WO2008035669A1 - Composition polymère hybride organique-inorganique contenant de fines particules d'oxyde et son procédé de fabrication - Google Patents

Composition polymère hybride organique-inorganique contenant de fines particules d'oxyde et son procédé de fabrication Download PDF

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WO2008035669A1
WO2008035669A1 PCT/JP2007/068079 JP2007068079W WO2008035669A1 WO 2008035669 A1 WO2008035669 A1 WO 2008035669A1 JP 2007068079 W JP2007068079 W JP 2007068079W WO 2008035669 A1 WO2008035669 A1 WO 2008035669A1
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organic
group
inorganic hybrid
oxide fine
hybrid polymer
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Japanese (ja)
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Tarou Kanamori
Keisuke Yajima
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Jsr Corporation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to an organic-inorganic hybrid polymer composition in which key oxide fine particles and / or metal oxide fine particles are highly dispersed in an organic solvent containing an organic-inorganic hybrid polymer, and a cured product thereof.
  • siloxane binder As a means for imparting various functions to a siloxane material having excellent durability, a binder having a siloxane skeleton (hereinafter, also referred to as “siloxane binder”! /, U), cation oxide fine particles, and various metals. Compounding with oxide fine particles (hereinafter collectively referred to as “oxide fine particles”) is being studied. At this time, the siloxane-based binder and oxide fine particles are often prepared in the form of a dispersion containing them. On the other hand, since siloxane-based binders are difficult to dissolve in water, it is necessary to use an organic solvent as a dispersion medium.
  • oxide fine particles tend to aggregate in an organic solvent and are often dispersed in an aqueous medium. . Therefore, in order to finely disperse oxide fine particles in an organic solvent, phosphoric acid, sulfonic acid or carboxylic acid having an organic group having 6 or more carbon atoms (see Patent Document 1), an organic compound having an oxyalkylene group, It was necessary to use an ester such as phosphoric acid having an oxyalkylene group (see Patent Document 2) or a silane compound having an oxyalkylene group (see Patent Document 3).
  • oxide fine particles and a siloxane-based binder are combined by a method of finely dispersing oxide fine particles in an organic solvent using these compounds, the dispersibility of the dispersion is good.
  • the compatibility between the above compound and the siloxane-based binder is poor.
  • the coating film may be whitened.
  • phosphoric acid having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group remains in this coating film. For this reason, problems such as coloration of the coating and generation of cracks may occur under ultraviolet irradiation.
  • the key oxide fine particles have an organic solvent dispersion that maintains dispersibility with its own surface charge. Although this dispersion has good dispersion stability, it is mixed with a siloxane binder. In this case, the silicon oxide fine particles may aggregate and whiten, or crack force S may occur.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-283822
  • Patent Document 2 Japanese Patent Laid-Open No. 2005-185924
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-99879
  • the present invention is intended to solve the problems associated with the prior art as described above, and has a polysiloxane-based cured body having various functions and excellent in transparency and outdoor weather resistance, and the present invention. It is an object of the present invention to provide an organic-inorganic hybrid polymer composition in which oxide fine particles are highly dispersed and a method for producing the same, from which such a cured product can be obtained.
  • the organic fine particle-containing organic-inorganic hybrid polymer composition according to the present invention is present in an organic solvent in the presence of a basic compound, an acidic compound, or a metal chelate compound.
  • R 1 number of carbon atoms;!. Represents a monovalent organic group having 1-8, when present two may be different from one another the same R 2 are each independently A C 1-5 alkyl group or a C 1-6 acyl group n is an integer of 0-2.
  • the oxide fine particles (A) are mixed with an organic-inorganic hybrid polymer obtained by hydrolysis / condensation reaction with a polymer (b2) having a silyl group containing a silicon atom bonded to a hydroxyl group. It is obtained by dispersing in a solvent.
  • the oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are preferably mixed in the presence of a basic compound.
  • the oxide fine particles (A) and the organic-inorganic hybrid polymer (B) are preferably mixed by a bead mill.
  • the organic-inorganic hybrid polymer (100 parts by weight of the oxide fine particles (A))
  • B) is preferably 1 to 1000 parts by weight in terms of complete hydrolysis condensate.
  • the silane compound (bl) and the polymer (b2) are combined into a completely hydrolyzed condensate content (Wbl) of the silane compound (bl) and a solid content content of the polymer (b2). Weight ratio with (Wb2)
  • the content of a silyl group containing a hydrolyzable group and / or a silicon atom bonded to a hydroxyl group is converted into the content of the silicon atom, 0.;! ⁇ 2 weight % Is preferred.
  • a cured product according to the present invention is obtained from the above-mentioned organic-inorganic hybrid polymer composition containing fine oxide particles.
  • a coating composition according to the present invention is characterized by comprising the above-mentioned organic fine particle-containing organic / inorganic hybrid polymer composition.
  • the laminate according to the present invention is characterized by having an organic base material and a coating film obtained from the coating composition provided on the organic base material.
  • oxide fine particles are highly developed in an organic solvent containing an organic-inorganic hybrid polymer without using a phosphoric acid having an organic group having 6 or more carbon atoms or a compound having an oxyalkylene group.
  • a dispersed composition is obtained.
  • This composition is excellent in dispersion stability and can form a transparent cured product containing fine oxide particles and the organic-inorganic hybrid polymer. Since this cured product does not substantially contain the above-mentioned compound, it does not easily turn yellow even if left in an environment such as outdoors where it is irradiated with ultraviolet rays. Also, it is flexible due to the action of the organic-inorganic hybrid polymer. And excellent trackability to the substrate.
  • a cured product using zinc oxide fine particles, cerium oxide fine particles, or rutile-type titanium oxide fine particles as oxide fine particles is useful as an ultraviolet cut material.
  • the oxide fine particle-containing organic-inorganic hybrid polymer composition according to the present invention comprises an oxide fine particle (A) and an organic-inorganic hybrid polymer (B), phosphoric acid or the like having an organic group having 6 or more carbon atoms.
  • the power S can be obtained by mixing and dispersing in an organic solvent in the presence of a basic compound, acidic compound or metal chelate compound without using a compound having a xyalkylene group.
  • the oxide fine particles (A) used in the present invention are silicon oxide fine particles and / or metal oxide fine particles.
  • the metal oxide fine particles are not particularly limited as long as they are metal element oxide fine particles.
  • antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, suboxide oxide Lead tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, anorenium oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, prasedium oxide, neodymium oxide, samarium oxide, pium oxide, gadolinium oxide Terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, lithium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, barium oxide, magnesium oxide, and these And metal oxide fine particles such as an oxide of a
  • the oxide fine particles may be used alone or in combination of two or more.
  • the oxide fine particles (A) can be appropriately selected depending on the function to be imparted. For example, in the case of imparting a high refractive property, the TiO fine particles are preferable in the ultraviolet region.
