JP5507357B2 - Curable composition, adhesive and sealant - Google Patents

Description

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

  Conventionally, various curable compositions mainly composed of a polymer having a crosslinkable hydrolyzable silyl group have been proposed. The curable composition is crosslinked in the atmosphere or by moisture contained in the adherend to form a cured product having excellent durability, weather resistance, transparency and adhesiveness.

  Accordingly, curable compositions are used in various applications such as paints, coatings, adhesives, pressure sensitive adhesives, sealants and sealants. Although these curable compositions crosslink by forming a siloxane bond, high curability may be required depending on applications.

  Therefore, Patent Document 1 includes an organic polymer (A) having a hydrolyzable silyl group at the terminal, a dialkyltin dicarboxylate (B) in which the carbon adjacent to the carboxy group forming the tin salt is a quaternary carbon, And a curable composition containing an amine compound (C).

  However, the curable composition described above has insufficient curability, and a curable composition having even higher curability is desired.

JP 2005-272540 A

  The present invention provides a curable composition having excellent curability.

但し、Ｒ¹とＲ⁴はそれぞれ独立して炭素数が１〜２０のアルキル基であるか、又は、Ｒ¹とＲ⁴はそれぞれ独立して炭素数が１〜２０のアルキレン基であり且つＲ¹とＲ⁴は化学結合を介して結合して環状構造を形成している。Ｒ²とＲ³はそれぞれ独立して炭素数が１〜２０のアルキル基であるか、又は、Ｒ²とＲ³はそれぞれ独立して炭素数が１〜２０のアルキレン基であり且つＲ²とＲ³は化学結合を介して結合して環状構造を形成している。 The curable composition of the present invention comprises 100 parts by weight of a polymer containing a hydrolyzable silyl group , 0.1 to 30 parts by weight of zirconium tributoxy monoacetylacetonate as an organometallic compound, and a compound represented by formula 1 It contains 0.1 to 30 parts by weight.

However, R ¹ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, or R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms and R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure. R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, or R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms and R ² and R ³ is bonded via a chemical bond to form a cyclic structure.

  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 modified in 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).

The curable composition of the present invention contains zirconium tributoxy monoacetylacetonate which is an organometallic compound as a silanol condensation catalyst .

  If the content of the organometallic compound in the curable composition is small, the moisture curing reaction rate of the curable composition is reduced, and if it is large, the organometallic compound may bleed out. Is limited to 0.1 to 30 parts by weight, and preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymer.

  The curable composition of this invention contains the compound shown by following formula 1.

However, R ¹ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, or R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms and R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure. R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, or R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms and R ² and R ³ is bonded via a chemical bond to form a cyclic structure.

R ¹ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, or R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms and R ¹ and R ⁴ is bonded via a chemical bond to form a cyclic structure, but R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms, and R ¹ and R ⁴ are a chemical bond. It is preferable that the ring structure is formed by bonding via a ring.

When R ¹ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like. R ¹ and R ⁴ may be the same or different from each other.

R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms, and R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure, ie, R ^{When 1} and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms and R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure, Methylene, ethylene, propylene, butylene, pentyl (amylene), hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene Group, heptadecylene group, octadecylene group, nonadecylene group, and eicosylene group. R ¹ and R ⁴ may be the same or different from each other.

R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure. Examples of the chemical bond connecting R ¹ and R ⁴ include a direct bond by a covalent bond, an oxygen atom And an ether bond (—O—), —NH—, —S— and the like which are bonded via a hydrogen atom, and a direct bond by a covalent bond is preferable. In the case of direct bonding by a covalent bond, the cyclic structure formed by directly bonding R ¹ and R ⁴ via a covalent bond is preferably a 4- to 8-membered ring.

R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, or R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms and R ² and R ³ is bonded through a chemical bond to form a cyclic structure, but R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms, and R ² and R ³ are a chemical bond. It is preferable that the ring structure is formed by bonding via a ring.

When R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like. R ² and R ³ may be the same or different from each other.

R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms, and R ² and R ³ are bonded via a chemical bond to form a cyclic structure, ie, R ^{When 2} and R ³ are each independently an alkyl group having 1 to 20 carbon atoms and R ² and R ³ are bonded via a chemical bond to form a cyclic structure, Methylene, ethylene, propylene, butylene, pentyl (amylene), hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene Group, heptadecylene group, octadecylene group, nonadecylene group, and eicosylene group. R ² and R ³ may be the same or different from each other.

R ² and R ³ are bonded via a chemical bond to form a cyclic structure. Examples of the chemical bond connecting R ² and R ³ include a direct bond by a covalent bond, an oxygen atom And an ether bond (—O—), —NH—, —S— and the like which are bonded via a hydrogen atom, and a direct bond by a covalent bond is preferable. In the case of direct bonding by covalent bond, the cyclic structure formed by directly bonding R ² and R ³ via a covalent bond is preferably a 4-9 membered ring.

  Examples of the compound represented by the above formula 1 include 1,8-diazabicyclo (5,4,0) undecene-7, 1,5-diazabicyclo (4,3,0) nonene-5. The compound represented by Formula 1 may be used alone or in combination of two or more.

  If the content of the compound represented by formula 1 in the curable composition is small, the moisture curing reaction rate of the curable composition is decreased, and if it is large, the compound represented by formula 1 may bleed out. The amount is limited to 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer containing a hydrolyzable silyl group.

  The curable composition of the present invention includes a viscosity modifier, a plasticizer, a silane coupling agent, a thixotropic agent, a filler, a tackifier, an antioxidant, a light stabilizer, and an ultraviolet ray as long as the physical properties are not impaired. Additives such as an absorbent, a solvent, a colorant, a flame retardant, a sagging inhibitor, a fragrance, a pigment, a dye, and a dehydrating agent may be contained.

