオン等のβ－ジケトン類；グリコール酸、乳酸等のヒドロキシカルボン酸等が配位した化合物が挙げられる。 The metal complex 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, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. The metal complex is preferably a compound in which a β-ketocarbonyl compound, β-ketoester compound, and α-hydroxyester compound are coordinated. Specifically, methyl acetoacetate, n-propyl acetoacetate, acetoacetic acid Β-ketoesters such as isopropyl, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5 -Β-diketones such as dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid Compound.
　上記金属有機酸塩は、金属イオンと有機酸から得られる塩であり、有機酸としては、酢酸、シュウ酸、酒石酸、安息香酸等のカルボン酸類；スルフォン酸、スルフィン酸等の含硫黄有機酸；フェノール化合物；エノール化合物；オキシム化合物；イミド化合物；芳香族スルフォンアミド；等の酸性を呈する有機化合物が挙げられる。 The metal organic acid salt is 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; sulfur-containing organic acids such as sulfonic acid and sulfinic acid; Organic compounds exhibiting acidity such as phenol compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides;
　また、上記２以上の水酸基若しくは加水分解性基を有する金属化合物は、上記金属錯体及び上記金属有機酸塩以外のものであり、例えば、金属水酸化物や、金属ｎ－プロポキシド、金属イソプロポキシド、金属ｎ－ブトキシド等の金属アルコラート等を挙げることができる。 The metal compound having two or more hydroxyl groups or hydrolyzable groups is other than the metal complex and the metal organic acid salt, and examples thereof include metal hydroxide, metal n-propoxide, metal isopropoxy. And metal alcoholates such as metal n-butoxide.
　上記金属錯体、上記金属有機酸塩、又は上記２以上の水酸基若しくは加水分解性基を有する金属化合物における加水分解性基としては、例えば、アルコキシ基、アシルオキシ基、ハロゲノ基、イソシアネート基が挙げられ、炭素数１～４のアルコキシ基、炭素数１～４のアシルオキシ基が好ましい。なお、２以上の水酸基若しくは加水分解性基を有するとは、加水分解性基及び水酸基の合計が２以上であることを意味する。 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 an alkoxy group, an acyloxy group, a halogeno group, and an isocyanate group. An alkoxy group having 1 to 4 carbon atoms and an acyloxy group having 1 to 4 carbon atoms 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.
　２以上の水酸基若しくは加水分解性基を有する金属化合物の加水分解物及び／又は縮合物としては、２以上の水酸基若しくは加水分解性基を有する金属化合物１モルに対して、０．５モル以上の水を用いて加水分解したものであることが好ましく、０．５～２モルの水を用いて加水分解したものであることがより好ましい。 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 hydrolyzed using water, more preferably hydrolyzed using 0.5 to 2 mol of water.
　また、金属錯体の加水分解物及び／又は縮合物としては、金属錯体１モルに対して、５～１００モルの水を用いて加水分解したものであることが好ましく、５～２０モルの水を用いて加水分解したものであることがより好ましい。 The hydrolyzate and / or condensate of the metal complex is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal complex. More preferably, it is hydrolyzed by use.
　また、金属有機酸塩の加水分解物及び／又は縮合物としては、金属有機酸塩１モルに対して、５～１００モルの水を用いて加水分解したものであることが好ましく、５～２０モルの水を用いて加水分解したものであることがより好ましい。 Further, the hydrolyzate and / or condensate of the metal organic acid salt is preferably one obtained by hydrolyzing with 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt. More preferably, it is hydrolyzed with molar water.
　また、これら金属錯体、金属有機酸塩、又は２以上の水酸基若しくは加水分解性基を有する金属化合物における金属としては、チタン（Ｔｉ）、ジルコニウム（Ｚｒ）、アルミニウム（Ａｌ）、ケイ素（Ｓｉ）、ゲルマニウム（Ｇｅ）、インジウム（Ｉｎ）、スズ（Ｓｎ）、タンタル（Ｔａ）、亜鉛（Ｚｎ）、タングステン（Ｗ）、鉛（Ｐｂ）等が挙げられ、これらの中でもチタン（Ｔｉ）、アルミニウム（Ａｌ）、ジルコニウム（Ｚｒ）、スズ（Ｓｎ）が好ましく、特にチタン（Ｔｉ）が好ましい。これらは１種単独で用いてもよいし、２種以上用いることもできる。 Examples of the metal in these metal complexes, metal organic acid salts, or metal compounds having two or more hydroxyl groups or hydrolyzable groups include titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), Examples include germanium (Ge), indium (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), etc. Among these, titanium (Ti), aluminum (Al ), Zirconium (Zr), and tin (Sn) are preferable, and titanium (Ti) is particularly preferable. These may be used alone or in combination of two or more.
　本発明において用いる光感応性化合物は、加水分解物及び／又は縮合物であることが好ましく、特に、金属錯体の加水分解物及び／又は縮合物が好ましく、その平均粒径としては、２０ｎｍ以下であることが好ましく、１０ｎｍ以下であることがより好ましい。これにより、有機無機複合体の透明性を向上させることができる。 The light-sensitive compound used in the present invention is preferably a hydrolyzate and / or a condensate, in particular, a hydrolyzate and / or a condensate of a metal complex, and its average particle size is 20 nm or less. It is preferable that the thickness is 10 nm or less. Thereby, the transparency of the organic-inorganic composite can be improved.
　光感応性化合物の含有量としては、その種類にもよるが、一般的に、有機ケイ素化合物中のＳｉに対して、光感応性化合物中の金属原子が０．０１～０．５モル当量、好ましくは０．０５～０．２モル当量であることが好ましい。　 The content of the photosensitive compound depends on its type, but generally 0.01 to 0.5 molar equivalent of metal atoms in the photosensitive compound with respect to Si in the organosilicon compound, It is preferably 0.05 to 0.2 molar equivalent. *
（３）ベンジルメチルケタール系光重合開始剤
　本発明で用いるベンジルメチルケタール系光重合開始剤は、波長が３７５ｎｍから４２０ｎｍの光を含むエネルギー線に対して吸光係数が小さい光重合開始剤であり、例えば２，２’－ジメトキシ－１，２－ジフェニルエタン－１－オン（ＢＡＳＦ製「Ｉｒｇａｃｕｒｅ（登録商標）６５１」）等が挙げられる。 (3) Benzylmethyl ketal photopolymerization initiator The benzylmethyl ketal photopolymerization initiator used in the present invention is a photopolymerization initiator having a small extinction coefficient with respect to energy rays containing light having a wavelength of 375 nm to 420 nm, Examples thereof include 2,2′-dimethoxy-1,2-diphenylethane-1-one (“Irgacure (registered trademark) 651” manufactured by BASF).
