JP5164942B2 - Curable composition, adhesive and sealant - Google Patents

Description

  The present invention relates to a curable composition, an adhesive, and a sealing material.

  Various curable compositions based on a polymer having a crosslinkable hydrolyzable silyl group as a main component have been proposed. These curable compositions are crosslinked by the atmosphere or moisture contained in the adherend, and give a cured product excellent in durability, weather resistance, transparency and adhesiveness. Therefore, the said curable composition is used for various uses, such as a coating material, a coating agent, an adhesive agent, a pressure sensitive adhesive, a sealant, and a sealing material.

  The curable composition crosslinks by forming siloxane bonds, but organic tin compounds such as dibutyltin dilaurate, tin octylate, and organic lead compounds such as lead octylate to control the rate of crosslinking. Metal compounds are used. However, organometallic compounds containing tin and lead have a problem of high toxicity.

  In order to solve this problem, Patent Documents 1 to 3 propose a technique using an organometallic compound such as titanium, bismuth, or hafnium as a moisture curing reaction promoting catalyst. However, when these moisture curing reaction promoting catalysts are used, there is a problem that the curability of the curable composition is not sufficient and the moisture curing reaction promoting catalyst is very expensive.

  Therefore, in order to solve the above problems, it is conceivable to use a carboxylic acid compound instead of the organometallic compound. However, there is a problem that the curing rate is remarkably slow as compared with the case where an organometallic compound is used, and the cured product is brittle and the resin film strength is low.

  It is conceivable to use amines or amine derivatives in addition to the carboxylic acid compound, but it has the same problems as the carboxylic acid compound, and is not practical in terms of toxicity and odor.

JP 05-311063 A JP 2001-342363 A JP 2004-043738 A

  The present invention provides a curable composition having low toxicity and high resin film strength after moisture curing and excellent curability.

  The curable composition of the present invention contains 100 parts by weight of a polymer containing a hydrolyzable silyl group, 0.1 to 50 parts by weight of a carboxylic acid anhydride and 0.1 to 20 parts by weight of a ketimine compound, and It is characterized by not containing an organometallic compound as a silanol condensation catalyst.

  The hydrolyzable silyl group in a polymer containing a hydrolyzable silyl group is a group in which a hydrolyzable group is bonded to a silicon atom, and can form a siloxane bond by reaction with moisture to be crosslinked. Indicates a group.

  The hydrolyzable group of the hydrolyzable silyl group is not particularly limited, and examples thereof include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, and a mercapto group. An alkoxy group is preferred because the hydrolysis reaction is gentle and easy to handle, and by-products generated during the hydrolysis are relatively excellent in safety.

  1 to 3 hydrolyzable groups can be bonded to one silicon atom. When a plurality of hydrolyzable groups are bonded to one silicon atom, the hydrolyzable groups are all May be the same type or a combination of different types.

  In addition, the number of hydrolyzable groups bonded to one silicon atom is preferably 2 or 3 from the viewpoint of curability and storage stability of the curable composition.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, an n-butoxy group, a t-butoxy group, a phenoxy group, and a benzyloxy group, and a methoxy group and an ethoxy group are preferable.

  The method for introducing the hydrolyzable silyl group into the polymer is not particularly limited. For example, (1) a hydrosilane having a hydrolyzable silyl group is allowed to act on a polymer having an unsaturated group introduced into the molecule. A method of hydrosilylation, (2) a method of reacting a polymer having an unsaturated group in the molecule with a compound having a mercapto group and a hydrolyzable silyl group, and (3) a polymer weight having a functional group in the molecule. Examples thereof include a method of reacting a compound having a functional group reactive with this functional group and a hydrolyzable silyl group, specifically, a reaction between an isocyanate group and a hydroxyl group, an isocyanate group, A reaction with an amino group, a reaction between an isocyanate group and a mercapto group, or the like can be used.