  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 Silane, mercaptomethyltriethoxysilane, γ-chloropropyltrimethoxysilane, tris (3-trimethoxysilylpropyl) isocyanurate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3- Examples include triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 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 manifested. If the content is large, the antioxidant may bleed out. 0.1-20 weight part is preferable with respect to 100 weight part of polymers containing a silyl 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, and if it is large, the curable composition may be colored. 0.1-20 weight part is preferable with respect to 100 weight part of polymers containing a silyl 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 organometallic compound and the above formula are contained in the polymer containing the hydrolyzable silyl group. The method of manufacturing a curable composition by adding the compound shown by 1 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.

  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).

  While supplying 100 parts by weight of an acrylate polymer having an alkoxysilyl group as a hydrolyzable silyl group produced as described above to a mixer equipped with a heating device, a cooling device, a decompression line and a nitrogen line, while kneading under reduced pressure The mixture was heated to 110 ° C. and subjected to heat dehydration treatment at 110 ° C. for 2 hours.

Next, the inside of the mixer is cooled to 30 ° C. while being kneaded under reduced pressure, and after the inside of the mixer is released under reduced pressure with nitrogen, 2 parts by weight of a dehydrating agent (trade name “S-210” manufactured by Chisso Corporation) 4 parts by weight of a silane coupling agent (trade name “KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd.), 3 parts by weight of zirconium tributoxy monoacetylacetonate (trade name “ZC-540” manufactured by Matsumoto Trading Co., Ltd.) and Formula 1 3 parts by weight of 1,5-diazabicyclo [4.3.0] nonene-5 (trade name “DBN” manufactured by San Apro Co., Ltd.) is supplied as a compound represented by the formula, and the mixture becomes uniform over 60 minutes in a nitrogen atmosphere. And degassed under reduced pressure, filled in a container, and sealed to obtain a curable composition.

(Comparative Example 1)
The curable composition was the same as in Example 1 except that 1,5-diazabicyclo (4.3.0) nonene-5 (trade name “DBN” manufactured by San Apro Co., Ltd.) was not used as the compound represented by Formula 1. Got.

(Comparative Example 2)
Other than not using 1,1,3,3-tetrabutyl-1,3-[(1-oxododecyl) oxy] -distannoxane (trade name “SCAT-01” manufactured by Sansha Co., Ltd.) as the organotin compound Obtained a curable composition in the same manner as in Example 1.

(Comparative Example 3)
A curable composition in the same manner as in Example 3 except that 1,5-diazabicyclo (4.3.0) nonene-5 (trade name “DBN” manufactured by San Apro) was not used as the compound represented by Formula 1. Got.

(Comparative Example 4)
A curable composition in the same manner as in Example 4 except that 1,5-diazabicyclo (4.3.0) nonene-5 (trade name “DBN” manufactured by San Apro) was not used as the compound represented by Formula 1. Got.

(Comparative Example 5)
Instead of 3 parts by weight of 1,1,3,3-tetrabutyl-1,3-[(1-oxododecyl) oxy] -distannoxane (trade name “SCAT-01” manufactured by Sansha Co., Ltd.) as the organotin compound A curable composition was obtained in the same manner as in Example 1 except that the amount was 40 parts by weight.

(Comparative Example 6)
Example 1 except that 1,5-diazabicyclo (4.3.0) nonene-5 (trade name “DBN” manufactured by San Apro Co., Ltd.) was changed to 40 parts by weight instead of 3 parts by weight as the compound represented by Formula 1. In the same manner, a curable composition was obtained.

  The resulting curable composition was measured for tack free time and bleed out in the following manner, and the results are shown in Table 1.

(Tack free time)
The tack-free time of the curable composition was measured in accordance with JIS A1439 (Testing method for building sealant). JIS A1439 stipulates that the sample should be flattened with a spatula or the like so as to have a thickness of about 3 mm. However, the curable compositions obtained in Examples and Comparative Examples have a low viscosity and may flow and change their thickness. Therefore, a flat rectangular frame is produced on a glass plate using a spacer having a thickness of 3 mm, and a curable composition is supplied into the frame so that the thickness of the curable composition is 3 mm. The test was conducted on a flat surface. Those with a tack free time of 300 minutes or more were described as 300 or more.

(Bleed out)
70 g / m ² of kraft paper was prepared, and the curable composition was coated on the kraft paper to a thickness of 1 mm.

  Next, the curable composition was cured for 12 hours in an atmosphere of 23 ° C. and 55% relative humidity, and the presence or absence of bleed-out was visually observed. As a method of evaluation, when bleed out to kraft paper within a range of 1 mm or less from the curable composition or when no bleed out was observed, “◯”, exceeding 1 mm and within 5 mm from the curable composition When the bleedout was made on the kraft paper within the range of △, “△” was evaluated.

Claims (3)

100 parts by weight of a polymer containing a hydrolyzable silyl group, 0.1 to 30 parts by weight of zirconium tributoxy monoacetylacetonate as an organometallic compound, and 0.1 to 30 parts by weight of a compound represented by Formula 1 A curable composition characterized by comprising:

However, R ¹ and R ⁴ are each independently an alkyl group having 1 to 20 carbon atoms, or R ¹ and R ⁴ are each independently an alkylene group having 1 to 20 carbon atoms and R ¹ and R ⁴ are bonded via a chemical bond to form a cyclic structure. R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms, or R ² and R ³ are each independently an alkylene group having 1 to 20 carbon atoms and R ² and R ³ is bonded via a chemical bond to form a cyclic structure. An adhesive comprising the curable composition according to claim 1 . A sealing material comprising the curable composition according to claim 1 .