　本発明において用いられる光重合開始剤の配合量は、電磁線硬化性化合物に対して、０．０１～２０質量％配合することが好ましく、０．１～１０質量％が、さらに好ましい。 The blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the electromagnetic radiation curable compound.
　なお、本発明においては、必要に応じて増感剤を添加することができる、例えば、トリメチルアミン、メチルジメタノールアミン、トリエタノールアミン、ｐ－ジメチルアミノアセトフェノン、ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジメチルアミノ安息香酸イソアミル、Ｎ，Ｎ－ジメチルベンジルアミン、及び４，４’－ビス（ジエチルアミノ）ベンゾフェノン等が使用できる。 In the present invention, a sensitizer can be added as necessary. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p- Isoamyl dimethylaminobenzoate, N, N-dimethylbenzylamine, 4,4′-bis (diethylamino) benzophenone, and the like can be used.
（４）電磁線硬化性化合物
　本発明の電磁線硬化性化合物は、前記光重合開始剤の存在下、電磁線の照射により重合反応を起こす官能基を有する化合物又は樹脂である。
　電磁線としては、紫外線、Ｘ線、放射線、イオン化放射線、電離性放射線（α線、β線、γ線、中性子線、電子線）を用いることができ、３５０ｎｍ以下の波長を含む光が好ましい。
　電磁線の照射には、超高圧水銀ランプ、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマーランプ、カーボンアークランプ、キセノンアークランプ等の公知の装置を用いて行うことができ、照射する光源としては、１５０～３５０ｎｍの範囲のいずれかの波長の光を含む光源であることが好ましく、２５０～３１０ｎｍの範囲のいずれかの波長の光を含む光源であることがより好ましい。
　また、有機無機複合体形成用組成物を十分に硬化させるために照射する光の照射光量は、０．１～１００Ｊ／ｃｍ２程度であり、組成物の硬化効率（照射エネルギーと組成物の硬化程度の関係）を考慮すると、０．４～１０Ｊ／ｃｍ２程度であることが好ましく、０．４～５Ｊ／ｃｍ２程度であることがより好ましい。 (4) Electromagnetic radiation curable compound The electromagnetic radiation curable compound of the present invention is a compound or resin having a functional group that undergoes a polymerization reaction upon irradiation with electromagnetic radiation in the presence of the photopolymerization initiator.
As the electromagnetic radiation, ultraviolet rays, X-rays, radiation, ionizing radiation, ionizing radiation (α rays, β rays, γ rays, neutron rays, electron beams) can be used, and light having a wavelength of 350 nm or less is preferable.
Irradiation of electromagnetic radiation can be performed using a known apparatus such as an ultra-high 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. Is preferably a light source including light of any wavelength in the range of 150 to 350 nm, and more preferably a light source including light of any wavelength in the range of 250 to 310 nm.
In addition, the amount of light irradiated to sufficiently cure the organic-inorganic composite-forming composition is about 0.1 to 100 J / cm 2 , and the curing efficiency of the composition (irradiation energy and curing of the composition) In consideration of the degree relationship), it is preferably about 0.4 to 10 J / cm 2 , and more preferably about 0.4 to 5 J / cm 2 .
　電磁線硬化性化合物としては、具体的には、（メタ）アクリレート系化合物を含むビニル化合物、エポキシ樹脂等が挙げられる。電磁線の照射により重合反応を起こす官能基の数は、１個以上であれば特に限定はない。 Specific examples of the electromagnetic radiation curable compound include a vinyl compound containing a (meth) acrylate compound, an epoxy resin, and the like. The number of functional groups that cause a polymerization reaction upon irradiation with electromagnetic radiation is not particularly limited as long as it is one or more.
　（メタ）アクリレート系化合物としては、具体的には、ポリウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート 、エポキシ（メタ）アクリレート 、ポリアミド（メタ）アクリレート、ポリブタジエン（メタ）アクリレート 、ポリスチリル（メタ）アクリレート 、ポリカーボネートジアクリレート、トリプロピレングリコールジ（メタ）アクリレート 、ヘキサンジオールジ（メタ）アクリレート 、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、（メタ）アクリロイルオキシ基を有するシロキサンポリマー等が挙げられるが、好ましくはポリエステル（メタ）アクリレート、ポリウレタン（メタ）アクリレート、エポキシポリ（メタ）アクリレートであり、より好ましくは、ポリウレタン（メタ）アクリレートである。 Specific examples of the (meth) acrylate compound include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, Polycarbonate diacrylate, tripropylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) Examples thereof include siloxane polymers having an acryloyloxy group, preferably polyester (meth) acrylate and polyurethane (meth) acrylic. Over DOO, an epoxy poly (meth) acrylate, more preferably a polyurethane (meth) acrylate.
　エポキシ（メタ）アクリレートは、低分子量のビスフェノール型エポキシ樹脂やノボラックエポキシ樹脂のオキシラン環とアクリル酸とのエステル化反応により得ることができる。
　ポリエステル（メタ）アクリレートは、多価カルボン酸と多価アルコールの縮合によって得られる、両末端に水酸基を有するポリエステルオリゴマーの水酸基をアクリル酸でエステル化することにより得られる。また、多価カルボン酸にアルキレンオキシドを付加して得られるオリゴマーの末端の水酸基をアクリル酸でエステル化することにより得られる。
　ウレタン（メタ）アクリレートは、ポリオールとジイソシアネートとを反応させて得られるイソシアネート化合物と、水酸基を有するアクリレートモノマーとの反応生成物であり、ポリオールとしては、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートジオール等が挙げられる。 Epoxy (meth) acrylate can be obtained by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin and acrylic acid.