  The main chain skeleton of the polymer containing a hydrolyzable silyl group is not particularly limited. For example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer Polymers, polyoxyalkylene polymers such as polyoxypropylene-polyoxybutylene copolymers, saturated hydrocarbon polymers, polychloroprene, polyisoprene, isoprene or copolymers of butadiene and acrylonitrile and / or styrene, polybutadiene , Copolymers of isoprene or butadiene, acrylonitrile and styrene, radical polymerization of monomers such as ethyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, Vinyl polymer obtained by radical polymerization of monomers such as tyrene, graft polymer obtained by polymerizing vinyl monomer in the above polymer, polysulfide polymer, nylon 6 by ring-opening polymerization of ε-caprolactam, hexa Nylon 6 · 6 by condensation polymerization of methylenediamine and adipic acid, nylon 6 · 10 by condensation polymerization of hexamethylenediamine and sebacic acid, nylon 11 by condensation polymerization of ε-aminoundecanoic acid, opening of ε-aminolaurolactam Nylon 12 by ring polymerization, a polyamide polymer such as copolymer nylon having two or more components of the above nylon, a polycarbonate polymer produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl phthalate heavy Examples include coalescence. In addition, (meth) acrylate means a methacrylate or an acrylate.

  As the main chain skeleton of a polymer containing a hydrolyzable silyl group, the glass transition temperature is relatively low and the polymer is easy to handle. Therefore, ethylene-propylene copolymer, polyisobutylene, isobutylene and isoprene are used. And hydrogenated products of the copolymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and other saturated hydrocarbon polymers, polyoxyalkylene polymers, and (meth) acrylate polymers. Furthermore, polyoxyalkylene polymers and (meth) acrylate polymers have high moisture permeability, so that they are excellent in deep part curability when made into a one-component composition, and are also excellent in adhesion. This is more preferable.

  When the glass transition temperature of the polymer containing a hydrolyzable silyl group is high, the viscosity of the polymer containing the hydrolyzable silyl group is increased, and the handleability of the curable composition is lowered. Is preferable, and 0 ° C. or lower is more preferable. In addition, the glass transition temperature of the polymer containing a hydrolyzable silyl group means what was measured by differential scanning calorimetry (DSC).

  The saturated hydrocarbon polymer will be described in more detail. The polymer does not contain a carbon-carbon unsaturated bond. Specifically, is it obtained by polymerizing an olefin monomer such as ethylene, propylene, butene and isobutylene? , Butadiene, isoprene and other diene compounds can be polymerized and then hydrogenated.

  The polyoxyalkylene polymer will be described in more detail. The main chain is represented by the general formula — (R—O) n — (wherein R represents an alkylene group having 1 to 14 carbon atoms). A polymer containing units. R is preferably an alkylene group having 1 to 4 carbon atoms. The main chain skeleton of the polyoxyalkylene polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units.

  The (meth) acrylate polymer will be described in more detail. The (meth) acrylate monomer constituting the main chain is not particularly limited. For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate , Tert-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isomyristyl acrylate, stearyl acrylate, isobornyl acrylate, benzyl acrylate, 2-butoxyethyl acrylate, 2- Phenoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, hexanediol diacrylate, ethylene glycol Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, epoxy acrylate, polyester acrylate, urethane acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, 3-hydroxy-3-methylbutyl Acrylate, 2-hydroxy- -Phenoxypropyl acrylate, 2- [acryloyloxy] ethyl-2-hydroxyethylphthalic acid, 2- [acryloyloxy] ethyl-2-hydroxypropylphthalic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, tert -Butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, isononyl methacrylate, isomyristyl methacrylate, stearyl methacrylate, isobornyl methacrylate, benzyl methacrylate, 2-butoxyethyl methacrylate, 2-phenoxyethyl Methacrylate, glycidyl methacrylate, tetrahydrofurfuryl meta Acrylate, hexanediol dimethacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylol, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate 6-hydroxyhexyl methacrylate, 3-hydroxy-3-methylbutyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, pentaerythritol trimethacrylate, 2- [methacryloyloxy] ethyl-2-hydroxyethylphthalic acid, 2- [Methacryloyloxy] ethyl-2-hydroxypropylphthalic acid and the like can be mentioned, and n-butyl acrylate and methyl methacrylate are preferable. The (meth) acrylic acid ester monomer may be used alone or in combination of two or more.