  • UV cut function ZrO fine particles are preferable in order to achieve both high properties and high refractive properties.
  • UV cut function UV cut function
  • cerium oxide fine particles and zinc oxide fine particles are preferable.
  • antimony oxide-doped tin oxide fine particles and indium tin-based composite oxide fine particles are preferable.
  • the primary average particle size of the oxide fine particles (A) is preferably 0.1 to 100 nm, more preferably 0. !! to 70 nm, and particularly preferably 0.;! To 50 nm.
  • the primary average particle diameter of the oxide fine particles (A) is in the above range, a cured product having excellent light transmittance can be obtained.
  • Such oxide fine particles (A) are dispersed in a solvent! /, N! /, Even when added in a powder state, in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. It may be added in the state of a dispersion dispersed therein.
  • the oxide fine particles (A) before the addition may be aggregated to form secondary particles.
  • it is preferable to use a powder because an appropriate organic solvent can be appropriately selected in consideration of the solubility of the organic-inorganic hybrid polymer (B).
  • the production method of the present invention is particularly effective when added in the form of powder.
  • the organic-inorganic hybrid polymer (B) used in the present invention contains a specific silane compound (bl ) And a polymer (b2) containing a specific silyl group are prepared by hydrolysis / condensation reaction. More specifically, it is prepared by adding a catalyst for promoting hydrolysis / condensation reaction and water to a mixture containing the silane compound (bl) and the polymer (b2) containing a silyl group.
  • the silane compound (b 1) used in the present invention has the following formula (1)
  • R 1 number of carbon atoms;!. Represents a monovalent organic group having 1-8, when present two may be different from one another the same R 2 are each independently A C 1-5 alkyl group or a C 1-6 acyl group n is an integer of 0-2.
  • organosilane (1) hydrolysates and organosilane (1) condensates
  • any one silane compound may be used, or any two silane compounds may be used in combination, or all three silane compounds may be used. You may mix and use a compound.
  • organosilane (1) when organosilane (1) is used as the silane compound (bl), organosilane (1) may be used alone or in combination of two or more.
  • the hydrolyzate and condensate of the organosilane (1) may be formed from one kind of organosilane (1), or may be formed by using two or more kinds of organosilane (1) in combination. Good.
  • the hydrolyzate of the organosilane (1) is sufficient if at least one of the 2 OR 4 groups contained in the organosilane (1) is hydrolyzed. It may be a product obtained by hydrolyzing an OR 2 group, a product obtained by hydrolyzing two or more OR 2 groups, or a mixture thereof.
  • the condensate of organosilane (1) is formed by condensation of silanol groups in the hydrolyzate generated by hydrolysis of organosilane (1) to form a Si—O—Si bond.
  • the condensate may be a product obtained by condensing a small part of silanol groups, most (including all) of the silanol groups, These mixtures are also included.
  • R 1 is a monovalent organic group having 1 to 8 carbon atoms, specifically, a methylol group, an ethyl group, an n propyl group, an i propyl group, an n butyl group.
  • alkyl group such as i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group;
  • Isacyl groups such as acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, trioyl group, force profile group;
  • Examples thereof include a bur group, an aryl group, a cyclohexyl group, a phenyl group, an epoxy group, a glycidyl group, a (meth) acryloxy group, a ureido group, an amide group, a fluoroacetamide group, and an isocyanate group.
  • examples of R 1 include substituted derivatives of the above organic groups.
  • examples of the substituent of the substituted derivative of R 1 include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexylene group, and (meth) An acryloxy group, a ureido group, an ammonium base, etc. are mentioned.
  • the carbon number of R 1 composed of these substituted derivatives is preferably 8 or less including the carbon atom in the substituent.
  • R 2 which is an alkyl group having 1 to 5 carbon atoms includes, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, and an n-pen.
  • R 2 which is an acyl group having 1 to 6 carbon atoms include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a force profile group.
  • a plurality of R 2 are present in the formula (1), they may be the same or different.
  • the trifunctional silane compound trialkoxysilanes are particularly preferable.
  • the bifunctional silane compound dialkoxysilanes are preferable.
  • the trifunctional silane compound / bifunctional silane compound is preferably 95/5 to 10% by weight ratio in terms of the total hydrolysis condensate of each. / 90, more preferably 90/10 to 30/70, particularly preferably 85/15 to 40/60.
  • the sum of the trifunctional silane compound and the bifunctional silane compound is 100. If the content of the trifunctional silane compound is too large, the dispersibility of the oxide fine particles may be inferior because it tends to aggregate. If the content of the trifunctional silane compound is too small, the functionality required for dispersing the oxide fine particles may be reduced.
  • the completely hydrolyzed condensate means a product in which the —OR group of a silane compound is hydrolyzed to 100% to be a SiOH group and further completely condensed to a siloxane structure.
  • one type of organosilane (1) may be used alone as the silane compound (bl), but two or more types of organosilane (1) may be used in combination.
  • the average value is n (hereinafter also referred to as “the average value of n”). ) Is preferably 0.5 to 1.9, more preferably 0 to 6 to 1.7, and particularly preferably 0.7 to 1.5.
  • the average value of n is less than the above lower limit, the storage stability of the organic-inorganic hybrid polymer composition may be inferior, and when the upper limit is exceeded, the curability of the cured body (coating film) may be inferior.
  • n can be adjusted to the above range by appropriately using a bifunctional to tetrafunctional silane compound and appropriately adjusting the blending ratio thereof.
  • organosilane (1) may be used as it is as silane compound (bl). However, a hydrolyzate and / or condensate of organosilane (1) can be used.
  • organosilane (1) When the organosilane (1) is used as a hydrolyzate and / or a condensate, it may be prepared by hydrolyzing and condensing the organosilane (1) in advance.
  • hybrid polymer (B) water is added to hydrolyze and condense the organosilane (1) with water to prepare a hydrolyzate and / or condensate of the organosilane (1). I like it! /
  • a condensate of organosilane (1) when used as the silane compound (b1) in the present invention, it may be prepared from the above organosilane (1) or may be obtained by shrinking a commercially available organosilane. A compound may be used.
  • Commercially available condensates of organosilane include Mitsubishi Chemical Corporation
  • MKC silicate Colcoat ethyl silicate, Toray Dow Coung Silicone Co., Ltd. silicone resin, GE Toshiba Silicone Co., Ltd. silicone resin, Shin-Etsu Chemical Co., Ltd. silicone resin And silicone oligomers, hydroxyl group-containing polydimethylsiloxane manufactured by Dow Co., Ltd., and silicone oligomers manufactured by Nippon Tunica.
  • silicone resin GE Toshiba Silicone Co., Ltd. silicone resin
  • Shin-Etsu Chemical Co., Ltd. silicone resin And silicone oligomers hydroxyl group-containing polydimethylsiloxane manufactured by Dow Co., Ltd.