The polyester (meth) acrylate is obtained by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with acrylic acid. It can also be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.
Urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol, polyether polyol, polycarbonate diol, and the like. It is done.
　また、アクリレート系化合物以外のビニル化合物としては、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、酢酸ビニル、スチレン、不飽和ポリエステル等が挙げられ、エポキシ樹脂としては、水素添加ビスフェノールＡジグリシジルエーテル、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート等が挙げられる。
　電磁線硬化性化合物の分子量は、有機無機複合体形成用組成物中に溶解する限り限度はないが、通常は質量平均分子量として５００～５０，０００、好ましくは１，０００～１０，０００である。 Examples of vinyl compounds other than acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. Epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxy (Cyclohexylmethyl) adipate and the like.
The molecular weight of the electromagnetic radiation curable compound is not limited as long as it dissolves in the composition for forming an organic-inorganic composite, but is usually 500 to 50,000, preferably 1,000 to 10,000 as a weight average molecular weight. .
　本発明において用いられる電磁線硬化性化合物の配合量は、有機ケイ素化合物及び／又はその縮合物、光感応性化合物、光重合開始剤、及び電磁線硬化性化合物の全固形分に対して、２～９８質量％、好ましくは５～９５質量％である。 The blending amount of the electromagnetic radiation curable compound used in the present invention is 2 with respect to the total solid content of the organosilicon compound and / or the condensate thereof, the photosensitive compound, the photopolymerization initiator, and the electromagnetic radiation curable compound. It is ˜98% by mass, preferably 5 to 95% by mass.
（５）Ｆｅｄｏｒｓの推算法により求められた溶解パラメーターに基づく有機ケイ素化合物と電磁線硬化性化合物の組合せ
　本発明に用いる有機ケイ素化合物は、式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）であることが好ましい。ＳＰ１とＳＰ２の差は、１．６～８．５が好ましく、１．６～７．２がより好ましい。
　本発明において用いる有機ケイ素化合物は、更にＳＰ１がＳＰ２よりも１．６未満小さい有機ケイ素化合物、又はＳＰ１がＳＰ２よりも大きい有機ケイ素化合物（Ｓｉ２）を含んでいても良く、Ｓｉ１とＳｉ２との比（Ｓｉ１：Ｓｉ２）は、５：５～１０：０であり、好ましくは、９：１～１０：０である。 (5) Combination of organosilicon compound and electromagnetic radiation curable compound based on solubility parameter determined by Fedors' estimation method The organosilicon compound used in the present invention is determined by R's Fedors estimation method in formula (I). The solubility parameter (SP1) is preferably an organosilicon compound (Si1) smaller than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. The difference between SP1 and SP2 is preferably 1.6 to 8.5, and more preferably 1.6 to 7.2.
The organosilicon compound used in the present invention may further contain an organosilicon compound in which SP1 is less than 1.6 less than SP2, or an organosilicon compound (Si2) in which SP1 is greater than SP2, and the ratio between Si1 and Si2 (Si1: Si2) is 5: 5 to 10: 0, and preferably 9: 1 to 10: 0.
　すなわち、本発明の有機無機複合体形成用組成物は、上記有機ケイ素化合物に加えて、前記光感応性化合物、前記ベンジルメチルケタール系光重合開始剤、及び前記電磁線硬化性化合物を含有する。 That is, the organic-inorganic composite-forming composition of the present invention contains the photosensitive compound, the benzyl methyl ketal photopolymerization initiator, and the electromagnetic radiation curable compound in addition to the organosilicon compound.
　有機ケイ素化合物は、電磁線硬化性化合物の種類に応じて異なる。有機ケイ素化合物及び電磁線硬化性化合物の溶解パラメータ（ＳＰ値）はＦｅｄｏｒｓの推算法に基づき計算することができるから、あらかじめ計算されたＳＰ値を基に、有機ケイ素化合物と電磁線硬化性化合物の組み合わせを決定することができる。
　前記式（Ｉ）において、ｎが２であり、かつ、Ｒが異なる場合、数値が大きい方のＳＰ値を前記ＳＰ１として、電磁線硬化性化合物との組み合わせを決定する。 The organosilicon compound differs depending on the type of electromagnetic radiation curable compound. Since the solubility parameter (SP value) of the organosilicon compound and the electromagnetic radiation curable compound can be calculated based on the Fedors' estimation method, the organosilicon compound and the electromagnetic radiation curable compound can be calculated based on the precalculated SP value. A combination can be determined.
In the formula (I), when n is 2 and R is different, the SP value having the larger numerical value is set as the SP1, and the combination with the electromagnetic radiation curable compound is determined.
　本発明に用いることができる有機ケイ素化合物の一例をＳＰ値と共に以下の表１に列記する。 Examples of organosilicon compounds that can be used in the present invention are listed in Table 1 below together with SP values.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　続いて、本発明に用いることができる代表的な電磁線硬化性化合物のＳＰ値を表２に列記する。 Subsequently, SP values of typical electromagnetic radiation curable compounds that can be used in the present invention are listed in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記の化合物以外の、ポリウレタン（メタ）アクリレート、ポリエステル（メタ）アクリレート、エポキシポリ（メタ）アクリレート、ポリアミド（メタ）アクリレート、ポリブタジエン（メタ）アクリレート、ポリスチリル（メタ）アクリレート、ポリカーボネートジアクリレート等のアクリレート系化合物については、そのＳＰ値は、含有する官能基の種類にもよるが、９～１１の範囲内である。 Other than the above compounds, acrylates such as polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy poly (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, etc. For compounds, the SP value is in the range of 9 to 11 depending on the type of functional group contained.