  In the (meth) acrylate polymer, other monomers can be copolymerized. Examples of such monomers include styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene. Styrene derivatives, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate and other compounds having a vinyl ester group, maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, ( (Meth) acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propylvinylether, n-butylvinylether, isobutylvinylether, tert-butyl Ru vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, triethylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene glycol Divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol Divinyl ether, di (4-vinyloxy) butyl isophthalate, glutar Di (4-vinyloxy) butyl acid, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol Examples thereof include compounds having a vinyloxy group such as monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether. These monomers may be used alone or in combination of two or more.

  The polymerization method of the (meth) acrylate polymer is not particularly limited, and a known method can be used. For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method can be used. Various polymerization methods such as a combination method, a living cationic polymerization method, and a living radical polymerization method may be mentioned.

  In the main chain skeleton of the polymer, for example, a bond generated by a reaction between an isocyanate group and an active hydrogen group may be contained. Examples of such a bond include a urethane bond formed by a reaction between an isocyanate group and a hydroxyl group, a urea bond formed by a reaction between an isocyanate group and an amino group, and a thiourethane bond formed by a reaction between an isocyanate group and a mercapto group. Etc.

  In the main chain skeleton of the polymer, a bond generated by a reaction between an active hydrogen contained in the above-described urethane bond, urea bond or thiourethane bond and an isocyanate group may be contained. These bonds are formed when a hydrolyzable silyl group is introduced by reacting a functional group in the polymer with a compound having a functional group reactive to this functional group and a hydrolyzable silyl group. There is a case.

  The main chain skeleton of the polymer containing a hydrolyzable silyl group may be linear or branched. The number average molecular weight of the polymer containing a hydrolyzable silyl group is preferably from 500 to 100,000, more preferably from 3,000 to 30,000. When the number average molecular weight of the polymer containing a hydrolyzable silyl group is smaller than 500, the extensibility of a cured product obtained by curing the curable composition may be lowered. When the number average molecular weight of the polymer containing a hydrolyzable silyl group is greater than 100,000, the viscosity of the curable composition is increased, so that the handleability is lowered. In addition, the number average molecular weight of the polymer containing a hydrolyzable silyl group means the polystyrene conversion number average molecular weight measured using Gel Permeation Chromatography system (GPC).

  A carboxylic acid anhydride refers to a compound having a carboxylic acid anhydride structure (—CO—O—CO—) in the molecule. As a method for obtaining a carboxylic acid anhydride structure, a known method can be used, and a method of dehydrating and condensing two molecules of carboxylic acid can be mentioned.

  Examples of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3. , 6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride Acid, 4-methylhexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, ethylene glycol bisanhydro trimellitate, glycerin bisanhydrotrimethyl Examples include melitrate monoacetate. Carboxylic anhydrides may be used alone or in combination of two or more.

  If the content of the carboxylic acid anhydride in the curable composition is small, the moisture curing reaction rate of the curable composition decreases, and if it is large, a bleedout problem occurs when the carboxylic acid anhydride is liquid. Therefore, it is limited to 0.1 to 50 parts by weight with respect to 100 parts by weight of the polymer containing a hydrolyzable silyl group, and preferably 5 to 30 parts by weight.