  • silicone oligomers manufactured by Nippon Tunica These commercially available condensates of organosilanes may be used as they are or after further condensation.
  • the polymer (b2) containing a specific silyl group used in the present invention (hereinafter also referred to as “specific silyl group-containing polymer (b2)”) is bound to a hydrolyzable group and / or a hydroxyl group. It contains a silyl group having a carbon atom (hereinafter referred to as “specific silyl group”).
  • the specific silyl group-containing polymer (b2) preferably has a specific silyl group at the terminal and / or side chain of the polymer molecular chain.
  • the hydrolyzable group and / or hydroxyl group in the specific silyl group is co-condensed with the silane compound (b 1) to form the organic-inorganic hybrid polymer (B).
  • polymer (B) and oxide fine particles (A) are mixed and dispersed in an organic solvent in the presence of a basic compound, acidic compound or metal chelate compound
  • the oxide fine particles (A) are highly dispersed in the organic solvent. This is because the hydrolyzable group and / or hydroxyl group in the specific silyl group remaining in the organic-inorganic hybrid polymer (B) is condensed on the surface of the oxide fine particles (A) by the catalytic action of a basic compound or the like. This is presumably because the surface of the fine particles (A) becomes hydrophobic and the oxide fine particles (A) are easily finely dispersed in the organic solvent.
  • the content of the specific silyl group in the specific silyl group-containing polymer (b2) is usually 0.;! To 2 with respect to the polymer before the introduction of the specific silyl group, in terms of the amount of silicon atoms. % By weight, preferably 0.3-; 1.7% by weight.
  • the specific silyl group content in the specific silyl group-containing polymer (b2) is less than the above lower limit, the covalent bond site with the silane compound (bl) and the specific silyl group remaining in the organic-inorganic hybrid polymer (B) Therefore, the effect of the mixed dispersion process may not be obtained.
  • gelation may occur during storage of the composition.
  • X represents a hydrolyzable group such as a halogen atom, an alkoxyl group, an acetoxy group, a phenoxy group, a thioalkoxyl group, an amino group, or a hydroxyl group
  • R 5 is a hydrogen atom having 1 to 10 carbon atoms.
  • Such a specific silyl group-containing polymer (b2) is obtained, for example, by the following methods (I) and (ii):
  • hydrosilane compound (I) A hydrosilane compound having a specific silyl group represented by the above formula (3) (hereinafter, simply referred to as “hydrosilane compound (I)”) is converted to a bulle having a carbon-carbon double bond.
  • a method of causing an addition reaction to the carbon-carbon double bond in a polymer hereinafter referred to as “unsaturated butyl polymer”.
  • hydrosilane compound (I) used in the above method (I) examples include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldimethoxysilane, methinolegoxysilane. , Pheninoresimethoxysilane, trimethoxysilane, acetoxysilane, triacetoxysilane, and other acyloxysilanes; methyldiaminoxysilane, triaminoxysilane, dimethyl'aminoxysilane, and other aminoxysilanes . These hydrosilane compounds (I) can be used alone or in combination of two or more.
  • the unsaturated bulle polymer used in the method (I) is not particularly limited as long as it is a polymer having a hydroxyl group.
  • the following (I 1) and (I 2) It can be produced by a method or a combination thereof.
  • a radical polymerization initiator for example, 4, 4'-azobis-4-cyanovaleric acid having (1-2) functional group
  • both radical polymerization initiator and chain transfer agent are used.
  • a compound having a functional group ( ⁇ ) for example, 4, 4'-azobis 4-cyananovaleric acid and dithio) Glycolic acid etc.
  • (co) polymerization of bulle monomers and the functional group ( ⁇ ) derived from radical polymerization initiator or chain transfer agent at one or both ends of the polymer molecular chain
  • the polymer is reacted with an unsaturated compound having a functional group ( ⁇ ) and a carbon / carbon double bond.
  • Examples of the reaction between the functional group ( ⁇ ) and the functional group (/ 3) in the methods (1-1) and (I 2) include, for example, esterification reaction between a carboxyl group and a hydroxyl group, carboxylic acid anhydride, Ring-opening esterification reaction between a hydroxyl group and a hydroxyl group, ring-opening esterification reaction between a carboxyl group and an epoxy group, amidation reaction between a carboxyl group and an amino group, ring-opening between a carboxylic anhydride group and an amino group amide And urethanation reaction between an epoxy group and an amino group, a urethanation reaction between a hydroxyl group and an isocyanate group, and a combination of these reactions.
  • Examples of the bull monomers having a functional group ( ⁇ ) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; maleic anhydride, anhydrous Unsaturated carboxylic acid anhydrides such as itaconic acid; 2-hydroxyethyl (meth) acrylate
  • Hydroxyl group-containing butyl monomers such as methylol (meth) acrylamide and 2-hydroxyethyl butyl ether; 2-aminoethinole (meth) acrylate, 2-aminopropynole (meth) acrylate, 3 aminopropyl (meth) attaly 1, 2, 1-trimethylamine (meth) acrylimide, 1 -methyl-1-ethylamine (meth) acrylimide, 1, 1 dimethyl 1 (2-Hydroxypropyl) amine (meth) acrylimide, 1, 1-dimethyl 1- (2, 2-phenyl 2, -hydro-chichetil) amamine (meth) acrylimide, 1, 1 dimethyl 1 ( 2 , hydroxy) 2 ,
  • bull monomers that can be copolymerized with a bull monomer having a functional group ( ⁇ )
  • ⁇ styrene, ⁇ -methyl styrene, 4 methyl styrene, 2 methyl styrene, 3 methyl styrene, 4-methoxy styrene, 2 hydroxymethyl styrene, 4-ethyl styrene, 4-ethoxy styrene, 3, 4 dimethyl styrene, 3, Aromatic bullets such as 4 Jetylstyrene, 2 Chlorostyrene, 3-Chlorostyrene, 4 Chloro-3-Methylstyrene, 4 t-Butyl Styrene, 2, 4-Dichlorostyrene, 2,6-Dichlorostyrene, 1-Burnaphthalene Mer;
  • ethylene glycol di (meth) acrylate diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylol Polyfunctional monomers such as propanetri (meth) acrylate and pentaerythritol tetra (meth) acrylate;
  • Acid amide compounds such as (meth) acrylamide, N methylol (meth) acrylamide, N methoxymethyl (meth) amide, diacetone acrylamide, maleic acid amide and maleimide; Bull compounds such as butyl chloride, vinylidene chloride and fatty acid butyl ester;
  • Cyanide bur compounds such as acrylonitrile and methacrylonitrile; Fluorine atom-containing monomers such as trifluoroethyl (meth) acrylate and pentadecafluorooctyl (meth) acrylate;
  • Examples include dicaprolataton. These can be achieved by using S alone or in combination of two or more.