　本発明においては、電磁線硬化性化合物が、（メタ）アクリレート系化合物である場合、有機ケイ素化合物（Ｓｉ１）と（Ｓｉ２）の組合せとしては、ビニルトリメトキシシランと３－メタクリロキシ－ｎ－プロピルトリメトキシシランの組み合わせ、ビニルトリメトキシシランと３－グリシジルオキシ－ｎ－プロピルトリメトキシシランの組み合わせ等が好ましい。 In the present invention, when the electromagnetic radiation curable compound is a (meth) acrylate compound, the combination of the organosilicon compound (Si1) and (Si2) includes vinyltrimethoxysilane and 3-methacryloxy-n-propyltri A combination of methoxysilane and a combination of vinyltrimethoxysilane and 3-glycidyloxy-n-propyltrimethoxysilane are preferred.
（６）その他の成分
　本発明に用いる溶媒としては、特に制限されるものではなく、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ヘキサン、オクタン等の脂肪族炭化水素類；シクロヘキサン、シクロペンタン等の脂環族炭化水素類；アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類；テトラヒドロフラン、ジオキサン等のエーテル類；酢酸エチル、酢酸ブチル等のエステル類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド等のアミド類；ジメチルスルホキシド等のスルホキシド類；メタノール、エタノール等のアルコール類；エチレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセテート等の多価アルコール誘導体類；等が挙げられる。これらの溶媒は１種単独で、あるいは２種以上を組み合わせて用いることができる。 (6) Other components The solvent 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; cyclohexane, Cycloaliphatic hydrocarbons such as cyclopentane; ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; N, N-dimethylformamide, N, N— Amides such as dimethylacetamide; Sulfoxides such as dimethyl sulfoxide; Alcohols such as methanol and ethanol; Polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; These solvents can be used alone or in combination of two or more.
　本発明の有機無機複合体形成用組成物には、その他、オルトギ酸メチル、オルト酢酸メチル、テトラエトキシシラン等の公知の脱水剤、各種界面活性剤、前記以外のシランカップリング剤、チタンカップリング剤、染料、分散剤、増粘剤、レベリング剤等の添加剤を添加することもできる。 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 those described above, and titanium couplings. Additives such as agents, dyes, dispersants, thickeners, and leveling agents can also be added.
　本発明の有機無機複合体形成用組成物中の固形分（有機ケイ素化合物及び／又はその縮合物、光感応性化合物、光重合開始剤、及び電磁線硬化性化合物）としては、１～７５質量％であることが好ましく、１０～６０質量％であることがより好ましい。 The solid content (organosilicon compound and / or condensate thereof, photosensitive compound, photopolymerization initiator, and electromagnetic radiation curable compound) in the composition for forming an organic-inorganic composite of the present invention is 1 to 75 masses. %, Preferably 10 to 60% by mass.
（７）有機無機複合体形成用組成物の調製方法
　本発明の有機無機複合体形成用組成物は、必要に応じて水及び／又は溶媒を加え、有機ケイ素化合物、光感応性化合物、光重合開始剤、及び電磁線硬化性化合物を混合して調製できる。 (7) Preparation method of composition for forming organic / inorganic composite The composition for forming an organic / inorganic composite of the present invention is added with water and / or a solvent, if necessary, to form an organosilicon compound, a photosensitive compound, and a photopolymerization. It can be prepared by mixing an initiator and an electromagnetic radiation curable compound.
　例えば、光感応性化合物を溶媒に混合し、所定量の水を加え、（部分）加水分解を行い、続いて、有機ケイ素化合物を添加して（部分）加水分解させる。一方、電磁線硬化性化合物を溶媒に溶解して光重合開始剤を添加し、その後、両溶液を混合する方法があげられる。また、溶媒に有機ケイ素化合物と光感応性化合物を加えて撹拌し、続いて所定量の水を加えて（部分）加水分解を行った後に、溶媒に電磁線硬化性化合物と光重合開始剤を添加した溶液と混合してもよい。
　これら４成分は、同時に混合することもでき、また、有機ケイ素化合物と光感応性化合物の混合方法については、有機ケイ素化合物と光感応性化合物を混合した後に、水を加えて（部分）加水分解する方法や、有機ケイ素化合物及び光感応性化合物を別々に（部分）加水分解したものを混合する方法を挙げることができる。水や溶媒は必ずしも加える必要はないが、水を加えて（部分）加水分解物としておくことが好ましい。所定量の水の量としては、光感応性化合物の種類にもよるが、例えば、光感応性化合物が２以上の水酸基若しくは加水分解性基を有する金属化合物の場合、金属化合物１モルに対して、０．５モル以上の水を用いることが好ましく、０．５～２モルの水を用いることがより好ましい。また、光感応性化合物が金属錯体又は有機酸金属塩化合物の場合、金属錯体又は金属有機酸塩化合物１モルに対して、５～１００モルの水を用いることが好ましく、５～２０モルの水を用いることがより好ましい。 For example, a photosensitive compound is mixed with a solvent, a predetermined amount of water is added, (partial) hydrolysis is performed, and then an organosilicon compound is added (partial) to cause hydrolysis. On the other hand, there is a method in which an electromagnetic radiation curable compound is dissolved in a solvent, a photopolymerization initiator is added, and then both solutions are mixed. In addition, an organosilicon compound and a photosensitive compound are added to a solvent and stirred, and then a predetermined amount of water is added to perform (partial) hydrolysis, and then an electromagnetic radiation curable compound and a photopolymerization initiator are added to the solvent. You may mix with the added solution.
These four components can be mixed at the same time. Also, regarding the method of mixing the organosilicon compound and the photosensitive compound, after mixing the organosilicon compound and the photosensitive compound, water is added (partial) hydrolysis. And a method of separately (partially) hydrolyzing an organosilicon compound and a photosensitive compound. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 1 mol of the metal compound. It is preferable to use 0.5 mol or more of water, more preferably 0.5 to 2 mol of water. In the case where the photosensitive compound is a metal complex or an organic acid metal salt compound, 5 to 100 mol of water is preferably used with respect to 1 mol of the metal complex or metal organic acid salt compound. It is more preferable to use
　本発明の有機ケイ素化合物の縮合物としては、有機ケイ素化合物を、公知のシラノール縮合触媒を用いて（部分）加水分解させたものを用いても良い。
　縮合物の平均粒子径は２ｎｍ～１００ｎｍが好ましく、５ｎｍ～３０ｎｍであることがより好ましい。平均粒子径が１００ｎｍより大きいと組成物が白濁し、組成物が不安定となりゲル化し易くなる。平均粒子径が２ｎｍより小さいと塗膜性に悪影響が出る場合がある。 As the condensate of the organosilicon compound of the present invention, a product obtained by (partially) hydrolyzing an organosilicon compound using a known silanol condensation catalyst may be used.
