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WO2014157247A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
curable composition
meth
acrylate
group
weight
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PCT/JP2014/058359
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English (en)
Japanese (ja)
Inventor
村山　之彦
Original Assignee
積水フーラー株式会社
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Application filed by 積水フーラー株式会社 filed Critical 積水フーラー株式会社
Priority to JP2014543390A priority Critical patent/JP5791824B2/ja
Priority to CN201480017940.XA priority patent/CN105073894B/zh
Publication of WO2014157247A1 publication Critical patent/WO2014157247A1/fr

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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

La présente invention concerne une composition durcissable qui est caractérisée en ce qu'elle comprend : 100 parties en poids d'un polymère de type polyoxyalkylène (A) ayant un groupe triméthoxysilyle; 10 à 100 parties en poids d'un polymère de type (méth)acrylate (B) ayant un groupe silyle hydrolysable et contenant un copolymère de (méth)acrylate d'éthyle et de (méth)acrylate de n-butyle ou un copolymère de (méth)acrylate de méthyle et de (méth)acrylate de n-butyle dans le squelette de chaîne principale; et un composé dioctylétain.
PCT/JP2014/058359 2013-03-25 2014-03-25 Composition durcissable WO2014157247A1 (fr)

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JP7022800B1 (ja) 2020-09-02 2022-02-18 サンスター技研株式会社 接着剤組成物及び接着構造体
WO2025063292A1 (fr) * 2023-09-22 2025-03-27 株式会社カネカ Composition durcissable

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CN111902485A (zh) * 2018-03-28 2020-11-06 株式会社钟化 加热固化型的固化物的制造方法和加热固化型的固化性组合物

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CN105073894B (zh) 2018-06-08
JP2015014014A (ja) 2015-01-22

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