WO2013047837A1 - Composition durcissable - Google Patents

Composition durcissable Download PDF

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Publication number
WO2013047837A1
WO2013047837A1 PCT/JP2012/075245 JP2012075245W WO2013047837A1 WO 2013047837 A1 WO2013047837 A1 WO 2013047837A1 JP 2012075245 W JP2012075245 W JP 2012075245W WO 2013047837 A1 WO2013047837 A1 WO 2013047837A1
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curable composition
meth
acrylate
group
polymer
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PCT/JP2012/075245
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Japanese (ja)
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村山　之彦
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積水フーラー株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages

Definitions

  • the present invention relates to a curable composition having excellent adhesion and weather resistance.
  • 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.
  • the hydrolyzable hydrolyzable silyl group of the polymer is hydrolyzed by the atmosphere or moisture contained in the adherend to form silanol groups, and then the silanol groups are bonded to each other. It hardens
  • Patent Document 1 by using a polyoxyalkylene polymer having a crosslinkable hydrolyzable silyl group, it is possible to cure in a short time and form a cured product having excellent transparency.
  • a curable composition is disclosed which is possible.
  • the curable composition of Patent Document 1 has a problem that although it can be cured in a short time, the adhesiveness is low, and the adhesive force of the obtained cured product to various substrates is not sufficient.
  • the curable composition of Patent Document 1 has a problem that a cured product obtained by curing the composition has low weather resistance. That is, the cured product of the curable composition of Patent Document 1 is affected by the external environment such as light, heat, rainwater, etc., so that it loses flexibility over time and becomes hard and brittle. There was a problem of causing deterioration such as a decrease in adhesive strength. Deterioration of a cured product formed with such a curable composition is promoted by light transmitted through the adherend when a substrate made of a transparent material such as glass is used as the adherend. Therefore, an improvement in weather resistance is desired for the curable composition of Patent Document 1.
  • an object of the present invention is to provide a curable composition capable of forming a cured product having excellent adhesion and weather resistance.
  • the curable composition of the present invention contains a polyoxyalkylene polymer (A) containing a trimethoxysilyl group, a (meth) acrylate polymer (B) containing a hydrolyzable silyl group, and silica. It is characterized by that.
  • the polyoxyalkylene polymer (A) containing a trimethoxysilyl group (—Si (OCH 3 ) 3 ) has a main chain of the general formula: — (RO) n — (wherein R represents the number of carbon atoms) Represents a alkylene group of 1 to 14, and n is the number of repeating units and is a positive integer).
  • 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, and the flexibility and extensibility are improved. A cured product having excellent weather resistance can be formed.
  • 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 adhesiveness of the curable composition be improved, but also the cured product obtained by curing the curable composition is imparted with excellent flexibility and extensibility, and the cured product. It is also possible to improve the weather resistance.
  • the polyoxyalkylene polymer (A) preferably further has a urethane bond in addition to the trimethoxysilyl group.
  • 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 polyoxyalkylene chain via a urethane bond. According to the polyoxyalkylene polymer (A) having a urethane bond in the vicinity of the trimethoxysilyl group, the adhesiveness of the curable composition can be further improved.
  • the polyoxyalkylene polymer (A) having a trimethoxysilyl group via a urethane bond at both ends of the polyoxyalkylene chain includes, for example, a prepolymer having hydroxyl groups at both ends of the polyoxyalkylene chain, trimethoxy It can be obtained by reacting a compound having a silyl group and an isocyanate group.
  • Prepolymers having hydroxyl groups at both ends of the polyoxyalkylene chain include polyoxyethylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, polyoxytetramethylene glycol, polyoxyethylene-polyoxypropylene glycol, and polyoxyethylene And propylene-polyoxybutylene glycol.
  • 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 3,000 to 50,000, and more preferably 10,000 to 20,000. If the number average molecular weight of the polyoxyalkylene polymer (A) is too large, the viscosity of the resulting curable composition will increase, and the coating properties of the curable composition may be reduced. If the number average molecular weight of the polyoxyalkylene polymer (A) is too small, the cured product of the resulting curable composition becomes brittle, and the mechanical strength, extensibility, and flexibility of the cured product may be reduced. There is.
