WO2014157247A1 - 硬化性組成物 - Google Patents
硬化性組成物 Download PDFInfo
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- WO2014157247A1 WO2014157247A1 PCT/JP2014/058359 JP2014058359W WO2014157247A1 WO 2014157247 A1 WO2014157247 A1 WO 2014157247A1 JP 2014058359 W JP2014058359 W JP 2014058359W WO 2014157247 A1 WO2014157247 A1 WO 2014157247A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- the present invention relates to a curable composition that can be cured in a short time and is excellent in adhesiveness and storage stability.
- curable compositions containing a polymer having a crosslinkable hydrolyzable silyl group as a main component are known. Curable compositions are used in various applications as paints, coating agents, adhesives, pressure sensitive adhesives, sealants and sealants.
- crosslinkable hydrolyzable silyl group of the polymer is hydrolyzed by the atmosphere or moisture contained in the adherend, followed by dehydration condensation, whereby the curable composition is cured and bonded. Forms a cured product with excellent strength.
- Patent Document 1 discloses a curable composition containing a polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group. By using a polyoxyalkylene polymer, a curable composition that can be cured in a short time can be provided.
- the curable composition of Patent Document 1 can be cured in a short time, it has low adhesion. For this reason, the cured product of the curable composition does not have sufficient adhesion to various substrates.
- the curable composition of Patent Document 1 has low storage stability.
- the curable composition is often stored for several months in a warehouse or a storefront after the production.
- the curable composition of Patent Document 1 is stored for a long period of time, the viscosity of the curable composition is rapidly increased and coating is likely to be difficult.
- an object of the present invention is to provide a curable composition that can be cured in a short time and is excellent in adhesion and storage stability.
- the curable composition of the present invention comprises 100 parts by weight of a polyoxyalkylene polymer (A) having a trimethoxysilyl group, a hydrolyzable silyl group, and ethyl (meth) acrylate and n- Copolymer of butyl (meth) acrylate, or (meth) acrylate polymer (B) containing a copolymer of methyl (meth) acrylate and n-butyl (meth) acrylate, and dioctyltin compound It is characterized by containing.
- A polyoxyalkylene polymer having a trimethoxysilyl group, a hydrolyzable silyl group, and ethyl (meth) acrylate and n- Copolymer of butyl (meth) acrylate
- B containing a copolymer of methyl (meth) acrylate and n-butyl (meth) acrylate, and dioctyl
- the polyoxyalkylene polymer (A) has a trimethoxysilyl group (—Si (OCH 3 ) 3 ).
- the main chain skeleton of the polyoxyalkylene polymer (A) has the formula: — (RO) n — (wherein R represents an alkylene group having 1 to 14 carbon atoms, and n is the number of repeating units. It is preferable that the polymer contains a repeating unit represented by the following formula:
- 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. According to the polyoxyalkylene polymer (A) having such a main chain skeleton, the curing rate of the curable composition can be improved.
- the main chain skeleton of the polyoxyalkylene polymer (A) includes polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene copolymer, and polyoxypropylene-poly Examples thereof include oxybutylene copolymers. Of these, polyoxypropylene is preferable. According to polyoxypropylene, not only can the curing rate of the curable composition be improved, but also the adhesiveness of the curable composition can be improved, and the cured product obtained by curing the curable composition is excellent. Flexibility and extensibility can be imparted.
- the polyoxyalkylene polymer (A) preferably further has a urethane bond in addition to the trimethoxysilyl group.
- the urethane bond can promote the hydrolysis reaction and dehydration condensation reaction of the trimethoxysilyl group, thereby improving the curing rate of the curable composition.
- the urethane bond can impart polarity to the polyoxyalkylene polymer (A), thereby improving the adhesiveness of the curable composition.
- the polyoxyalkylene polymer (A) preferably has a trimethoxysilyl group at both ends of the main chain skeleton via urethane bonds. According to the polyoxyalkylene polymer (A) having a urethane bond in the vicinity of the trimethoxysilyl group, the curing rate and adhesiveness of the curable composition can be further improved.
- a polyoxyalkylene polymer (A) having a trimethoxysilyl group via urethane bonds at both ends of the main chain skeleton includes, for example, a prepolymer having hydroxy groups at both ends of the polyoxyalkylene chain, and trimethoxysilyl It is obtained by reacting a compound having a group and an isocyanate group.
- prepolymers having hydroxy groups at both ends of the polyoxyalkylene chain include poly (oxyethylene) glycol, poly (oxypropylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, and poly (oxyethylene).
- poly (oxyethylene) glycol poly (oxypropylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, and poly (oxyethylene).