  • Examples of the unsaturated compound having a functional group (/ 3) and a carbon-carbon double bond include, for example, a bull monomer similar to a bull monomer having a functional group ( ⁇ ), An isocyanate group-containing unsaturated compound obtained by reacting the hydroxyl group-containing vinyl monomer and the diisocyanate compound in an equimolar amount can be exemplified.
  • CH CHSi (CH) (OCH)
  • CH CHSi (OCH)
  • CH CHSi (CH) C1
  • CH CHSiCl
  • bulle monomers to be copolymerized with the unsaturated silane compound include, for example, a bulle type monomer having the functional group ( ⁇ ) exemplified in the method (I 1) above! And other vinyl monomers.
  • Examples of the method for producing the specific silyl group-containing polymer (b2) include, for example, a method in which each monomer is added at once and polymerized. Continuously Alternatively, there may be mentioned a method in which polymerization is carried out by intermittent addition, or a method in which a monomer is continuously added from the start of polymerization. These polymerization methods may be combined.
  • the polymerization method includes solution polymerization.
  • the solvent used in the solution polymerization is not particularly limited as long as it can produce the specific silyl group-containing polymer (b2).
  • alcohols aromatic hydrocarbons, ethers, ketones, esters The ability to list things.
  • the alcohols include methanol, ethanol, n-propylenoleanolone, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol monole, tert-butylenorenolenole, and n-hexenoleanoreconole.
  • Ethylene glycolate Diethyleneglycolanol, Triethyleneglycolanol, Ethyleneglycolanol Monobutyl ether, Ethyleneglycolmonoethyletheracetate, Diethyleneglycolenomonoethylenoate, Propyleneglycolole Examples thereof include monomethylenoatenole, propylene monomethyl ether acetate, diacetone alcohol and the like.
  • examples of aromatic hydrocarbons include benzene, toluene, xylene, etc.
  • examples of ethers include tetrahydrofuran, dioxane, etc.
  • examples of ketones include acetonitrile, methyl ethyl ketone, and methyl isobutyl ketone.
  • esters include ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, normal propyl lactate, isopropyl lactate, methyl 3-ethoxypropionate, 3 — Ethyl ethoxypropionate and the like.
  • These organic solvents may be used alone or in combination of two or more.
  • the specific silyl group-containing polymer (b2) in addition to the specific silyl group-containing polymer polymerized as described above, the specific silyl group-containing epoxy resin, the specific silyl group-containing polyester resin Other specific silyl group-containing polymers such as can also be used.
  • the specific silyl group-containing epoxy resin is, for example, in epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, aliphatic polydaricidyl ether, and aliphatic polyglycidyl ester.
  • Amino silanes, bur silanes, carboxy silanes, darines having specific silyl groups on the epoxy group of It can be produced by reacting sidylsilanes.
  • the above-mentioned specific silyl group-containing polyester resin is produced, for example, by reacting a carboxyl group or hydroxyl group contained in the polyester resin with aminosilanes, carboxysilanes, darisidylsilanes, etc. having a specific silyl group. can do.
  • the Mw in terms of polystyrene measured by the GPC method of the specific silyl group-containing polymer (b2) is preferably 2,000-100,000, more preferably 3,000-50,000.
  • the specific silyl group-containing polymer (b2) is determined by the power to use alone or in combination of two or more.
  • the silane compound (a) and the specific silyl group-containing polymer (b) it is preferred to add a catalyst to the mixture.
  • a catalyst By adding a catalyst, the degree of crosslinking of the organic-inorganic hybrid polymer (B) obtained can be increased, and the molecular weight of the polysiloxane produced by the polycondensation reaction of the organosilane (1) is increased. As a result, A cured product having excellent strength and long-term durability can be obtained, and the coating film can be thickened and applied easily.
  • the addition of the catalyst promotes the reaction between the silane compound (bl) and the specific silyl group-containing polymer (b2), and sufficient reaction sites (alkoxy groups) are formed in the organic-inorganic hybrid polymer (B). .
  • this organic-inorganic hybrid polymer (B) and oxide fine particles (A) are mixed and dispersed in an organic solvent in the presence of a basic compound or the like, the oxide fine particles (A) are highly dissolved in the organic solvent. Distributed. This is because the organic / inorganic hybrid polymer (B) is condensed on the surface of the oxide fine particles (A), the surface of the oxide fine particles (A) becomes hydrophobic, and the oxide fine particles (A) are finely dispersed in the organic solvent. This is presumed to be easier.
  • Examples of the catalyst used for promoting the hydrolysis' condensation reaction include basic compounds, acidic compounds, salt compounds, and metal chelate compounds.
  • Examples of the basic compound include ammonia (including aqueous ammonia), organic amine compounds, alkali metals such as sodium hydroxide and potassium hydroxide, and hydroxides of alkaline earth metals. And alkali metal alkoxides such as sodium methoxide and sodium ethoxide. Of these, ammonia and organic amine compounds are preferred.
  • organic amines examples include anolequinoleamine, alkoxyamine, alkanolamine, and arylamine.
  • alkylamine examples include methenoreamine, ethenoreamine, propylamine, butylamine, hexylamine, octylamine, N, N dimethylamine, N, N dimethylamine, N, N dipropylamine, N, N dibutylamine, trimethinoreamine, triethinoreamine, Examples thereof include alkylamines having an alkyl group having 1 to 4 carbon atoms such as tripropylamine and tributylamine.
  • alkoxyamines include methoxymethylamine, methoxyethylamine, methoxypropylamine, methoxybutylamine, ethoxymethylamine, ethoxyethylamine, ethoxypropylamine, ethoxybutylamine, propoxymethyl.
  • Alkoxy groups having an alkoxy group having 1 to 4 carbon atoms such as amines, propoxychetylamines, propoxypropylamines, propoxybutylamines, butoxymethylamines, butoxysethylamines, butoxypropylamines, butoxybutylamines. Min etc. are mentioned.
  • alkanolamines include methanolamine, ethanolamine, propanolamine, butanolamine, N-methylmethanolamine, N-ethylmethanolamine, N-propylmethanolamine, N-butylmethanolamine.
  • arylamine examples include aniline and N-methylaniline.
  • Tetraalkylammonium hydride such as tetraptylammonium hydroxide; tetraalkylethylenediamine such as tetramethylethylenediamine, tetraethylethylenediamine, tetrapropylethylenediamine, tetrabutylethylenediamine Methylaminomethylamine, methylaminoethylamine, methylaminopropylamine, methylaminobutyramine, ethylaminomethylamine, ethylaminoethylamine, ethylaminopropylamine, Tilaminobutylamine, propylaminomethylamine, propylaminoethylamine, propylaminopropylamine, propylaminobutylamine, butylaminoaminomethylamine, butylaminoethylamine, butylaminopropylamine, The Alkylaminoalkylamines such as
  • Such basic compounds may be used singly or in combination of two or more. Of these, triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferable.