  A ketimine compound refers to a compound in which the oxygen of the carbonyl group of the ketone is substituted with an imino group. Examples of ketimine compounds include 1,2-ethylenebis (isopentylideneimine), 1,2-hexylenebis (isopentylideneimine), p, p′-biphenylenebis (isopentylideneimine), 1,2- Ethylenebis (isopropylideneimine), 1,3-propylenebis (isopropylideneimine), p-phenylenebis (isopentylidenimine), 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl 3,6,9-triaza-2,9-undecadiene, 2,10-diphenyl-3,6,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-3 , 10-tridecadiene, 3,11-diethyl-4,7,10-triaza-3,10-tridecadiene, 2,4,12,14-teto Lamethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza-4,19-trieicosadiene, 2,4 15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 9- (3-butoxy-2-hydroxypropyl) 5,13-dimethyl-6,9,12-triaza -5,12-heptadecadiene, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine A ketimine compound containing a hydrolyzable silyl group in the molecule is preferred. A ketimine compound may be used independently or 2 or more types may be used together. The ketimine compound is commercially available from Asahi Kasei Wacker under the trade name “NF-1104”.

  When the content of the ketimine compound in the curable composition is small, the deep curability of the curable composition is decreased, resulting in a decrease in adhesive strength. When the content is large, the curable composition is chemically reacted with moisture. Since the amount of volatile components generated in the process increases, the amount is limited to 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer containing a hydrolyzable silyl group, and preferably 1 to 10 parts by weight.

  The curable composition of the present invention does not contain an organometallic compound as a silanol condensation catalyst. For example, there is no problem of high toxicity as in the case where a tin-based compound is contained as an organometallic compound.

  Examples of the organometallic compound include dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, a reaction product of dibutyltin oxide and phthalate, dibutyltin diacetylacetonate, dibutyltin bistriethoxysilicate, tetrabutyl-bistriethoxy Organotin compounds such as silicate distannoxane, organotitanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate, aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminumethyl Organoaluminum compounds such as acetoacetate, gold such as germanium, lead, boron, gallium, indium, zirconium Compound and an organometallic compound which is a reaction product of an organic compound can be exemplified.

  The curable composition of the present invention includes a reactive resin, a viscosity modifier, a plasticizer, a silane coupling agent, a thixotrope agent, a filler, a tackifier, an antioxidant, a light within a range that does not impair the physical properties. Additives such as stabilizers, ultraviolet absorbers, solvents, colorants, flame retardants, sagging inhibitors, fragrances, pigments, dyes, and dehydrating agents may be contained.

  Examples of the reactive resin include an epoxy resin. As the epoxy resin, a commonly used epoxy resin that is cured by an epoxy curing agent can be used. For example, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, 3, Examples include 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,4-butanediol diglycidyl ether, phthalic acid diglycidyl ester, triglycidyl isocyanurate, and the like.

  If the content of the epoxy resin in the curable composition is small, the effect of adding the epoxy resin may not be exhibited, and if it is large, the film of the cured product obtained by curing the curable composition becomes hard, Since low temperature characteristics, such as adhesiveness, fall, 0.5-300 weight part is preferable with respect to 100 weight part of polymers containing a hydrolyzable silyl group.

  Although it does not specifically limit as a viscosity modifier, The compound excellent in compatibility with the polymer containing a hydrolysable silyl group is preferable. Examples of viscosity modifiers include acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutenes, polyolefins, polyalkylene oxides, polyurethanes, and polyamides. , Natural rubber, polybutadiene, polyisoprene, nitrobutadiene rubber (NBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polystyrene-block-poly (ethylene) -Co-butylene) -block-polystyrene (SEBS), hydrogenated nitrobutadiene rubber (hydrogenated NBR), hydrogenated styrene-butadiene-styrene block copolymer (hydrogenated SBS), hydrogenated styrene-isopropyl Down - styrene block copolymer (hydrogenated SIS), hydrogenated polystyrene -block-poly (ethylene -co- butylene) -block-polystyrene (hydrogenated SEBS) and the like. A viscosity modifier may be used independently or 2 or more types may be used together.