- -Poly (oxypropylene) glycol and poly (oxypropylene) -poly (oxybutylene) glycol examples include poly (oxyethylene) glycol, poly (oxypropylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, and poly (oxyethylene).
- Examples of the compound having a trimethoxysilyl group and an isocyanate group include 1-isocyanate methyltrimethoxysilane, 2-isocyanateethyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatebutyltrimethoxysilane, 3-isocyanatepentyltril. Examples include methoxysilane and 1-isocyanatopropyltrimethoxysilane.
- a prepolymer having hydroxy groups at both ends of the polyoxyalkylene chain By mixing a compound having a trimethoxysilyl group and an isocyanate group to obtain a mixture, and stirring the mixture to react the hydroxy group of the prepolymer with the isocyanate group of the compound to form a urethane bond. It can be carried out. Moreover, reaction can be accelerated
- the number average molecular weight of the polyoxyalkylene polymer (A) is preferably 5,000 to 50,000, more preferably 8,000 to 30,000, and particularly preferably 8,000 to 20,000. According to the polyoxyalkylene polymer (A) having a number average molecular weight of 5,000 or more, it is possible to further improve the adhesive force, mechanical strength, and extensibility of the cured product of the curable composition. In addition, according to the polyoxyalkylene polymer (A) having a number average molecular weight of 50,000 or less, the viscosity of the curable composition can be kept low, whereby excellent coating of the curable composition can be achieved. Sex can be secured.
- the number average molecular weight of the polyoxyalkylene polymer (A) is measured by conversion with polystyrene using a GPC (gel permeation chromatography) method. Specifically, after 6-7 mg of polyoxyalkylene polymer (A) is supplied to a test tube, orthodichlorobenzene (o-DCB) containing 0.05% by weight of dibutylhydroxytoluene (BHT) in the test tube The solution is added to prepare a diluted solution having a polyoxyalkylene polymer (A) concentration of 1 mg / mL.
- o-DCB orthodichlorobenzene
- BHT dibutylhydroxytoluene
- the diluted solution is shaken for 1 hour at 145 ° C. at a rotation speed of 25 rpm, and the polyoxyalkylene polymer (A) is dissolved in the o-DCB solution to obtain a measurement sample.
- the number average molecular weight of the polyoxyalkylene polymer (A) can be measured by the GPC method using this measurement sample.
- the number average molecular weight in the polyoxyalkylene polymer (A) can be measured by, for example, the following measuring apparatus and measuring conditions.
- Product name "HLC-8121GPC / HT" manufactured by TOSOH Measurement conditions Column: TSKgelGMHHR-H (20) HT ⁇ 3 TSKguardcolumn-HHR (30) HT ⁇ 1
- Detector Blythe refractometer Standard material: Polystyrene (Molecular weight: 500-8420000, manufactured by TOSOH) Elution conditions: 145 ° C
- the measurement of the weight average molecular weight of the (meth) acrylate polymer (B) described later can also be performed by the same method as the method for measuring the number average molecular weight of the polyoxyalkylene polymer (A) described above.
- the viscosity at 25 ° C. of the polyoxyalkylene polymer (A) is preferably 1,000 to 30,000 mPa ⁇ s, more preferably 4,000 to 25,000 mPa ⁇ s, and 5,000 to 15,000 mPa ⁇ s. Is particularly preferred. According to the polyoxyalkylene polymer (A) having a viscosity of 1,000 mPa ⁇ s or more, the adhesive force, mechanical strength, and extensibility of the cured product of the curable composition can be further improved.
- the viscosity of the curable composition can be kept low, whereby excellent coating of the curable composition is achieved. Sex can be secured.
- the viscosity of the polyoxyalkylene polymer (A) at 25 ° C. can be measured as follows. First, the polyoxyalkylene polymer (A) is allowed to stand at 25 ° C. for 24 hours, and then, according to JIS K7117-1, using a B-type viscometer under the condition of a rotation speed of 10 rpm. Thus, the viscosity of the polyoxyalkylene polymer (A) can be measured.
- polyoxyalkylene polymer (A) containing a trimethoxysilyl group a commercially available product can be used.
- a polyoxyalkylene polymer having a main chain skeleton of polyoxypropylene and having a trimethoxysilyl group at the end of the main chain skeleton and no urethane bond Exastar A2551 manufactured by Asahi Glass Co., Ltd .; Examples include Silyl SAX510, SAX520, SAX530, and SAX580 manufactured by Kaneka Corporation.
- Desmosal (registered trademark) XP2749 manufactured by Bayer Corporation can be used as a polyoxyalkylene polymer having a main chain skeleton of polyoxypropylene and having a trimethoxysilyl group at the end of the main chain skeleton via a urethane bond.