  • Examples of the acidic compound include organic acids and inorganic acids.
  • Examples of organic acids include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, maleic anhydride, and methylmalonic acid.
  • the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
  • Such acidic compounds may be used singly or in combination of two or more.
  • maleic acid maleic anhydride, methanesulfonic acid, and acetic acid are particularly preferred.
  • the salt compound examples include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid.
  • metal chelate compounds examples include organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates thereof are collectively referred to as “organic metal compounds”). It is done.
  • organometallic compounds include, for example, the following formula (a):
  • M represents at least one metal atom selected from the group consisting of zirconium, titanium and aluminum, and R 7 and R 8 are each independently a methyl group, an ethyl group, or an n-propyl group.
  • a monovalent hydrocarbon group having 1 to 6 carbon atoms such as a group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, and phenyl group.
  • R 9 represents the carbon number;!
  • organic compound (a) (Hereinafter referred to as “organometallic compound (a)”)
  • organic metal compound of tetravalent tin (hereinafter referred to as “organotin compound”) in which 1 to 2 alkyl groups having 1 to 10 carbon atoms are bonded to one tin atom, or
  • tetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium, tetraipropoxytitanium, tetranbutoxytitanium; mesopropyltriethoxysilane, nhexyltrimethoxysilane, cyclohexyltri Ethoxysilane, phenyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2 aminoethyl) aminopropyltrimethoxysilane, 3 — (2-Aminoethyl) monoaminopropyltriethoxysilane, 3- (2aminoethyl) -aminopropylmethyldimethoxysilane, 3-anilinopropyltri
  • organometallic compound (a) for example, tetra-n-butoxyzirconium, tri-n-butoxy-ethylacetoacetate zirconium, di-n-butoxy'bis (ethylacetylacetate) zirconium, n-butoxy'tris (ethyl)
  • Organic zirconium compounds such as acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium;
  • Carboxylic acid-type organotin compounds such as
  • Mercaptide-type organotin compounds such as
  • Sulfide-type organotin compounds such as
  • Organic tin oxides such as (C H) SnO and (C H) SnO, and these organic tin oxides
  • Reaction products of side and ester compounds such as silicate, dimethyl maleate, jetyl maleate, dioctyl phthalate;
  • Such metal chelate compounds may be used singly or in combination of two or more. Of these, tri-n-butoxy ethyl acetate acetate, di-propoxy bis (acetyl acetate) titanium, zi-propoxy ethyl acetate acetate, tris (ethyl acetate acetate) aluminum, or These partial hydrolysates are preferred.
  • the catalyst can also be used by mixing with a zinc compound or other reaction retarder.
  • the amount of the catalyst used is 100 parts by weight of the silane compound (bl) (in terms of a completely hydrolyzed condensate of the organosilane (1)). Usually from 0.001 to 100 parts by weight, preferably from 0.0 to 80 parts by weight, more preferably from 0.1 to 50 parts by weight.
  • the catalyst is an organometallic compound, it is usually 100 parts by weight or less, preferably 0. 0 parts by weight based on 100 parts by weight of the silane compound (bl) (in terms of complete hydrolysis condensate of organosilane (1)). ! To 80 parts by weight, more preferably 0.5 to 50 parts by weight. If the amount of the catalyst used exceeds the upper limit, the storage stability of the composition may be lowered, or the degree of crosslinking of the organic-inorganic hybrid polymer (B) may be too high.
  • water is added to the mixture of the silane compound (bl) and the specific silyl group-containing polymer (b2) to co-condense the silane compound (bl) and the specific silyl group-containing polymer (b2). It is preferable to prepare the organic / inorganic hybrid polymer (B).
  • the amount of water added at this time is usually 0.1-1 to 1.0 monole, preferably (or 0.2-0 to 1 mol of all OR 2 groups in the silane compound (bl)). 8 Monole, more preferably (between 0.25 and 0.6 mol.
  • a composition in which gelation hardly occurs when the amount of water added is in the above range shows good storage stability.
  • Fully cross-linked organic inorganic when the amount of water added is in the above range A hybrid polymer (B) is obtained, and a cured product having excellent mechanical strength can be obtained by using a composition containing such an organic-inorganic hybrid polymer (B).
  • the silane compound (bl) and the specific silyl group-containing polymer (b2) may be hydrolyzed and condensed in an organic solvent.
  • the organic solvent used in the preparation of the silyl group-containing polymer (b2) can be used as it is.
  • an organic solvent can be added if necessary.
  • the organic solvent used in the preparation of the silyl group-containing polymer (b2) may be removed and a new organic solvent may be added.
  • the organic solvent used in the preparation of the silyl group-containing polymer (b2) is used as it is, and the organic-inorganic hybrid polymer (B ) When the solid concentration at the time of preparation is in the above range, an organic solvent may be added or not.
  • the reactivity of the silane compound (bl) and the specific silyl group-containing polymer (b2) can be controlled by adjusting the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B). If the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B) is less than the above lower limit, the reactivity between the silane compound (bl) and the specific silyl group-containing polymer (b2) may be lowered. If the solid content concentration during the preparation of the organic-inorganic hybrid polymer (B) exceeds the upper limit, gelation may occur.
  • the amount of solid content at the solid content concentration mentioned here is the amount used in terms of solid hydrolysis condensate of the silane compound (bl) (Wbl) and the amount used in terms of solid content of the specific silyl group-containing polymer (b 2). This is the total amount of (Wb2).
  • the organic solvent is not particularly limited as long as the above components can be mixed uniformly.
  • the organic-inorganic hybrid polymer (B) in order to improve the storage stability of the organic-inorganic hybrid polymer composition, particularly the organic-inorganic hybrid polymer (B), the organic-inorganic hybrid polymer (B) is prepared, and if necessary, the stability is increased. It is preferable to add an improver.
  • the stability improver used in the present invention is represented by the following formula (6):
  • R 1Q is methyl group, ethyl group, n-propyl group, i-propyl group, n butyl group, sec butyl group, t butyl group, n pentyl group, n hexyl group, cyclohexyl group, Represents a monovalent hydrocarbon group having 6 to 6 carbon atoms, such as a phenyl group, and R 11 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, or a methoxy group, an ethoxy group, n- (Represents an alkoxyl group having 1 to 16 carbon atoms such as propoxy group, i-poxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryloxy group, and stearoxy group.)
  • organometallic compounds are used as the catalyst, it is preferable to add a stability improver represented by the above formula (6).