The average particle size of the condensate is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. When the average particle size is larger than 100 nm, the composition becomes cloudy, the composition becomes unstable and is easily gelled. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.
（８）有機無機複合体及びその製造方法
　本発明の有機無機複合体は、例えば、基材上に前記有機無機複合体形成用組成物を塗布して得られる有機無機複合薄膜等である。
　本発明の有機無機複合体が形成可能な基体としては、金属、セラミックス、ガラス、プラスチック等が挙げられる。これらのうちでは、プラスチックが好適に挙げられ、具体的には、タッチパネル用のプラスチック基板等が挙げられる。従来、薄膜のプラスチック基体への形成は困難であり、ガラス等の無機基体に限定されていたが、本発明の薄膜は、形成の難しいプラスチック基体であっても、容易に形成でき、プラスチック製光学部品に対しても適している。かかるプラスチック基材としては、例えば、ポリカーボネート基材、アクリル樹脂基材、ポリイミド基材、ポリエステル基材、エポキシ樹脂基材、液晶ポリマー基材、ポリエーテルスルホン基材が挙げられる。 (8) Organic-inorganic composite and production method thereof The organic-inorganic composite of the present invention is, for example, an organic-inorganic composite thin film obtained by applying the organic-inorganic composite-forming composition on a substrate.
Examples of the substrate on which the organic-inorganic composite of the present invention can be formed include metals, ceramics, glass, and plastics. Among these, plastic is preferably used, and specifically, a plastic substrate for a touch panel can be used. Conventionally, it has been difficult to form a thin film on a plastic substrate, and it has been limited to inorganic substrates such as glass. However, the thin film of the present invention can be easily formed even if it is difficult to form a plastic substrate. Also suitable for parts. 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 polyethersulfone substrate.
　また、有機無機複合体形成用組成物の塗布方法としては、公知の塗布方法を用いることができ、例えば、ディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法、カーテンコート法、グラビア印刷法、シルクスクリーン法、インクジェット法等を挙げることができる。また、形成する薄膜の膜厚としては、特に制限されるものではなく、例えば、０．０５～２００μｍ程度である。 Moreover, as a coating method of the composition for forming an organic / inorganic composite, a known coating method can be used. For example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, A gravure printing method, a silk screen method, an inkjet method, etc. can be mentioned. Further, the thickness of the thin film to be formed is not particularly limited, and is, for example, about 0.05 to 200 μm.
　有機無機複合体形成用組成物を塗布して形成した薄膜の乾燥処理としては、例えば、４０～２００℃で、１～１２０分程度行うことが好ましく、６０～１２０℃で、１０～６０分程度行うことがより好ましい。 The thin film formed by applying the organic-inorganic composite-forming composition is preferably dried, for example, at 40 to 200 ° C. for about 1 to 120 minutes, and at 60 to 120 ° C. for about 10 to 60 minutes. More preferably.
　本発明の有機無機複合体の硬化方法としては、上記有機無機複合体形成用組成物に、３５０ｎｍ以下の波長を含む光を照射する方法を挙げることができる。 Examples of the method for curing the organic-inorganic composite of the present invention include a method in which the organic-inorganic composite-forming composition is irradiated with light having a wavelength of 350 nm or less.
　３５０ｎｍ以下の波長を含む光の照射は、例えば、高圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、エキシマーランプ等の公知の装置を用いて行うことができ、照射する光としては、１５０～３５０ｎｍの範囲のいずれかの波長の光を含有する光であることが好ましく、２５０～３１０ｎｍの範囲のいずれかの波長の光を含有する光であることがより好ましい。かかる範囲の波長に感応し、３５０ｎｍ、好ましくは３１０ｎｍを超える光に反応しないものであれば、太陽光によりほとんど影響を受けることはない。また、照射する光の照射光量としては、例えば、０．１～１００Ｊ／ｃｍ２程度が挙げられ、硬化効率（照射エネルギーと膜硬化程度の関係）を考慮すると、０．２～２０Ｊ／ｃｍ２程度であることが好ましく、０．５～１０Ｊ／ｃｍ２程度であることがより好ましい。
　なお、３５０ｎｍ以下の波長の光の照射とは、３５０ｎｍ以下のいずれかの波長の光を成分とする光源を用いる照射、好ましくは、３５０ｎｍ以下のいずれかの波長の光を主成分とする光源を用いる照射をいう。 Irradiation with light having a wavelength of 350 nm or less can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp. The irradiation light is in the range of 150 to 350 nm. It is preferable that the light contains light having any one of the above wavelengths, and it is more preferable that the light contains light having any wavelength in the range of 250 to 310 nm. As long as it is sensitive to wavelengths in this range and does not react to light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight. In addition, the irradiation light quantity of the light to be irradiated is, for example, about 0.1 to 100 J / cm 2, and considering the curing efficiency (relation between irradiation energy and film curing degree), 0.2 to 20 J / cm 2. Is preferably about 0.5 to 10 J / cm 2 .
Note that irradiation with light having a wavelength of 350 nm or less is irradiation using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. The irradiation used.