- Desmosal (registered trademark) XP2749 manufactured by Bayer Corporation can be used as a polyoxyalkylene polymer having a main chain skeleton of polyoxypropylene and having a trimethoxysilyl group at the end of the main chain skeleton via a urethane bond.
- the (meth) acrylate polymer (B) has a hydrolyzable silyl group.
- the hydrolyzable silyl group is a group in which 1 to 3 hydrolyzable groups are bonded to a silicon atom. According to the (meth) acrylate polymer (B), the adhesion of the curable composition is improved without inhibiting the improvement of the curing rate of the curable composition by the polyoxyalkylene polymer (A). Can do.
- 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. Group, an alkenyloxy group, and the like.
- an alkoxysilyl group is preferable because the curing rate of the curable composition can be improved.
- alkoxysilyl groups include trialkoxysilyl groups such as trimethoxysilyl group, triethoxysilyl group, triisopropoxysilyl group, and triphenoxysilyl group; dimethoxysilyl groups such as dimethoxymethylsilyl group and diethoxymethylsilyl group and monoalkoxysilyl groups such as a methoxydimethoxysilyl group and an ethoxydimethylsilyl group.
- a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.
- the main chain skeleton of the (meth) acrylate polymer (B) is a copolymer of ethyl (meth) acrylate and n-butyl (meth) acrylate, or a copolymer of methyl (meth) acrylate and n-butyl (meth) acrylate.
- the adhesiveness of the curable composition can be improved without inhibiting the improvement of the curing rate of the curable composition by the polyoxyalkylene polymer (A). It can be improved further.
- the main chain skeleton of the (meth) acrylate polymer (B) is preferably a copolymer of ethyl acrylate and n-butyl acrylate.
- (meth) acrylate means a methacrylate or an acrylate.
- the polymerization method of the (meth) acrylate polymer (B) is not particularly limited, and a known method can be used.
- a free radical polymerization method an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, Various polymerization methods such as a living anionic polymerization method, a living cation polymerization method, and a living radical polymerization method may be mentioned.
- the method for introducing the hydrolyzable silyl group into the (meth) acrylate polymer (B) is not particularly limited.
- a copolymer of ethyl (meth) acrylate and n-butyl (meth) acrylate, or methyl It is possible to use a method of hydrosilylation by introducing a hydrosilane having a hydrolyzable silyl group after introducing an unsaturated group into the molecule of the copolymer of (meth) acrylate and n-butyl (meth) acrylate. it can.
- the weight average molecular weight of the (meth) acrylate polymer (B) is preferably 2,000 to 50,000, more preferably 2,500 to 10,000, and particularly preferably 2,500 to 5,000. According to the (meth) acrylate polymer (B) having a weight average molecular weight of 2,000 or more, it is possible to further improve the adhesive strength, mechanical strength, and extensibility of the cured product of the curable composition. In addition, according to the (meth) acrylate polymer (B) having a weight average molecular weight of 50,000 or less, the viscosity of the curable composition can be kept low, whereby an excellent coating of the curable composition can be achieved. Workability can be secured.
- the content of the (meth) acrylate polymer (B) in the curable composition is 10 to 100 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A), but 10 to 60 parts by weight. Part is preferable, and 30 to 50 parts by weight is more preferable.
- the adhesiveness of the curable composition can be sufficiently improved.
- the high cure rate of a curable composition is securable by making content of the (meth) acrylate type polymer (B) in a curable composition into 100 weight part or less.
- the curable composition of the present invention contains a dioctyltin compound as a silanol condensation catalyst.
- the silanol condensation catalyst is a catalyst for promoting a dehydration condensation reaction between silanol groups.
- the silanol group means a hydroxy group ( ⁇ Si—OH) directly bonded to a silicon atom.
- the silanol group is formed by hydrolyzing a hydrolyzable silyl group such as a trimethoxysilyl group.
- Dioctyltin compounds include dioctyltin diacetate, dioctyltin monodecanate, dioctyltin bisethoxysilicate, dioctyltin diacetate, dioctyltin monodecanate, dioctyltin bisethoxysilicate, reaction product of dioctyltin oxide and alkoxysilane compound, and dioctyl The reaction material of a tin dicarboxylate and an alkoxysilane compound is also mentioned. According to these dioctyltin compounds, the adhesiveness and storage stability of the curable composition can be improved.
- a dioctyl tin compound may be used independently or 2 or more types may be used together.
- examples of the alkoxysilane compound include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, and hydrolysates thereof.