  If the content of the viscosity modifier in the curable composition is small, the effect of adding the viscosity modifier may not be manifested. If it is large, the viscosity of the curable composition is increased and the curable composition is handled. Therefore, 0.1 to 50 parts by weight is preferable with respect to 100 parts by weight of the polymer containing a hydrolyzable silyl group, and 0.3 to 20 parts by weight is more preferable.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid-basic acid esters such as glycerol monooleate, and dioctyl adipate. Fatty acid dibasic acid esters, aliphatic esters such as butyl oleate and methyl acetylricillinoleate, trimellitic acid esters, chlorinated paraffins, alkyl diphenyls, hydrocarbon oils such as partially hydrogenated terphenyls, processes Oils, epoxidized soybean oil, epoxy plasticizers such as epoxy benzyl stearate, vinyl polymers obtained by polymerizing vinyl monomers, diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester, etc. Polyester plastics obtained from esters of realkylene glycol, dibasic acids such as sebacic acid, adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol And polyethers such as agents, polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, or derivatives obtained by converting hydroxyl groups of the polyether polyols to ester groups, ether groups, and the like.

  If the number average molecular weight of the plasticizer is low, the plasticizer may bleed out. If the number average molecular weight is high, the viscosity of the curable composition may increase, and the handleability of the curable composition may decrease. ˜15000 is preferred.

  If the content of the plasticizer in the curable composition is small, the effect of adding the plasticizer may not be exhibited. If the content is large, the mechanical strength of the cured product obtained by curing the curable composition is lowered. Therefore, the amount is preferably 5 to 150 parts by weight with respect to 100 parts by weight of the polymer containing a hydrolyzable silyl group.

  The silane coupling agent is not particularly limited. For example, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltrimethylsilane. Methoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methacryloyloxymethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ -Aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) L) Aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane , Γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ- (2- (2-aminoethyl) aminoethyl) aminopropyltrimethoxysilane, γ- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino) -2-methylpropyltrimethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, γ-ureidopropyl Trimethoxy Run, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenylaminomethyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ- Aminopropyltriethoxysilane, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxy Silane, (2-aminoethyl) aminomethyltrimethoxysilane, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Sisilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, (isocyanatemethyl) trimethoxysilane, (isocyanatemethyl) dimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, γ -Mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxy Examples include silane, mercaptomethyltriethoxysilane, γ-chloropropyltrimethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate, a reaction product of aminosilane and glycidylsilane, a reaction product of aminosilane and isocyanate silane, and the like. A silane coupling agent may be used independently or 2 or more types may be used together.

  When the content of the silane coupling agent in the curable composition is small, the effect of adding the silane coupling agent may not be exhibited, and when it is large, the moisture curing rate of the curable composition may be decreased. Therefore, 0.1-30 weight part is preferable with respect to 100 weight part of polymers containing a hydrolyzable silyl group, and 1-20 weight part is more preferable.

  The thixotropic agent is not particularly limited as long as it can develop thixotropic properties in the curable composition. Examples of thixotropic agents include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, glass beads, polyamide waxes, hydrogenated castor oil derivatives, calcium stearate, aluminum stearate, barium stearate and other metal soaps. And so on. The thixotropic agents may be used alone or in combination of two or more.

  If the content of the thixotropic agent in the curable composition is small, it may not be possible to impart thixotropic properties to the curable composition. If it is large, the viscosity of the curable composition will be high, and the curable composition will be high. Therefore, the amount is preferably 0.1 to 200 parts by weight, more preferably 1 to 150 parts by weight based on 100 parts by weight of the polymer containing a hydrolyzable silyl group.

  The extender is not particularly limited. For example, silica, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, titanium dioxide, carbon black, bentonite, organic bentonite, shirasu balloon, glass micro Examples thereof include balloons, organic microballoons composed of phenolic resins and vinylidene chloride resins, resin powders such as polyvinyl chloride resin powders and polymethyl methacrylate powders. A bulking agent may be used independently or 2 or more types may be used together.

  If the content of the extender in the curable composition is small, the effect of adding the extender may not be manifested. If the content is large, the extensibility of the cured product obtained by curing the curable composition is lowered. Therefore, the amount is preferably 1 to 700 parts by weight, more preferably 5 to 500 parts by weight, based on 100 parts by weight of the polymer containing a hydrolyzable silyl group.