  • the number average molecular weight of the polyoxyalkylene polymer (A) is a polystyrene-converted value measured by a GPC (gel permeation chromatography) method. Specifically, 6 to 7 mg of the polyoxyalkylene polymer (A) was sampled, and the collected polyoxyalkylene polymer (A) was supplied to the test tube, and then 0.05 wt% of the test tube was added. A dilute solution is prepared by adding an o-DCB (orthodichlorobenzene) solution containing BHT (dibutylhydroxytoluene) and diluting the polyoxyalkylene polymer (A) to a concentration of 1 mg / mL.
  • o-DCB orthodichlorobenzene
  • 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 x 3 TSK guard column-HHR (30) HT x 1
  • Detector Bryce refractometer Standard material: Polystyrene (Molecular weight: 500 to 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 using the same method as described above.
  • the viscosity of the polyoxyalkylene polymer (A) at 25 ° C. is preferably 1000 to 30000 mPa ⁇ s, more preferably 4000 to 25000 mPa ⁇ s, and particularly preferably 5000 to 15000 mPa ⁇ s. If the viscosity of the polyoxyalkylene polymer (A) is too high, the viscosity of the resulting curable composition will be high, and the coatability of the curable composition may be reduced.
  • the viscosity of the polyoxyalkylene polymer (A) at 25 ° C. can be measured by a method based on JIS K1557.
  • a commercially available polyoxyalkylene polymer (A) containing a trimethoxysilyl group can be used.
  • a polyoxyalkylene polymer having a main chain skeleton of polyoxypropylene, having a trimethoxysilyl group at the end of the main chain skeleton and not having a urethane bond Exastar A2551 manufactured by Asahi Glass Co., Ltd. Can be mentioned.
  • 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 hydrolyzable silyl group in the (meth) acrylate polymer (B) is a group formed by bonding 1 to 3 hydrolyzable groups to a silicon atom.
  • 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, alkenyloxy group and the like.
  • an alkoxysilyl group is preferable because the adhesiveness 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) includes a (meth) acrylate polymer obtained by radical polymerization of a (meth) acrylate monomer.
  • (meth) acrylate means a methacrylate or an acrylate.
  • Specific examples of the (meth) acrylate monomer constituting the main chain of the (meth) acrylate polymer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl.
  • (meth) acrylate polymer (B) other monomers can be copolymerized.
  • monomers include styrene, indene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, and the like.
  • 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 Ruvinyl 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
  • the main chain skeleton of the (meth) acrylate polymer (B) is preferably a copolymer of ethyl (meth) acrylate and n-butyl (meth) acrylate, and a copolymer of ethyl acrylate and n-butyl acrylate It is more preferable that According to the (meth) acrylate polymer (B) whose main chain skeleton is composed of the above copolymer, the adhesiveness of the curable composition can be further improved.
  • 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.
  • the hydrolysis is performed on the (meth) acrylate polymer having an unsaturated group introduced in the molecule.
  • a method of hydrosilylating by reacting hydrosilane having a functional silyl group can be used.
  • the weight average molecular weight of the (meth) acrylate polymer (B) is preferably 2,000 to 50,000, more preferably 2,500 to 15,000, and particularly preferably 2,500 to 5,000. If the weight average molecular weight of the (meth) acrylate polymer (B) is too large, the adhesiveness of the curable composition may be reduced. Moreover, when the weight average molecular weight of the (meth) acrylate polymer (B) is too low, the cured product of the curable composition becomes brittle, and the mechanical strength, elongation, and weather resistance of the cured product may be reduced. is there. Moreover, when the weight average molecular weight of a (meth) acrylate type polymer (B) is too small, there exists a possibility that the adhesiveness of a curable composition may fall.
  • the content of the (meth) acrylate polymer (B) in the curable composition is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A), and 10 to 70 parts by weight. Is more preferable, and 30 to 50 parts by weight is particularly preferable. If the content of the (meth) acrylate polymer (B) in the curable composition is too low, the adhesiveness of the curable composition may not be sufficiently improved. Moreover, when content of the (meth) acrylate type polymer (B) in a curable composition is too high, the hardened
  • the curable composition of this invention can form the hardened
  • Silica includes hydrophobic silica and hydrophilic silica, with hydrophobic silica being preferred.
  • hydrophobic silica examples include silica that is surface-treated with a silane compound containing a hydrophobic group such as a methyl group, a dimethyl group, or a trimethyl group.
  • silane compound containing a hydrophobic group examples include silane compounds containing a methyl group and a halogen atom.
  • the halogen atom include a chlorine atom and a bromine atom.
  • Specific examples of the silane compound containing a methyl group and a halogen atom include dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, benzyldimethylchlorosilane, and bromomethyldimethylchlorosilane. Of these, dimethyldichlorosilane is preferable.