- Monoalkyltrialkoxysilanes such as triethoxymethylsilane, triethoxyethylsilane, triethoxypropylsilane, triethoxyisopropylsilane, triethoxybutylsilane and hydrolysates thereof; diethoxydimethylsilane, diethoxydiethylsilane, diethoxy; Dialkyl dialkoxysilanes and their hydrolysates such as dipropylsilane, diethoxydiisopropylsilane, and diethoxydibutylsilane; Chirushiran, ethoxy triethylsilane, triethoxy propyl silane, ethoxy triisopropylsilane, and the like trialkyl monoalkoxysilanes and hydrolysates thereof such as ethoxy tributyl silane.
- a reaction product of dioctyltin oxide and an alkoxysilane compound is formed by a reaction between a group represented by —Sn ( ⁇ O) — in dioctyltin oxide and an alkoxy group bonded to a silicon atom in the alkoxysilane compound. It is a compound.
- a reaction product of dioctyltin oxide and an alkoxysilane compound specifically, dioctyltin oxybisethoxysilicate, dioctyltin oxybismethoxysilicate, dioctyltin bis (triethoxysilicate), and dioctyltin bis (trimethoxysilicate) Etc.
- examples of dioctyltin dicarboxylate include dioctyltin diacetate, dioctyltin dilaurate, and dioctyltin distearate.
- the alkoxysilane compound may be the same as the alkoxysilane compound described above in the reaction product of dioctyltin oxide and alkoxysilane compound.
- a reaction product of dioctyltin dicarboxylate and an alkoxysilane compound is a compound formed by a reaction between a carboxylate group in dioctyltin dicarboxylate and an alkoxy group bonded to a silicon atom in the alkoxysilane compound. is there.
- a reaction product of dioctyltin dicarboxylate and alkoxysilane compound specifically, dioctyltin oxybisethoxysilicate, dioctyltin oxybismethoxysilicate, dioctyltin bis (triethoxysilicate), dioctyltin bis (trimethoxysilicate) ) And the like.
- dioctyltin compound a dioctyltin diacetate, a reaction product of dioctyltin oxide and an alkoxysilane compound is preferable, a reaction product of dioctyltin oxide and an alkoxysilane compound is more preferable, dioctyltin oxybisethoxysilicate, And dioctyltin bis (triethoxysilicate) are particularly preferred.
- the content of the dioctyltin compound in the curable composition is preferably 1 to 10 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
- the curable composition of the present invention preferably further contains an aminosilane coupling agent.
- the aminosilane coupling agent means a compound having a silicon atom having an alkoxy group bonded in one molecule and a functional group containing a nitrogen atom.
- aminosilane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and N-2- (aminoethyl) -3-aminopropyltrimethoxy.
- aminosilane coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -3-aminopropyltrimethyl. Ethoxysilane is preferred, and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is more preferred. According to these aminosilane coupling agents, a synergistic effect with the (meth) acrylate polymer (B) can be easily obtained, and the adhesiveness of the curable composition can be further improved.
- the content of the aminosilane coupling agent in the curable composition is preferably 0.5 to 10 parts by weight and more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
- the curable composition of the present invention preferably further contains a dehydrating agent. According to the dehydrating agent, when the curable composition is stored, the curable composition can be prevented from being cured by moisture contained in the air.
- dehydrating agents include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxysilane; and methyl orthoformate And ester compounds such as ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate.
- dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferable.
- the content of the dehydrating agent in the curable composition is preferably 0.5 to 20 parts by weight, more preferably 5 to 20 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer (A). 12 parts by weight is particularly preferred.
- the curable composition of the present invention preferably further contains a filler. According to the filler, a curable composition capable of obtaining a cured product having excellent mechanical strength can be provided.
- filler examples include calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, anhydrous silicic acid, finely divided silica, calcium silicate, titanium dioxide, clay, talc, carbon black, and glass balloon. These fillers may be used alone or in combination of two or more. Of these, calcium carbonate is preferably used.
- the average particle size of calcium carbonate is preferably 0.01 to 5 ⁇ m, more preferably 0.05 to 2.5 ⁇ m. According to the calcium carbonate having such an average particle size, a cured product having excellent mechanical strength and extensibility can be obtained, and a curable composition having excellent adhesiveness can be obtained. Can be provided.
- Calcium carbonate is preferably surface-treated with a fatty acid or a fatty acid ester. According to the calcium carbonate surface-treated with a fatty acid, a fatty acid ester, or the like, thixotropic properties can be imparted to the curable composition and aggregation of calcium carbonate can be suppressed.
- the content of the filler in the curable composition is preferably 1 to 700 parts by weight and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
- the curable composition of the present invention preferably further contains a weathering stabilizer.
- a weathering stabilizer include an antioxidant, an ultraviolet absorber, and a light stabilizer.
- a weathering stabilizer may be used individually by 1 type, and may use 2 or more types together.