　本発明の有機無機複合体は、
ａ）式（Ｉ）
ＲｎＳｉＸ４－ｎ・・・（Ｉ）
（式（Ｉ）中、Ｒは式（Ｉ）中のＳｉに炭素原子が直接結合する有機基を表し、Ｘは夫々水酸基又は加水分解性基を表す。ｎは１又は２を表し、ｎが２のとき各Ｒは同一でも異なっていてもよく、（４－ｎ）が２以上のとき各Ｘは同一でも異なっていてもよい。）で表され、かつ、
ｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種からなる有機ケイ素化合物の縮合物、又は、
ｉｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種と、
式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、前記溶解パラメータ（ＳＰ２）より１．６未満小さい又は前記溶解パラメータ（ＳＰ２）と等しいか大きい有機ケイ素化合物（Ｓｉ２）の少なくとも１種とからなり、
前記有機ケイ素化合物（Ｓｉ１）と前記有機ケイ素化合物（Ｓｉ２）のモル比Ｓｉ１：Ｓｉ２が５：５～１０：０である有機ケイ素化合物の縮合物、
ｂ）金属錯体、金属有機酸塩、２以上の水酸基若しくは加水分解性基を有する金属化合物、それらの加水分解物、及びそれらの縮合物からなる群より選ばれる少なくとも１種の３５０ｎｍ以下の波長の光に感応する光感応性化合物及び／又はその誘導体、
ｃ）ベンジルメチルケタール系光重合開始剤、及び
ｄ）電磁線硬化性化合物の硬化物
を含有する。 The organic-inorganic composite of the present invention is
a) Formula (I)
R n SiX 4-n (I)
(In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in formula (I), X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n represents And when R 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.
i) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. A condensate of an organosilicon compound comprising at least one of small organosilicon compounds (Si1), or
ii) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. At least one small organosilicon compound (Si1);
An organosilicon compound in which the solubility parameter (SP1) obtained by the estimation method of R Fedors in formula (I) is less than 1.6 or less than or equal to the solubility parameter (SP2). Consisting of at least one of Si2),
A condensate of an organosilicon compound having a molar ratio Si1: Si2 of the organosilicon compound (Si1) and the organosilicon compound (Si2) of 5: 5 to 10: 0,
b) At least one wavelength of 350 nm or less selected from the group consisting of metal complexes, metal organic acid salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound and / or a derivative thereof sensitive to light,
c) a benzyl methyl ketal photopolymerization initiator, and d) a cured product of an electromagnetic radiation curable compound.
　原料である有機無機複合体形成用組成物中の有機ケイ素化合物又はその縮合物及び電磁線硬化性化合物は、有機無機複合体中では、それぞれ、有機ケイ素化合物の縮合物及び電磁線硬化性化合物の硬化物となる。
　有機無機複合体に含まれる光感応性化合物は、有機ケイ素化合物の縮合物に光感応性化合物及び／又はその誘導体が非結合状態で分散されてなるものや、有機ケイ素化合物の縮合物に光感応性化合物及び／又はその誘導体が結合してなるもの（例えば、Ｓｉ－Ｏ－Ｍ結合を有するもの（Ｍは光感応性化合物中の金属原子を表す。））や、その混合状態からなるものが包含される。 In the organic-inorganic composite, the organosilicon compound or the condensate thereof and the electromagnetic curable compound in the organic-inorganic composite-forming composition as the raw material are the condensate of the organosilicon compound and the electromagnetic curable compound, respectively. It becomes a cured product.
The photo-sensitive compound contained in the organic-inorganic composite is a photo-sensitive compound and / or derivative thereof dispersed in a non-bonded state in a condensate of an organosilicon compound, or a photo-sensitive compound in a condensate of an organosilicon compound. Or a derivative thereof (for example, a compound having a Si—OM bond (M represents a metal atom in a photosensitive compound)) or a mixture thereof. Is included.
　上記各成分の配合割合は、有機無機複合体形成用組成物の固形分中の各成分の配合割合と同様である。
　本発明の有機無機複合体は、形成過程において無機成分である有機ケイ素化合物の縮合物が、表面部分に偏析する。相対的に有機成分である電磁線硬化性化合物は、表面部分で少なくなる。そのため、表面部分は、炭素濃度が内部に比して低く、ケイ素濃度は逆に高くなる。すなわち、表面側が内部よりも無機化された状態となり、表面側が高い硬度を有する。
　よって、本発明の有機無機複合体形成用組成物を基材に塗布、硬化させることで、表面側が高い硬度を有する積層体が得られる。 The blending ratio of each component is the same as the blending ratio of each component in the solid content of the composition for forming an organic-inorganic composite.
In the organic-inorganic composite of the present invention, a condensate of an organic silicon compound, which is an inorganic component, is segregated on the surface portion in the formation process. The electromagnetic radiation curable compound, which is a relatively organic component, decreases at the surface portion. Therefore, the carbon concentration of the surface portion is lower than that of the inside, and the silicon concentration is higher. That is, the surface side becomes mineralized more than the inside, and the surface side has high hardness.
Therefore, the laminated body which the surface side has high hardness is obtained by apply | coating and hardening the composition for organic-inorganic composite_body | complex formation of this invention to a base material.
　以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples. However, the technical scope of the present invention is not limited to these examples.
［実施例１］
（有機無機複合体形成用組成物の調製）
　ビニルトリメトキシシラン（信越化学工業（株）製、「ＫＢＭ－１００３」）５．９５ｇと、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業（株）製、「ＫＢＭ－５０３」）４．０７ｇを混合した液に、工業用エタノール（日本アルコール販売製、「ソルミックス（登録商標）ＡＰ－７」）１０．６３ｇとジイソプロポキシビスアセチルアセトナートチタン（日本曹達（株）製、「Ｔ－５０」、酸化チタン換算固形分：１６．５質量％）２．７８ｇを加え、３０分間撹拌を行った。その後、超純水を３．１０ｇ加え、さらに室温で２時間攪拌を行いポリシロキサン溶液［Ａ－１］を得た。
　ウレタンアクリレートオリゴマー（日本合成化学工業（株）製、「ＵＶ１７００Ｂ」）１２．１６ｇをメチルイソブチルケトン１７．８８ｇに溶解させた。この溶液に光重合開始剤として２，２’－ジメトキシ－１，２－ジフェニルエタン－１－オン（ＢＡＳＦ製「Ｉｒｇａｃｕｒｅ（登録商標）６５１」）０．４４６ｇ（全固形分濃度に対して３．２質量％）を加え、溶液［Ｂ－１］を得た。
　固形分濃度の割合が［Ａ－１］／［Ｂ－１］＝１０質量％／９０質量％となるように、［Ａ－１］４．４７ｇと［Ｂ－１］３０．４９ｇを混合し、有機無機複合体形成用組成物［Ｃ－１］（固形分濃度３９．９質量％）を調製した。 [Example 1]
(Preparation of composition for forming organic-inorganic composite)
5.95 g of vinyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.) and 4.07 g of 3-methacryloxypropyltrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.) To the mixed solution, 10.63 g of industrial ethanol (manufactured by Nippon Alcohol Sales, “Solmix (registered trademark) AP-7”) and diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., “T- 50 ”, titanium oxide equivalent solid content: 16.5 mass%) 2.78 g was added and stirred for 30 minutes. Thereafter, 3.10 g of ultrapure water was added, and the mixture was further stirred at room temperature for 2 hours to obtain a polysiloxane solution [A-1].