  • silica has a silanol group on its surface. Then, by treating the surface of the silica with a silane compound containing a methyl group and a halogen atom, the silanol group present on the silica surface reacts with the halogen atom contained in the silane compound, and the silica surface Hydrophobic silica is obtained by introducing a methyl group into.
  • the silanol group means a hydroxy group ( ⁇ Si—OH) directly bonded to a silicon atom.
  • hydrophobic silica surface-treated with a silane compound containing a methyl group and a halogen atom it is possible to provide a curable composition capable of forming a cured product having better weather resistance. it can.
  • a well-known method is used as a method of performing the surface treatment of silica with a silane compound containing a hydrophobic group.
  • a method of mixing a silane compound containing a hydrophobic group and silica, or a method of applying or spraying a solution containing a silane compound containing a hydrophobic group on the surface of silica is used.
  • the average primary particle diameter of silica is preferably 5 to 30 nm, more preferably 10 to 20 nm.
  • Silica having an average primary particle diameter of less than 5 nm is likely to aggregate and has low dispersibility, so that there is a possibility that sufficient effects cannot be obtained by adding silica.
  • the average primary particle diameter of a silica exceeds 30 nm, there exists a possibility that the viscosity of the curable composition obtained may become high too much, or the thixotropy of a curable composition may fall.
  • the average primary particle diameter of silica can be measured according to the following procedure.
  • the silica was photographed with a transmission electron microscope at a magnification of 50,000 to 100,000 times, and the primary particle diameter of 10 or more, especially 100 or more of silica was measured from the obtained photographed image, and the obtained value was obtained.
  • the average primary particle diameter of silica can be calculated by arithmetic averaging. Note that the primary particle diameter of silica means the diameter of the smallest perfect circle that can surround the primary particles of silica.
  • BET specific surface area of silica is preferably 50 ⁇ 300m 2 / g, more preferably 100 ⁇ 200m 2 / g.
  • silica having a BET specific surface area of less than 50 m 2 / g the viscosity of the resulting curable composition may be too high, or the thixotropy of the curable composition may be reduced.
  • silica having a BET specific surface area of more than 300 m 2 / g has low dispersibility, so that there is a possibility that sufficient effects cannot be obtained by adding silica.
  • the BET specific surface area of silica can be measured by a method based on DIN 66131.
  • the content of silica in the curable composition is preferably 10 to 100 parts by weight and more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). If the content of silica in the curable composition is too low, there is a possibility that sufficient effects cannot be obtained due to the addition of silica. Moreover, when content of the silica in a curable composition is too high, there exists a possibility that the viscosity of the curable composition obtained may become high too much, or the thixotropy of a curable composition may fall.
  • the curable composition of the present invention preferably further contains a plasticizer. According to the plasticizer, the flexibility and elongation of the cured product of the curable composition can be improved, and as a result, the weather resistance of the cured product can be improved.
  • Plasticizers include: dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinormal hexyl phthalate, bis (2-ethylhexyl) phthalate, dinormal octyl phthalate, diisononyl phthalate, dinonyl phthalate, Phthalates such as diisodecyl phthalate, diisoundecyl phthalate, and bisbutylbenzyl phthalate; non-aromatic dibasic esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate; butyl oleate; And aliphatic esters such as methyl acetylricinoleate; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol
  • plasticizer phthalate is preferably used, and diisodecyl phthalate is more preferable. According to these plasticizers, the weather resistance of the cured product of the curable composition can be further improved.
  • the content of the plasticizer in the curable composition is preferably 10 to 100 parts by weight and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
  • content of the plasticizer in a curable composition is too low, the viscosity of the obtained curable composition will become high and there exists a possibility that the applicability
  • content of the plasticizer in a curable composition is too high, there exists a possibility that a plasticizer may ooze out on the hardened
  • the curable composition of the present invention preferably further contains an aminosilane coupling agent.
  • the aminosilane coupling agent means a compound containing a silicon atom having an alkoxy group bonded in one molecule and a functional group containing a nitrogen atom.
  • an aminosilane coupling agent is used in combination with the above-described (meth) acrylate polymer (B), the adhesiveness of the curable composition can be further improved by these synergistic effects.
  • 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). If the content of the aminosilane coupling agent in the curable composition is too low, the adhesiveness of the curable composition may not be sufficiently improved. Further, if the content of the aminosilane coupling agent in the curable composition is too high, the curing rate of the curable composition becomes too high, and the storage stability and handleability of the curable composition may be reduced. .