- antioxidants examples include hindered phenolic antioxidants, monophenolic antioxidants, bisphenolic antioxidants, and polyphenolic antioxidants. Of these, hindered phenol antioxidants are preferred. Specific examples of hindered phenol antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (melting point: 118 ° C.), octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] (melting point 52 ° C.), and N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4 -Hydroxyphenylpropionamide)] (melting point: 158 ° C.), and octyl 3- (4-hydroxy-3,5-diisopropylphenyl) propionate (melting point: 5
- the content of the antioxidant in the curable composition is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). .
- UV absorbers examples include benzotriazole UV absorbers and benzophenone UV absorbers. Of these, benzotriazole-based ultraviolet absorbers are preferred. Specific examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol (melting point 130 ° C.), 2- (2H-benzotriazol-2-yl) -4- 6-bis (1-methyl-1-phenylethyl) phenol (melting point 139 ° C.), 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (Melting point 139 ° C.), 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (melting point 84 ° C.), and 2- (2H-benzotriazol-2-yl) -4 -(1,1,3,3-tetramethylbutyl) phenol (mel
- the content of the ultraviolet absorber in the curable composition is preferably 0.1 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). .
- light stabilizers include hindered amine light stabilizers. Specifically, a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate (melting point: 10 ° C.
- the content of the light stabilizer in the curable composition is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). .
- the melting point of the weather resistance stabilizer is preferably 10 ° C. or less, more preferably ⁇ 20 to 10 ° C., and particularly preferably ⁇ 20 to 5 ° C. According to the weather stabilizer having a melting point of 10 ° C. or lower, excellent adhesiveness can be imparted to the curable composition.
- the melting point of the weather stabilizer means the melting point of each weather stabilizer.
- the melting point of the weather stabilizer is a value measured by a visual method according to JIS K0064 (1922).
- the curable composition of the present invention may contain other additives such as a thixotropic agent, a pigment, a dye, and an anti-settling agent, a solvent, and the like in addition to the components described above.
- Another additive and solvent may be used individually by 1 type, and may use 2 or more types together.
- the thixotropic agent may be any one that can express thixotropic properties in the curable composition.
- Preferred examples of the thixotropic agent include hydrogenated castor oil, fatty acid bisamide, and fumed silica.
- the content of the thixotropic agent in the curable composition is preferably 0.1 to 200 parts by weight and more preferably 1 to 150 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
- Production of the curable composition of the present invention includes a polyoxyalkylene polymer (A) containing a trimethoxysilyl group, a (meth) acrylate polymer (B) containing a hydrolyzable silyl group, and a dioctyltin compound.
- A polyoxyalkylene polymer
- B (meth) acrylate polymer
- dioctyltin compound e.g., a dioctyltin compound.
- other additives and solvents can be mixed by a predetermined weight ratio. Mixing is preferably performed under reduced pressure.
- the curable composition of the present invention is rapidly cured by moisture in the air or moisture contained in the adherend, and forms a cured product having excellent adhesion to various substrates.
- a substrate is not particularly limited, and is a fluorine resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, polyamide resin, polyester resin, polyurethane resin, polyvinyl alcohol resin, Synthetic resin board containing synthetic resin such as ethylene-vinyl acetate copolymer resin, chlorinated polypropylene resin, and melamine resin; natural wood, plywood, medium density fiber board (MDF) particle board, rigid fiber board, semi-rigid fiber board, And wood such as laminated wood; inorganic boards; and metal plates containing metals such as aluminum, iron, stainless steel, and steel sheets.
- MDF medium density fiber board
- examples of the base material include a synthetic resin-coated metal plate in which at least a part of the surface of the metal plate is coated with a synthetic resin.
- examples of the synthetic resin used for the synthetic resin-coated metal plate include polyvinyl chloride resin, polyolefin resin, polyester resin, and fluorine resin.
- examples of the metal plate used for the synthetic resin-coated metal plate include metal plates made of metals such as aluminum, iron, stainless steel, and steel plates.
- the curable composition of this invention is used suitably for base materials, such as a synthetic resin board and a synthetic resin coating metal plate.
- base materials such as a synthetic resin board and a synthetic resin coating metal plate.
- Conventional curable compositions have low adhesion to these substrates, and can particularly demonstrate the effects of the present invention.
- the curable composition of the present invention since the curable composition of the present invention has excellent adhesiveness, it is used for civil engineering, architectural, vehicle, electrical products, electronic parts, miscellaneous goods, sealing agents, It can be used for various applications as a coating agent, a sealant and a sealing agent, and a coating agent and primer agent for civil engineering or building base materials.