12.16 g of urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “UV1700B”) was dissolved in 17.88 g of methyl isobutyl ketone. 0.446 g of 2,2′-dimethoxy-1,2-diphenylethane-1-one (“Irgacure (registered trademark) 651” manufactured by BASF) was used as a photopolymerization initiator in this solution. 2% by mass) to obtain a solution [B-1].
4.47 g of [A-1] and 30.49 g of [B-1] were mixed so that the solid content concentration ratio was [A-1] / [B-1] = 10 mass% / 90 mass%. Then, an organic-inorganic composite-forming composition [C-1] (solid content concentration 39.9% by mass) was prepared.
［比較例１］
　実施例１の［Ｂ－１］の調製において、光重合開始剤を２－メチル－１－（メチルチオフェニル）－２－モルフォリノプロパン－１－オン（ＢＡＳＦ製、「Ｉｒｇａｃｕｒｅ（登録商標）９０７」）に変更した以外は、実施例１と同様に調製して有機無機複合体形成用組成物［ＲＣ－１］を得た。 [Comparative Example 1]
In the preparation of [B-1] of Example 1, the photopolymerization initiator was 2-methyl-1- (methylthiophenyl) -2-morpholinopropan-1-one (manufactured by BASF, “Irgacure® 907”). The organic-inorganic composite-forming composition [RC-1] was prepared in the same manner as in Example 1 except that the above was changed.
［実施例２］
（有機無機複合体形成基板の作製）
　実施例１で得られた有機無機複合体形成用組成物［Ｃ－１］を白色アクリル基板上に約６μｍとなるようにバーコート成膜し、温風循環型乾燥機にて８０℃で３分間加熱を行った後、集光型高圧水銀灯（３６５ｎｍ、３１３ｎｍ、２５４ｎｍの波長の光を主成分とするＵＶ光、アイグラフィックス社製、１灯型、１２０Ｗ／ｃｍ、ランプ高９．８ｃｍ、コンベア速度４．６ｍ／分）で積算照射量が４００ｍＪ／ｃｍ２となるよう紫外線を照射して、有機無機複合体形成基板［Ｄ－１］を得た。 [Example 2]
(Preparation of organic / inorganic composite substrate)
The organic-inorganic composite-forming composition [C-1] obtained in Example 1 was bar-coated on a white acrylic substrate so as to have a thickness of about 6 μm, and 3 ° C. at 80 ° C. with a hot air circulating dryer. After heating for a minute, a condensing type high-pressure mercury lamp (UV light mainly composed of light having wavelengths of 365 nm, 313 nm, and 254 nm, manufactured by Eye Graphics, one lamp type, 120 W / cm, lamp height of 9.8 cm, The organic-inorganic composite-formed substrate [D-1] was obtained by irradiating with ultraviolet rays so that the integrated irradiation amount was 400 mJ / cm 2 at a conveyor speed of 4.6 m / min.
［比較例２］
　有機無機複合体形成用組成物として、［Ｃ－１］の代わりに、［ＲＣ－１］を用いる以外実施例２と同様に行い、有機無機複合体形成基板［ＲＤ－１］を得た。 [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].
［薄膜の評価］
　得られた基板［Ｄ－１］及び［ＲＤ－１］について以下の評価を行った。
（着色の評価）
　基板［Ｄ－１］、基板［ＲＤ－１］、及び未処理基板の着色の程度を調べるため、色彩濁度測定器（ＣＯＨ４００、日本電色工業）を用いてｂ＊値（黄色味）を測定した。結果を表３に示す。本発明の［Ｄ－１］は、［ＲＤ－１］と比較して着色が低減されていることがわかった。 [Evaluation of thin film]
The obtained substrates [D-1] and [RD-1] were evaluated as follows.
(Evaluation of coloring)
In order to investigate the degree of coloring of the substrate [D-1], the substrate [RD-1], and the untreated substrate, the b * value (yellowishness) was measured using a color turbidity measuring device (COH400, Nippon Denshoku Industries Co., Ltd.). It was measured. The results are shown in Table 3. [D-1] of the present invention was found to have reduced coloring compared to [RD-1].
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（耐熱性評価）
　基板［Ｄ－１］及び基板［ＲＤ－１］を、１００℃に温度管理された温風循環型乾燥機にて各々、１０分間、３０分間、６０分間、１２０分間加熱処理をした後、室温で５分間冷却を行い、色彩濁度測定器を用いて加熱処理前後のｂ＊値を測定した。結果を表４に示す。本発明の基板［Ｄ－１］は、基板［ＲＤ－１］と比較して加熱処理前後の着色変化が少なく、耐熱黄変性に優れることがわかった。 (Heat resistance evaluation)
Substrate [D-1] and Substrate [RD-1] were heated for 10 minutes, 30 minutes, 60 minutes, and 120 minutes, respectively, in a hot air circulating dryer controlled at 100 ° C. Was cooled for 5 minutes, and b * values before and after the heat treatment were measured using a color turbidity measuring device. The results are shown in Table 4. It was found that the substrate [D-1] of the present invention has less color change before and after the heat treatment compared to the substrate [RD-1] and is excellent in heat-resistant yellowing.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
（耐光性評価）
　基板［Ｄ－１］及び基板［ＲＤ－１］に、実施例２と同様の条件で積算照射量が各々５００ｍＪ／ｃｍ２、１５００ｍＪ／ｃｍ２、３０００ｍＪ／ｃｍ２、５０００ｍＪ／ｃｍ２となるように紫外線を照射した後、室温で５分冷却を行い、色彩濁度測定器を用いて照射前後のｂ＊値を測定した。結果を表５に示す。本発明の基板［Ｄ－１］は、基板［ＲＤ－１］と比較して紫外線照射による着色変化が少なく、耐光黄変性に優れることがわかった。 (Light resistance evaluation)
The substrate [D-1] and the substrate [RD-1], Example 2 and the total irradiation amount is respectively 500 mJ / cm 2 under the same conditions, 1500mJ / cm 2, 3000mJ / cm 2, 5000mJ / cm 2 become as After irradiating with ultraviolet rays, it was cooled at room temperature for 5 minutes, and b * values before and after irradiation were measured using a color turbidity measuring device. The results are shown in Table 5. It has been found that the substrate [D-1] of the present invention has less color change due to ultraviolet irradiation and is excellent in light yellowing resistance compared to the substrate [RD-1].