  The tackifier is not particularly limited, and examples thereof include a styrene block copolymer or a hydrogenated product thereof, a phenol resin, a modified phenol resin, a terpene phenol resin, a xylene-phenol resin, a cyclopentadiene-phenol resin, and a coumarone indene. Resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, C5 hydrocarbon resin, C9 hydrocarbon resin, C5C9 hydrocarbon copolymer resin, etc. petroleum resin, hydrogenated petroleum resin, terpene resin, DCPD resin petroleum resin Etc. Tackifying resins may be used alone or in combination of two or more.

  If the content of the tackifying resin in the curable composition is small, the effect of adding the tackifying resin may not be manifested, and if it is large, the heat resistance of the cured product obtained by curing the curable composition is low. Since it may fall, 1-200 weight part is preferable with respect to 100 weight part of polymers containing a hydrolysable silyl group, and 5-100 weight part is more preferable.

  The antioxidant is not particularly limited, and examples thereof include hindered phenols, monophenols, bisphenols, and polyphenols. If the content of the antioxidant in the curable composition is small, the effect of adding the antioxidant may not be exhibited. If the content is large, the problem of bleeding out may occur. 0.1-20 weight part is preferable with respect to 100 weight part of polymers containing a group, and 0.3-10 weight part is more preferable.

  Examples of the light stabilizer include hindered amine light stabilizers. If the content of the light stabilizer in the curable composition is small, the effect of adding the light stabilizer may not be exhibited. If the content is large, the light stabilizer may bleed out. 0.1-20 weight part is preferable with respect to 100 weight part of polymers containing group, and 0.1-10 weight part is more preferable.

  Examples of the UV absorber include benzotriazole UV absorbers and benzophenone UV absorbers, and benzotriazole UV absorbers are preferred. If the content of the ultraviolet absorber in the curable composition is small, the effect of adding the ultraviolet absorber may not be manifested. If the content is large, the curable composition may be colored. 0.1-20 weight part is preferable with respect to 100 weight part of polymers containing group, and 0.1-10 weight part is more preferable.

  The curable composition of the present invention may contain a solvent as long as the physical properties are not impaired. Examples of the solvent include aliphatic hydrocarbon solvents such as n-hexane, n-pentane, paraffin and mineral spirits, alicyclic hydrocarbon solvents such as cyclohexane, and aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene. Examples thereof include solvents, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol, or halogen-substituted compounds thereof. A solvent may be used independently or 2 or more types may be used together.

  Next, the manufacturing method of a curable composition is demonstrated. The method for producing the curable composition is not particularly limited. For example, an additive is added to a polymer containing a hydrolyzable silyl group as necessary, followed by heating under reduced pressure for dehydration treatment. Thereafter, the polymer containing the hydrolyzable silyl group is cooled to near room temperature and then released under reduced pressure using nitrogen, and then the carboxylic acid anhydride and ketimine are contained in the polymer containing the hydrolyzable silyl group. The method of manufacturing a curable composition by adding a compound and mixing in nitrogen atmosphere is mentioned.

  The curable composition thus obtained has excellent curability, and is cured by crosslinking with moisture in the air or moisture contained in the adherend, resulting in mechanical strength and adhesiveness. An excellent resin film is formed. Therefore, the curable composition of the present invention can be used in various applications such as adhesives, sealants, paints, coating agents, pressure-sensitive adhesives, and sealants.

  Since the curable composition of the present invention has the configuration as described above, it has excellent curability, and the resin film formed by curing has excellent mechanical strength and adhesiveness. ing.

  And the curable composition of this invention adjusts the compounding ratio of the polymer containing a hydrolyzable silyl group, a carboxylic acid anhydride, and a ketimine compound, so that an organometallic compound is conventionally used as a silanol condensation catalyst. Curability and adhesiveness such as tack free time equivalent to the case of using can be expressed, and it can be developed for various uses.