- a curable composition was prepared by mixing the following components in a sealed stirrer until the mixture was uniform in a sealed stirrer so as to have the blending amounts shown in Table 1, respectively.
- Polyoxyalkylene polymer (A1) Polyoxyalkylene polymer (A1) having a main chain skeleton of polyoxypropylene and having trimethoxysilyl groups at both ends of the main chain skeleton via urethane bonds (viscosity at 25 ° C.
- Polyoxyalkylene polymer (A2) A polyoxyalkylene polymer (A2) having a main chain skeleton of polyoxypropylene, having a trimethoxysilyl group at both ends of the main chain skeleton and having no urethane bond (number average molecular weight 25,000, 25 Viscosity at 25,000 mPa ⁇ s, Silyl SAX580 manufactured by Kaneka Corporation) [(Meth) acrylate polymer (B1)] (Meth) acrylate polymer (B1) having a trimethoxysilyl group and the main chain skeleton being a copolymer of ethyl acrylate and n-butyl acrylate (Alfone US-6170, manufactured by Toagosei Co., Ltd., weight average molecular weight) 2,800) [(Meth)
- tack free time In accordance with JIS A5758, tack-free time (minutes) of the curable composition was measured in an environment of a temperature of 23 ° C. and a relative humidity of 50%.
- adherend As the adherend, a lauan plywood, a stainless steel plate, and a fluororesin-coated steel plate were prepared. A curable composition is applied on each adherend in a bead shape (width 5 mm, thickness 4 mm) and cured by leaving it to stand in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% for 7 days. Got. Then, the cured product is peeled from the adherend at a tensile speed of 100 mm / min from one end to the other end in the length direction with a finger, and the destruction state of the cured product at this time is visually confirmed. did.
- the cohesive failure of the cured product means a state in which the cured product is destroyed when the cured product is peeled from the adherend.
- cured material means the state which peeled in the interface of a to-be-adhered body and hardened
- test body was produced using the curable composition, and tensile adhesive strength T [N / mm ⁇ 2 >] was measured about this test body.
- a specific measurement procedure is as follows. A mortar plate (thickness 15 mm, length 70 mm ⁇ width 70 mm) was prepared as a base sample, and a polystyrene foam heat insulating plate (thickness 5 mm, length 40 mm ⁇ width 40 mm) was prepared as a finished sample. The curable composition was applied to the entire lower surface of the finished sample so that the coating thickness was 1 mm. After the finished samples were placed on the base sample, they were left in an environment of a temperature of 23 ° C.
- the test body by which the ground sample and the finishing sample were bonded together by the hardened
- the test specimen was subjected to a tensile bond strength test, and the maximum load P [N] until the bonded surface was broken was measured. Then, the tensile adhesive strength T [N / mm 2 ] was calculated by dividing the maximum load P [N] by the application area W (1600 [mm 2 ]) of the curable composition.
- the curable composition was filled in a container, sealed, and left in an atmosphere at a temperature of 23 ° C. for 1 day.
- the viscosity T 1 [mPa ⁇ s] at 23 ° C. of the curable composition after standing was measured using a viscometer (Brookfield B8U viscometer, rotor: No. 7, rotation speed: 10 rpm).
- the curable composition was filled in a container and sealed, and left in an atmosphere at a temperature of 50 ° C. for 28 days.
- the viscosity T 2 [mPa ⁇ s] at 23 ° C. of the curable composition after standing was measured in the same manner as described above.
- the curable composition of the present invention can be cured in a short time and is excellent in adhesiveness and storage stability. Therefore, such a curable composition is suitably used for bonding various adherends.