  • the stability improver coordinates to the metal atom of the organometallic compound, and this coordination is excessive between the silane compound (bl) and the specific silyl group-containing polymer (b2). It is considered that the storage stability of the obtained organic-inorganic hybrid polymer composition, particularly the organic-inorganic hybrid polymer (B), can be further improved by suppressing the co-condensation reaction.
  • stability improvers include acetylacetone, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, i-propyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, acetoacetate t.
  • the stability improver may be used alone or in combination of two or more.
  • the amount of the stability improver used in the present invention is usually 2 moles or more, preferably 3 to 20 moles per mole of the organometallic compound of the organometallic compound. If the amount of the stability improver is less than the above lower limit, the effect of improving the storage stability of the resulting composition will be insufficient.
  • the organic-inorganic hybrid polymer (B) used in the present invention can be prepared by co-condensing the silane compound (bl) and the specific silyl group-containing polymer (b2). Particularly preferably, it can be prepared by adding a hydrolysis / condensation reaction application catalyst and water to a mixture of the silane compound (bl) and the specific silyl group-containing polymer (b2) to perform cocondensation.
  • Wbl is a value converted into a complete hydrolysis condensate of the silane compound (M)
  • Wb2 is a value converted into a solid content of the specific silyl group-containing polymer (b2).
  • the organic substrate surface such as an acrylic plate is organic without being treated with a primer or the like. Good adhesion to the substrate.
  • the organic-inorganic hybrid polymer (B) is preferably prepared by the following methods (1) to (3).
  • organosilane (1) as the silane compound (bl), adding water in the above range to the temperature, temperature of 40-80 ° C, time of 0.5-; Carry out the hydrolysis-condensation reaction of (1).
  • the specific silyl group-containing polymer (b2) and a catalyst for hydrolysis / condensation reaction are added and mixed, and further, the condensation reaction is carried out at a temperature of 40 to 80 ° C., a reaction time of 0.5 to 12 hours, and organic inorganic A hybrid polymer (B) is prepared. Then, if necessary, add other additives such as stability improvers.
  • the acidic compound used for neutralization the acidic compounds exemplified above can be used.
  • the amount of the acidic compound used is usually 0.5 to 2.0 monole, preferably 0.8 to 1.5 monole, more preferably 0.9 to 1. mol per 1 mol of the basic compound used for hydrolysis condensation. 3 mono.
  • an acidic compound is used by dissolving in water, it is usually 10 to 500 parts by weight, preferably 20 to 200 parts by weight with respect to 100 parts by weight in total of the silane compound (bl) and the specific silyl group-containing polymer (b2). Dissolve in 300 parts, more preferably 30-200 parts of water. After neutralization, the mixture is sufficiently stirred and allowed to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, the lower layer moisture is removed.
  • the water used for the water washing after neutralization is usually 10 to 500 parts by weight, preferably 20 to 300 parts per 100 parts by weight in total of the silane compound (bl) and the specific silyl group-containing polymer (b2). 30 to 200 parts, more preferably 30 to 200 parts.
  • washing with water is performed by adding water, stirring sufficiently, and then allowing to stand, and after confirming phase separation between the aqueous phase and the organic solvent phase, removing the moisture in the lower layer.
  • the number of washings is preferably 1 or more times, more preferably 2 or more times.
  • a metal chelate compound is used as the hydrolysis-condensation catalyst, it is preferable to add the stability improver after the reaction.
  • the weight-average molecular weight of the organic-inorganic hybrid polymer (B) obtained by the above method is usually 3,0 in terms of polystyrene measured by gel permeation chromatography.
  • the organic fine particle-containing organic / inorganic hybrid polymer composition according to the present invention comprises an oxide fine particle (A) and an organic / inorganic hybrid polymer (B), phosphoric acid having an organic group having 6 or more carbon atoms or an oxyalkylene group. It can be obtained by mixing with an organic solvent in the presence of a basic compound, an acidic compound or a metal chelate compound and subjecting it to a dispersion treatment, without using a compound having s.
  • organic solvent examples include the organic solvents exemplified in the organic-inorganic hybrid polymer (B).
  • organic solvents other than alcohols such as methyl ethyl ketone, methyl isobutyl ketone, diisoptyl ketone, and the like in that the dispersion stability of the organic inorganic hybrid polymer composition containing fine oxide particles is good.
  • Toluene, xylene, ethyl acetate, butyl acetate, and mixtures thereof are preferred.
  • These organic solvents are preferably used in a state where moisture has been removed by dehydration in advance.
  • the amount of the organic solvent used is not particularly limited as long as it is an amount that can uniformly disperse the oxide fine particles (A)! /, But the solid content of the obtained organic / inorganic hybrid polymer composition containing oxide fine particles is not limited.
  • the concentration is preferably 5 to 80% by weight, more preferably 7 to 70% by weight, and particularly preferably 10 to 60% by weight.
  • Examples of the basic compound, acidic compound, and metal chelate compound include the compounds exemplified in the organic-inorganic hybrid polymer (B).
  • organic-inorganic hybrid polymer (B) examples include the compounds exemplified in the organic-inorganic hybrid polymer (B).
  • acidic compounds and metal chelate compounds basic compounds and acidification Triethylamine, tetramethylammonium hydroxide, and pyridine are particularly preferred, in which a basic compound in which a compound is preferred and an organic amine compound in which a compound is preferred is more preferred.
  • the basic compound, acidic compound or metal chelate compound is usually added to the oxide fine particle-containing organic-inorganic hybrid polymer composition of the present invention in an amount of 0.00 with respect to 100 parts by weight of the oxide fine particles (A). ! ⁇ 20 parts by weight, preferably 0.005 ⁇ 10 parts by weight, more preferably 0.0;! ⁇ 5 parts by weight, more preferably 0.01 ⁇ ; It is desirable to contain 5 parts by weight.
  • the composition of the oxide fine particle-containing polysiloxane exhibits good dispersion stability.
  • the above-mentioned organic / inorganic hybrid polymer composition containing fine oxide particles is obtained by adding oxide fine particles (A), an organic / inorganic hybrid polymer (B), a basic compound, an acidic compound or a metal chelate compound to an organic solvent.
  • the oxide fine particles (A) can be prepared by dispersing them sufficiently in an organic solvent.
  • a known disperser such as a ball mill, a sand mill (bead mill, a high shear bead mill), a homogenizer, an ultrasonic homogenizer, a nanomizer, a propeller mixer, a high shear mixer, or a paint shaker.
  • a dispersed fine particle dispersion ball mill and a sand mill are preferably used.
  • the oxide fine particles (A) are mixed with the organic / inorganic nano- or hybrid polymer (B) in the presence of a basic compound, acidic compound or metal chelate compound, the basic compound, acidic compound or metal chelate is mixed.
  • the organic-inorganic hybrid polymer (B) condensation reaction proceeds on the surface of the oxide fine particles (A) by the catalytic action of the oxide compound, and the surface of the oxide fine particles (A) becomes hydrophobic and is finely dispersed in the organic solvent. It is assumed that it will be easy to do.