  Hereinafter, embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
In a 0.5 liter separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, 100 parts by weight of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3-methacryloyloxypropylmethyldimethoxysilane (Shin-Etsu) (Product name “KBM-502” manufactured by Kagaku Co., Ltd.) 1.8 parts by weight, 0.8 part by weight of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts by weight of ethyl acetate are supplied and mixed uniformly to obtain a mixed solution. It was.

  Nitrogen gas was bubbled into this mixed solution for 20 minutes to remove dissolved oxygen in the mixed solution, and then the inside of the separable flask was replaced with nitrogen gas and the mixed solution was heated until it reached reflux with stirring. .

  After the mixed solution was brought to reflux, 0.024 parts by weight of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator was diluted with 1 part by weight of ethyl acetate. The polymerization was started by feeding into the mixed solution.

  One hour after the start of polymerization, a solution prepared by diluting 0.036 parts by weight of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 part by weight of ethyl acetate was polymerized. After 2 hours from the start of polymerization, a solution obtained by diluting 0.048 parts by weight of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was used, and 3 hours after the start of polymerization, A solution obtained by diluting 0.12 part by weight of (3,5,5-trimethylhexanoyl) peroxide with 1 part by weight of ethyl acetate was added with di (3,5,5-trimethylhexahexane after 4 hours from the start of polymerization. Noyl) A solution prepared by diluting 0.36 parts by weight of peroxide with 1 part by weight of ethyl acetate was added to each mixed solution.

  After 7 hours from the start of polymerization, the mixed solution was cooled to room temperature to complete the polymerization. Next, ethyl acetate was removed from the mixed solution under reduced pressure using an evaporator to obtain an acrylate polymer having a number average molecular weight of about 20,000 and having an alkoxysilyl group as a hydrolyzable silyl group. In addition, the average number of silyl functional groups of the obtained acrylate polymer was 1.9. The number average molecular weight of the acrylate polymer refers to the number average molecular weight in terms of polystyrene measured using Gel Permeation Chromatography System (GPC).

  80 parts by weight of an acrylate polymer having an alkoxysilyl group as a hydrolyzable silyl group produced as described above in a mixer equipped with a heating device, a cooling device, a decompression line and a nitrogen line, calcium carbonate 120 parts by weight of Whiten P30 ”) and 40 parts by weight of calcium carbonate (trade name“ Calfine 200M ”manufactured by Maruo Calcium Co., Ltd.) were supplied and kneaded until uniform under reduced pressure.

  Further, 20 parts by weight of an acrylate polymer having an alkoxysilyl group as a hydrolyzable silyl group produced as described above was supplied to the mixer and kneaded until uniform under reduced pressure. The temperature was raised to 0 ° C., and heat dehydration was performed at 110 ° C. for 2 hours.

  Next, the inside of the mixer is cooled to 30 ° C. while mixing under reduced pressure, and the inside of the mixer is released under reduced pressure with nitrogen, and then 2 parts by weight of a dehydrating agent (trade name “S-210” manufactured by Chisso Corporation) is added to the mixer. -Carboxylic anhydride (trade name “Ricacid MH700” manufactured by Shin Nippon Rika Co., Ltd.) containing 70% by weight of methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride, and hydrolyzable in the molecule Supply 5 parts by weight of a ketimine compound that does not contain a silyl group (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.), mix in a nitrogen atmosphere for 60 minutes until uniform, and degas the container under reduced pressure. And sealed to obtain a curable composition.

(Example 2)
10 parts by weight instead of 20 parts by weight of a carboxylic acid anhydride (trade name “Rikacid MH700” manufactured by Shin Nippon Rika Co., Ltd.) containing 70% by weight of 4-methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride A curable composition was obtained in the same manner as in Example 1 except that.

(Example 3)
3 parts by weight instead of 20 parts by weight of a carboxylic acid anhydride (trade name “Ricacid MH700” manufactured by Nippon Chemical Co., Ltd.) containing 70% by weight of 4-methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride A curable composition was obtained in the same manner as in Example 1 except that.