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Abstract
Description
ポリオキシアルキレン系重合体(A)は、トリメトキシシリル基(-Si(OCH3)3)を有している。ポリオキシアルキレン系重合体(A)の主鎖骨格は、式:-(R-O)n-(式中、Rは炭素数が1~14のアルキレン基を表し、nは繰り返し単位の数であって正の整数である。)で表される繰り返し単位を含有する重合体を含んでいることが好ましい。ポリオキシアルキレン系重合体の主鎖骨格は一種のみの繰り返し単位からなっていてもよいし、二種以上の繰り返し単位からなっていてもよい。このような主鎖骨格を有しているポリオキシアルキレン系重合体(A)によれば、硬化性組成物の硬化速度を向上させることができる。
測定装置 TOSOH社製 商品名「HLC-8121GPC/HT」
測定条件 カラム:TSKgelGMHHR-H(20)HT×3本
TSKguardcolumn-HHR(30)HT×1本
移動相:o-DCB 1.0mL/分
サンプル濃度:1mg/mL
検出器:ブライス型屈折計
標準物質:ポリスチレン(TOSOH社製 分子量:500~8420000)
溶出条件:145℃
SEC温度:145℃
(メタ)アクリレート系重合体(B)は加水分解性シリル基を有している。加水分解性シリル基とは、珪素原子に1~3個の加水分解性基が結合している基である。(メタ)アクリレート系重合体(B)によれば、ポリオキシアルキレン系重合体(A)による硬化性組成物の硬化速度の向上を阻害することなく、硬化性組成物の接着性を向上させることができる。
本発明の硬化性組成物は、シラノール縮合触媒として、ジオクチル錫化合物を含有している。シラノール縮合触媒とは、シラノール基同士の脱水縮合反応を促進させるための触媒である。なお、シラノール基とは、ケイ素原子に直接結合しているヒドロキシ基(≡Si-OH)を意味する。シラノール基は、トリメトキシシリル基などの加水分解性シリル基が加水分解することにより形成される。
本発明の硬化性組成物は、アミノシランカップリング剤をさらに含有していることが好ましい。アミノシランカップリング剤とは、一分子中にアルコキシ基が結合した珪素原子と、窒素原子を含有する官能基とを有している化合物を意味する。アミノシランカップリング剤を上述した(メタ)アクリレート系重合体(B)と組合せて用いると、これらの相乗効果により、ポリオキシアルキレン系重合体(A)による硬化性組成物の硬化速度の向上を阻害することなく、硬化性組成物の接着性をより向上させることができる。
本発明の硬化性組成物は、脱水剤をさらに含んでいることが好ましい。脱水剤によれば、硬化性組成物を保存している際に、空気中などに含まれている水分によって硬化性組成物が硬化することを抑制することができる。
本発明の硬化性組成物は、充填剤をさらに含んでいることが好ましい。充填剤によれば、機械的強度に優れている硬化物を得ることが可能な硬化性組成物を提供することができる。
本発明の硬化性組成物は、耐候安定剤をさらに含んでいることが好ましい。耐候安定剤としては、酸化防止剤、紫外線吸収剤、及び光安定剤が好ましく挙げられる。耐候安定剤は、一種単独で用いられてもよく、二種以上を併用してもよい。
下記成分を、それぞれ表1に示した配合量となるようにして、密封した攪拌機中で減圧しながら均一になるまで混合することにより硬化性組成物を調製した。
[ポリオキシアルキレン系重合体(A1)]
主鎖骨格がポリオキシプロピレンであり、且つ主鎖骨格の両末端にウレタン結合を介してトリメトキシシリル基を有しているポリオキシアルキレン系重合体(A1)(25℃における粘度5,000mPa・s、バイエル社製 Desmoseal(登録商標)XP2749)
[ポリオキシアルキレン系重合体(A2)]
主鎖骨格がポリオキシプロピレンであり、主鎖骨格の両末端にトリメトキシシリル基を有し且つウレタン結合を有していないポリオキシアルキレン系重合体(A2)(数平均分子量25,000、25℃における粘度25,000mPa・s、株式会社カネカ製 サイリルSAX580)
[(メタ)アクリレート系重合体(B1)]
トリメトキシシリル基を有し、且つ主鎖骨格がエチルアクリレート及びn-ブチルアクリレートの共重合体である(メタ)アクリレート系重合体(B1)(東亞合成株式会社製 アルフォンUS-6170、重量平均分子量2,800)
[(メタ)アクリレート系重合体(B2)]
トリメトキシシリル基を有し、且つ主鎖骨格がn-ブチルアクリレート及びメチルメタクリレートの共重合体である(メタ)アクリレート系重合体(B2)(東亞合成株式会社製 ARUFON US-6110、重量平均分子量3,200)
[(メタ)アクリレート系重合体(B3)]
トリメトキシシリル基を有し、且つ主鎖骨格が2-エチルヘキシルアクリレート及びメチルメタクリレートの共重合体である(メタ)アクリレート系重合体(B3)(東亜合成株式会社製 ARUFON US-6100、重量平均分子量2,500)
[シラノール縮合触媒]
シラノール縮合触媒(1)(ジオクチル錫ジアセテート)
シラノール縮合触媒(2)(ジオクチル錫ビス(トリエトキシシリケート)、日東化成株式会社 製品名「ネオスタン S-1」)