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (5)

  1. ａ）式（Ｉ）
    ＲｎＳｉＸ４－ｎ・・・（Ｉ）
    （式（Ｉ）中、Ｒは式（Ｉ）中のＳｉに炭素原子が直接結合する有機基を表し、Ｘは夫々水酸基又は加水分解性基を表す。ｎは１又は２を表し、ｎが２のとき各Ｒは同一でも異なっていてもよく、（４－ｎ）が２以上のとき各Ｘは同一でも異なっていてもよい。）で表され、かつ、
    ｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメーター（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種からなる有機ケイ素化合物及び／又はその縮合物、又は、
    ｉｉ）式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、電磁線硬化性化合物のＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ２）よりも１．６以上小さい有機ケイ素化合物（Ｓｉ１）の少なくとも１種と、
    式（Ｉ）中のＲのＦｅｄｏｒｓの推算法により求められた溶解パラメータ（ＳＰ１）が、前記溶解パラメータ（ＳＰ２）より１．６未満小さい又は前記溶解パラメータ（ＳＰ２）と等しいか大きい有機ケイ素化合物（Ｓｉ２）の少なくとも１種とからなり、
    前記有機ケイ素化合物（Ｓｉ１）と前記有機ケイ素化合物（Ｓｉ２）のモル比Ｓｉ１：Ｓｉ２が５：５～１０：０である有機ケイ素化合物及び／又はその縮合物、
    ｂ）金属錯体、金属有機酸塩、２以上の水酸基若しくは加水分解性基を有する金属化合物、それらの加水分解物、及びそれらの縮合物からなる群より選ばれる少なくとも１種の３５０ｎｍ以下の波長の光に感応する光感応性化合物、
    ｃ）ベンジルメチルケタール系光重合開始剤、及び
    ｄ）電磁線硬化性化合物
    を含有する有機無機複合体形成用組成物。     a) Formula (I)
    R n SiX 4-n (I)
    (In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in formula (I), X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n represents And when R 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.
    i) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. An organosilicon compound comprising at least one of small organosilicon compounds (Si1) and / or a condensate thereof, or
    ii) The solubility parameter (SP1) obtained by the estimation method of R Fedors in the formula (I) is 1.6 or more than the solubility parameter (SP2) obtained by the Fedors estimation method of the electromagnetic radiation curable compound. At least one small organosilicon compound (Si1);
    An organosilicon compound in which the solubility parameter (SP1) obtained by the estimation method of R Fedors in formula (I) is less than 1.6 or less than or equal to the solubility parameter (SP2). Consisting of at least one of Si2),
    An organosilicon compound in which the molar ratio Si1: Si2 of the organosilicon compound (Si1) and the organosilicon compound (Si2) is 5: 5 to 10: 0 and / or a condensate thereof,
    b) At least one wavelength of 350 nm or less selected from the group consisting of metal complexes, metal organic acid salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A light-sensitive compound that is sensitive to light,
    The composition for organic-inorganic composite formation containing c) benzyl methyl ketal type photoinitiator and d) electromagnetic radiation curable compound.
  2. 光感応性化合物の金属がＴｉ、Ａｌ、Ｚｒ、又はＳｎである、請求項１に記載の有機無機複合体形成用組成物。 The composition for organic-inorganic composite formation of Claim 1 whose metal of a photosensitive compound is Ti, Al, Zr, or Sn.
  3. ベンジルメチルケタール系光重合開始剤が２，２’－ジメトキシ－１，２－ジフェニルエタン－１－オンである、請求項１又は２に記載の有機無機複合体形成用組成物。 The composition for forming an organic-inorganic complex according to claim 1 or 2, wherein the benzylmethyl ketal photoinitiator is 2,2'-dimethoxy-1,2-diphenylethane-1-one.
  4. 電磁線硬化性化合物が（メタ）アクリレート系化合物である、請求項１又は２に記載の有機無機複合体形成用組成物。 The composition for organic-inorganic composite formation of Claim 1 or 2 whose electromagnetic radiation curable compound is a (meth) acrylate type compound.
  5. 基材に請求項１～４のいずれかに記載の有機無機複合体形成用組成物を塗布して得られる積層体。 A laminate obtained by applying the organic-inorganic composite-forming composition according to any one of claims 1 to 4 to a substrate.
PCT/JP2016/002072 2015-04-24 2016-04-18 Composition for forming organic-inorganic composite WO2016170771A1 (en)

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JP2005179499A (en) * 2003-12-19 2005-07-07 Olympus Corp Organic-inorganic composite material and optical system using the same
WO2007119627A1 (en) * 2006-04-10 2007-10-25 Ube Industries, Ltd. Curable composition, cured silsesquioxanes, and process for production of both
JP2009015309A (en) * 2007-05-25 2009-01-22 Sumitomo Bakelite Co Ltd Resin composition, resin spacer film, and semiconductor device
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JP2014015547A (en) * 2012-07-10 2014-01-30 Nippon Soda Co Ltd Organic and inorganic composite thin-film

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