Example 4
40 parts by weight of carboxylic acid anhydride (trade name “Ricacid MH700” manufactured by Shin Nippon Chemical Co., Ltd.) containing 70% by weight of 4-methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride instead of 20 parts by weight A curable composition was obtained in the same manner as in Example 1 except that.

(Example 5)
Curability in the same manner as in Example 1 except that the ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) was changed to 15 parts by weight instead of 5 parts by weight. A composition was obtained.

(Example 6)
Except that the ketimine compound (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) containing no hydrolyzable silyl group in the molecule was changed to 0.5 parts by weight instead of 5 parts by weight, it was carried out in the same manner as in Example 1. A curable composition was obtained.

(Example 7)
Ketimine compound containing hydrolyzable silyl group in the molecule instead of 5 parts by weight of ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) Product name “NF-1104”) A curable composition was obtained in the same manner as in Example 1 except that 5 parts by weight were used.

(Example 8)
Ketimine compound containing hydrolyzable silyl group in the molecule instead of 5 parts by weight of ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) Product name “NF-1104”) A curable composition was obtained in the same manner as in Example 1 except that 15 parts by weight were used.

Example 9
Ketimine compound containing hydrolyzable silyl group in the molecule instead of 5 parts by weight of ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) Product name “NF-1104”) A curable composition was obtained in the same manner as in Example 1 except that 0.5 part by weight was used.

(Example 10)
Instead of 5 parts by weight of a ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “EpiCure H30” manufactured by Japan Epoxy Resin Co., Ltd.), as a ketimine compound containing a hydrolyzable silyl group in the molecule, Except for using 5 parts by weight of a mixture of triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate (trade name “KBM-9103” manufactured by Shin-Etsu Chemical Co., Ltd.) A curable composition was obtained in the same manner as in Example 1.

(Comparative Example 1)
A curable composition was obtained in the same manner as in Example 1 except that a ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) was not used.

(Comparative Example 2)
Example 1 except that a carboxylic acid anhydride (trade name “Licacid MH700” manufactured by Shin Nippon Rika Co., Ltd.) containing 70% by weight of 4-methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride was not used. Similarly, a curable composition was obtained.

(Comparative Example 3)
Instead of 20 parts by weight, 70 parts by weight of a carboxylic acid anhydride (trade name “Ricacid MH700” manufactured by Nippon Chemical Co., Ltd.) containing 70% by weight of 4-methylhexahydrophthalic anhydride and 30% by weight of hexahydrophthalic anhydride A curable composition was obtained in the same manner as in Example 1 except that.

(Comparative Example 4)
Curability in the same manner as in Example 1 except that the ketimine compound containing no hydrolyzable silyl group in the molecule (trade name “Epicure H30” manufactured by Japan Epoxy Resin Co., Ltd.) was changed to 40 parts by weight instead of 5 parts by weight. A composition was obtained.

  About the obtained curable composition, tack free time and adhesiveness were measured in the following way, and the result was shown to Table 1,2.

(Tack free time)
The tack-free time of the curable composition was measured in accordance with JIS A1439 (Testing method for building sealant). In addition, those with a tack free time of 300 minutes or more were described as 300 or more.

(Adhesiveness)
Based on the gap filling test of JIS A5550 (adhesive for floor joists), the compression shear bond strength of the curable composition was measured.

Claims (4)

Contains 100 parts by weight of a polymer containing hydrolyzable silyl groups, 0.1 to 50 parts by weight of carboxylic acid anhydride and 0.1 to 20 parts by weight of a ketimine compound, and contains an organometallic compound as a silanol condensation catalyst A curable composition characterized by not. The curable composition according to claim 1, wherein the ketimine compound contains a hydrolyzable silyl group in the molecule. An adhesive comprising the curable composition according to claim 1 or 2. A sealing material comprising the curable composition according to claim 1 or 2.