シラノール縮合触媒(3)(ジブチル錫ジアセチルアセトナート)
[アミノシランカップリング剤]
アミノシランカップリング剤(1)(N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、信越化学工業株式会社製 KBM-603)
アミノシランカップリング剤(2)(3-アミノプロピルトリメトキシシラン、信越化学工業株式会社製 KBM-903)
[脱水剤]
脱水剤(ビニルトリメトキシシラン、信越化学工業株式会社製 KBM-1003)
[充填剤]
充填剤(脂肪酸により表面処理されてなるコロイダル炭酸カルシウム、丸尾カルシウム株式会社製 カルファイン200M、平均粒子径0.05μm)
[耐候安定剤]
ヒンダードフェノール系酸化防止剤(1)(ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、融点118℃、BASF社製 IRGANOX(登録商標)1010)
ベンゾトリアゾール系紫外線吸収剤(1)(2-[5-クロロ(2H)-ベンゾトリアゾール-2-イル]-4-メチル-6-(tert-ブチル)フェノール、融点139℃、BASF社製 TINUVIN(登録商標)326)
ヒンダードフェノール系酸化防止剤(2)(3-(4-ヒドロキシ-3,5-ジイソプロピルフェニル)プロピオン酸オクチル、融点5℃、BASF社製 IRGANOX(登録商標)1135)
ベンゾトリアゾール系紫外線吸収剤(2)(融点10℃以下、BASF社製 TINUVIN(登録商標)384-2)
硬化性組成物について、タックフリータイム、接着性、引張接着強さ、及び貯蔵安定性を下記手順に従って評価した。結果をまとめて表1に示す。
JIS A5758に準拠して、温度23℃、相対湿度50%の環境下で、硬化性組成物のタックフリータイム(分)を測定した。
被着体として、ラワン合板、ステンレス板、及びフッ素樹脂塗装鋼板を用意した。硬化性組成物を、各被着体上にビード状(幅5mm、厚さ4mm)に塗布し、温度23℃、相対湿度50%の雰囲気下に7日間放置させることにより硬化させて、硬化物を得た。そして、硬化物をその長さ方向における一方の端部から他方の端部に向かって指により100mm/分の引張速度で被着体から剥離し、この時の硬化物の破壊状態を目視により確認した。表1において、被着体から硬化物を剥離する際に、硬化物が全て凝集破壊したものを「優(excellent)」とし、硬化物が凝集破壊した部分と界面破壊した部分とがあったものを「良(good)」とし、硬化物が全て界面破壊したものを「不良(bad)」とした。
JIS A5547 5.2に準拠して、硬化性組成物を用いて試験体を作製し、この試験体について引張接着強さT[N/mm2]を測定した。具体的な測定手順は、次に示す通りである。下地試料としてモルタル板(厚み15mm、縦70mm×横70mm)、及び仕上試料としてポリスチレンフォーム保温板(厚み5mm、縦40mm×横40mm)を用意した。仕上試料の下面全面に硬化性組成物を、塗布厚みが1mmとなるようにして塗布した。仕上試料を下地試料の上に載せた後、これらを温度23℃、相対湿度50%の環境下に14日間放置して、硬化性組成物を硬化させた。これにより、下地試料と仕上試料とが硬化性組成物の硬化物によって貼り合わされた試験体を得た。試験体について引張接着強さ試験を行い、接着面が破断するまでの最大荷重P[N]を測定した。そして、最大荷重P[N]を硬化性組成物の塗布面積W(1600[mm2])で除することにより、引張接着強さT[N/mm2]を算出した。
硬化性組成物を、容器中に充填した後に密閉し、温度23℃の雰囲気下に1日放置した。放置後の硬化性組成物の23℃における粘度T1[mPa・s]を、粘度計(ブルックフィールド社製 B8U型粘度計、ローター:No.7、回転数10rpm)を用いて測定した。
Claims (6)
- トリメトキシシリル基を有するポリオキシアルキレン系重合体(A)100重量部、
加水分解性シリル基を有し、且つ主鎖骨格にエチル(メタ)アクリレート及びn-ブチル(メタ)アクリレートの共重合体、又はメチル(メタ)アクリレート及びn-ブチル(メタ)アクリレートの共重合体を含む(メタ)アクリレート系重合体(B)10~100重量部、及び
ジオクチル錫化合物を含有することを特徴とする硬化性組成物。 - ポリオキシアルキレン系重合体(A)が、ウレタン結合を有していることを特徴とする請求項1に記載の硬化性組成物。
- (メタ)アクリレート系重合体(B)の主鎖骨格が、エチル(メタ)アクリレート及びn-ブチル(メタ)アクリレートの共重合体であることを特徴とする請求項1に記載の硬化性組成物。
- ジオクチル錫化合物が、ジオクチル錫オキサイドとアルコキシシラン化合物との反応物を含むことを特徴とする請求項1に記載の硬化性組成物。
- ジオクチル錫化合物を、ポリオキシアルキレン系重合体(A)100重量部に対して、1~10重量部含有することを特徴とする請求項1に記載の硬化性組成物。
- アミノシランカップリング剤を含有することを特徴とする請求項1に記載の硬化性組成物。
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