  • the organic / inorganic hybrid polymer composition containing fine oxide particles of the present invention is preferably an organic-inorganic hybrid polymer (B) based on 100 parts by weight of the fine oxide particles (A) in terms of complete hydrolysis condensate. 1 to 1000 parts by weight, more preferably 5 to 900 parts by weight, and particularly preferably 10 to 800 parts by weight.
  • the above-mentioned organic / inorganic hybrid polymer composition containing fine oxide particles comprises fine oxide particles.
  • the child (A) is a highly dispersed composition having a volume average dispersed particle size of 300 nm or less, preferably 200 nm or less, more preferably 150 nm or less.
  • Power S can be. Since this cured product contains the organic-inorganic hybrid polymer (B), it is excellent in weather resistance, flexibility and followability to the substrate.
  • the said base material is an organic base material
  • the adhesiveness of a base material and a hardening body improves further by processing the surface of an organic base material with a primer.
  • the weight ratio (Wbl / Wb2) of the content (Wbl) of the silane compound (bl) and the content (Wb2) of the specific silyl group-containing polymer (b2) is preferably 50 / 50-95 / 5, More preferably, when the organic / inorganic hybrid polymer (B) of 60/40 to 85/15 is used, the effect of primer treatment is great.
  • the primer include a solution containing the specific silyl group-containing polymer (b2).
  • the weight average molecular weights of the specific silyl group-containing polymer and the organic-inorganic hybrid polymer are shown as polystyrene conversion values measured by gel permeation chromatography under the following conditions.
  • the appearance of the obtained composition was visually observed.
  • the volume average dispersed particle size of the composition in which no sedimentation of the fine particles was observed was measured using a microtrack ultrafine particle size distribution meter (manufactured by Nikkiso Co., Ltd. UPA150 ”) and evaluated according to the following criteria.
  • Dispersibility was also evaluated according to the following criteria. That is, the appearance of the obtained composition was visually observed.
  • the volume average dispersed particle size of the composition in which no sedimentation of fine particles was observed was measured with a Microtrac ultrafine particle size distribution meter (“UPA150” manufactured by Nikkiso Co., Ltd.) and evaluated according to the following criteria.
  • AA No separation / sedimentation. Volume average dispersed particle size ⁇ 150nm.
  • A No separation / sedimentation. 150 nm ⁇ volume average dispersed particle size ⁇ 200 nm.
  • a cured product having a thickness of 5 m was produced on a quartz glass plate by drying and curing at 00 ° C. for 1 hour.
  • the cured product was measured for spectral transmittance at a wavelength of 500 to 700 nm with an ultraviolet-visible spectrophotometer and evaluated according to the following criteria.
  • Light transmittance is 70% or more and 90% or less.
  • the obtained composition was applied on a quartz glass plate so that the dry film thickness was 5 in, and then dried and cured at 100 ° C. for 1 hour to form a cured product having a thickness of 5 m on the quartz glass plate.
  • the light transmittance of this cured product at a wavelength of 450 nm was measured with an ultraviolet-visible spectrophotometer and evaluated according to the following criteria.
  • the primer treatment was carried out using 100 parts by weight of the solution containing the specific silyl group-containing polymer (b2-1) obtained in Preparation Example 11 below, and i-butyl alcohol solution of dioctyltin dimaleate ester (solid content concentration: about 10%) A solution obtained by adding 10 parts of the mixture and stirring sufficiently was applied so that the dry coating film was 1, im.
  • ⁇ Preparation Example 1 In a reactor equipped with a reflux condenser and a stirrer, add 55 parts of methyl methacrylate, 5 parts of 2 - ethyl hexyl acrylate, 5 parts of cyclohexyl methacrylate, 10 parts of ⁇ ⁇ -methacryloxypropyltrimethoxysilane , Add 20 parts of glycidyl metatalylate, 4 parts of 4- (meth) atalyloyloxy 2, 2, 6, 6 5 parts of tetramethylpiperidine, 75 parts of i-butyl alcohol, 50 parts of methyl ethyl ketone and 25 parts of methanol, and stir. While heating to 80 ° C.
  • a solution containing the union (b2 1) was obtained.
  • a reactor equipped with a reflux condenser and a stirrer was charged with 30 parts of methyl methacrylate, 10 parts of n-propyl acrylate, 10 parts of ⁇ -methacryloxypropyltrimethoxysilane, glycidyl methacrylate.
  • Powdered zinc oxide fine particles (primary average particle size:
  • a metal oxide fine particle-containing organic-inorganic hybrid polymer composition (2) having a solid content concentration of 20% by weight was prepared in the same manner as in Example 1 except that 100 parts by weight were used. The results of the evaluation of the properties of this composition are shown in Table 21.
  • a fine particle-containing organic-inorganic hybrid polymer composition (3) was prepared. The results of evaluating the properties of this composition are shown in Table 21.
  • Example 21 Similar to Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-2) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1). Thus, an organic-inorganic hybrid polymer composition (5) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 21.
  • Example 2 Similar to Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-3) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1).
  • an organic-inorganic hybrid polymer composition (6) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 2. Shown in 1.
  • Example 2 The same as Example 2 except that 500 parts by weight of the solution containing the organic-inorganic hybrid polymer (B-4) (100 parts by weight in terms of solid content) was used instead of the solution containing the organic-inorganic hybrid polymer (B-1).
  • an organic-inorganic hybrid polymer composition (7) containing metal oxide fine particles having a solid content concentration of 20% by weight was prepared. The results of evaluating the properties of this composition are shown in Table 21.
  • Powdery rutile type titanium oxide fine particles were dispersed in methylisoptyl ketone in the same manner as in Example 1 except that triethylamine was not used, but the titanium oxide fine particles settled.
  • Example 1 except that the solution containing the organic-inorganic hybrid polymer (B-1) was used.
  • powdery rutile-type titanium oxide fine particles were dispersed in methylisobutyl ketone, but the titanium oxide fine particles settled.
  • Titanium oxide fine particle water dispersion (Ishihara Sangyo Co., Ltd. “STS-01”, TiO concentration 30% by weight, titanium oxide fine particle volume level)
  • Uniformly dispersed particle size 60 nm, organic dispersant: 0 wt%) 300 parts by weight is put in a container, and 500 parts by weight of the solution containing the above organic-inorganic hybrid polymer (B-1) is added (100% in terms of solid content). Part by weight) and 400 parts by weight of methylisobutyl ketone, and further 2000 parts by weight of 0.1 mm diameter zircoyu beads were added to this mixture, and the mixture was stirred at 1500 rpm for 1 hour using bead minole. The titanium oxide fine particles settled.
  • polysiloxane with Mw 20,000 (GE Toshiba Silicone Co., Ltd., trade name: XR31—B2733U00 parts by weight and methinoisoisobutyl ketone 400 weights)
  • a metal oxide fine particle-containing polysiloxane composition (C5) having a solid content concentration of 20% by weight was obtained in the same manner as in Example 1 except that the solution containing the components was used. Is shown in Table 2-2.

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Abstract

L'invention concerne une composition polymère hybride organique-inorganique contenant de fines particules d'oxyde, obtenue en mélangeant (A) de fines particules d'oxyde de silicium et/ou de fines particules d'oxyde métallique avec (B) un polymère hybride organique-inorganique, obtenu par une réaction d'hydrolyse/condensation d'au moins un composé de silane (b1) choisi dans le groupe comprenant au moins un organosilane représenté par la formule (1) ci-dessous, les produits d'hydrolyse de l'organosilane et les produits de condensation de l'organosilane, et un polymère (b2) comprenant un groupement silyle contenant un atome de silicium relié avec un groupement hydrolysable et/ou un groupement hydroxyle, dans un solvant organique en présence d'un composé basique, d'un composé acide ou d'un composé de chélate métallique, dispersant ainsi les fines particules d'oxyde (A) dans le solvant organique. R1nSi(OR2)4-n (1) (Dans la formule, R1 représente un groupement organique monovalent ayant de 1 à 8 atomes de carbone ; R2 représente un groupement alkyle ayant de 1 à 5 atomes de carbone ou un groupement acyle ayant de 1 à 6 atomes de carbone ; et n représente un entier de 0 à 2.
PCT/JP2007/068079 2006-09-19 2007-09-18 Composition polymère hybride organique-inorganique contenant de fines particules d'oxyde et son procédé de fabrication WO2008035669A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010077409A (ja) * 2008-08-26 2010-04-08 Jgc Catalysts & Chemicals Ltd 樹脂被覆金属酸化物粒子分散ゾルの製造方法および該樹脂被覆金属酸化物粒子を含む透明被膜形成用塗布液ならびに透明被膜付基材
JP4968491B1 (ja) * 2011-09-20 2012-07-04 大日本印刷株式会社 赤外線反射性フィルム
WO2013111735A1 (fr) 2012-01-25 2013-08-01 コニカミノルタアドバンストレイヤー株式会社 Film optique
WO2013168714A1 (fr) 2012-05-08 2013-11-14 コニカミノルタ株式会社 Verre stratifié
WO2014156822A1 (fr) 2013-03-29 2014-10-02 コニカミノルタ株式会社 Verre feuilleté
WO2014162864A1 (fr) 2013-04-02 2014-10-09 コニカミノルタ株式会社 Verre feuilleté de protection contre les rayons thermiques et son procédé de production
JP2017020020A (ja) * 2015-07-14 2017-01-26 国立研究開発法人産業技術総合研究所 表面改質された球状単分散コアシェル型酸化セリウムポリマーハイブリッドナノ粒子
KR20170030532A (ko) 2014-07-14 2017-03-17 스미토모 오사카 세멘토 가부시키가이샤 금속 산화물 입자 분산액, 금속 산화물 입자 함유 조성물, 도막, 및 표시 장치
JPWO2016031931A1 (ja) * 2014-08-29 2017-07-27 住友大阪セメント株式会社 樹脂組成物、塗膜、塗膜付きプラスチックフィルム、及び表示装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10183062A (ja) * 1996-10-30 1998-07-07 Jsr Corp コーティング用組成物
JPH1147688A (ja) * 1997-08-07 1999-02-23 Jsr Corp 樹脂成形品
JP2005113063A (ja) * 2003-10-09 2005-04-28 Jsr Corp コーティング組成物および構造体
WO2006025535A1 (fr) * 2004-09-03 2006-03-09 Jsr Corporation Composition de revêtement, composition de sous-couche, corps multicouche ayant un film de revêtement formé d'une telle composition, film de revêtement photocatalyseur et corps moulé
WO2007108281A1 (fr) * 2006-03-16 2007-09-27 Jsr Corporation Formule de polysiloxane contenant des particules d'oxyde et sa méthode de production
WO2007119517A1 (fr) * 2006-03-31 2007-10-25 Jsr Corporation Composition de polysiloxane contenant des particules d'oxyde de metal et son procede de production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10183062A (ja) * 1996-10-30 1998-07-07 Jsr Corp コーティング用組成物
JPH1147688A (ja) * 1997-08-07 1999-02-23 Jsr Corp 樹脂成形品
JP2005113063A (ja) * 2003-10-09 2005-04-28 Jsr Corp コーティング組成物および構造体
WO2006025535A1 (fr) * 2004-09-03 2006-03-09 Jsr Corporation Composition de revêtement, composition de sous-couche, corps multicouche ayant un film de revêtement formé d'une telle composition, film de revêtement photocatalyseur et corps moulé
WO2007108281A1 (fr) * 2006-03-16 2007-09-27 Jsr Corporation Formule de polysiloxane contenant des particules d'oxyde et sa méthode de production
WO2007119517A1 (fr) * 2006-03-31 2007-10-25 Jsr Corporation Composition de polysiloxane contenant des particules d'oxyde de metal et son procede de production

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010077409A (ja) * 2008-08-26 2010-04-08 Jgc Catalysts & Chemicals Ltd 樹脂被覆金属酸化物粒子分散ゾルの製造方法および該樹脂被覆金属酸化物粒子を含む透明被膜形成用塗布液ならびに透明被膜付基材
JP4968491B1 (ja) * 2011-09-20 2012-07-04 大日本印刷株式会社 赤外線反射性フィルム
WO2013111735A1 (fr) 2012-01-25 2013-08-01 コニカミノルタアドバンストレイヤー株式会社 Film optique
WO2013168714A1 (fr) 2012-05-08 2013-11-14 コニカミノルタ株式会社 Verre stratifié
WO2014156822A1 (fr) 2013-03-29 2014-10-02 コニカミノルタ株式会社 Verre feuilleté
WO2014162864A1 (fr) 2013-04-02 2014-10-09 コニカミノルタ株式会社 Verre feuilleté de protection contre les rayons thermiques et son procédé de production
KR20170030532A (ko) 2014-07-14 2017-03-17 스미토모 오사카 세멘토 가부시키가이샤 금속 산화물 입자 분산액, 금속 산화물 입자 함유 조성물, 도막, 및 표시 장치
JPWO2016031931A1 (ja) * 2014-08-29 2017-07-27 住友大阪セメント株式会社 樹脂組成物、塗膜、塗膜付きプラスチックフィルム、及び表示装置
JP2017020020A (ja) * 2015-07-14 2017-01-26 国立研究開発法人産業技術総合研究所 表面改質された球状単分散コアシェル型酸化セリウムポリマーハイブリッドナノ粒子

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