  • 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 1 to 10 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer (A). 5 parts by weight is particularly preferred. If the content of the dehydrating agent in the curable composition is too low, the effect obtained by the dehydrating agent may not be sufficient. Moreover, when content of the dehydrating agent in a curable composition is too high, there exists a possibility that the sclerosis
  • the curable composition of the present invention preferably further contains a weathering stabilizer.
  • a weathering stabilizer include antioxidants, ultraviolet absorbers, and light stabilizers. By using these weather stabilizers, the weather resistance of the cured product of the curable composition can be improved.
  • 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.). Moreover, as a hindered phenolic antioxidant, commercial items, such as IRGANOX (trademark) 1135 (melting
  • 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). 0.5 to 5 parts by weight is particularly preferable.
  • 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, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A). 0.5 to 5 parts by weight is particularly preferable.
  • 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.
  • dimethyl succinate Such as polycondensates of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (mp 63 ° C.) and the like.
  • the content of the light stabilizer in the curable composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, with respect to 100 parts by weight of the polyoxyalkylene polymer (A). ⁇ 5 parts by weight is particularly preferred.
  • the melting point of the weather resistance stabilizer is preferably 10 ° C. or less, more preferably ⁇ 20 to 5 ° C. According to the weather stabilizer having a melting point of 10 ° C. or lower, the weather resistance of the cured product of the curable composition can be further improved.
  • 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 may contain a weathering stabilizer having a melting point of 10 ° C. or less and a weathering stabilizer having a melting point exceeding 10 ° C.
  • the weather resistance of the cured product can be improved.
  • the curable composition contains only a weathering stabilizer having a melting point of 10 ° C. or lower.
  • 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). If the content of the thixotropic agent in the curable composition is small, there is a possibility that thixotropic properties cannot be imparted to the curable composition. Moreover, when there is much content of the thixotropy imparting agent in a curable composition, there exists a possibility that the viscosity of a curable composition may become high and the handleability of a curable composition may fall.
  • silanol condensation catalyst In the curable composition of the present invention, the use of the silanol condensation catalyst is omitted by using the above-mentioned polyoxyalkylene polymer (A), (meth) acrylate polymer (B), and silica in combination. Can do.
  • the silanol condensation catalyst is a silanol formed by hydrolyzing a dialkoxysilyl group of the polyoxyalkylene polymer (A) or a hydrolyzable silyl group of the (meth) acrylate polymer (B). It is a catalyst for promoting a dehydration condensation reaction between groups.
  • the silanol group means a hydroxy group ( ⁇ Si—OH) directly bonded to a silicon atom.
  • Silanol condensation catalysts include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin lauric acid) oxide, dibutyltin bis (acetylacetonate), dibutyltin bis (monoester maleate) , Tin octylate, dibutyltin octoate, dioctyltin oxide, dibutyltin bis (triethoxysilicate), dioctyltin dilaurate, bis (dibutyltin bistriethoxysilicate) oxide, dibutyltin oxybisethoxysilicate, and 1,1,3,3 Organotin compounds such as 3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane; organotitanium compounds such as tetra-n-butoxy titanate and t
  • Content of the silanol condensation catalyst in a curable composition shall be less than 0.001 weight part with respect to 100 weight part of polymers (A), especially 0 weight part.
  • 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, silica, and As needed, it can carry out by the method of mixing a weather resistance stabilizer, another additive, and a solvent so that it may become a predetermined weight ratio, respectively. 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. . Further, the cured product formed from the curable composition of the present invention not only has excellent flexibility and extensibility, but can maintain such excellent flexibility and extensibility over a long period of time. it can. Therefore, even when the cured product of the curable composition is exposed to an external environment such as light, heat, rainwater for a long period of time, the cured product does not cause deterioration such as cracking or decrease in adhesive force, and is excellent. Weather resistance. Furthermore, the curable composition of the present invention and the cured product thereof are also excellent in transparency.
  • the curable composition of the present invention can be used for various applications such as adhesives, sealants, paints, coating agents, pressure-sensitive adhesives, sealants, and the like, and in particular, a transparent substrate made of a transparent material such as glass. Is suitably used for applications in which an adherend is used.
  • TINUVIN registered trademark
  • 384-2 hindered amine light stability Agent
  • hindered amine light stability Agent bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and a mixture of methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, melting point 10 ° C. or less, Toyokuni Oil) HS ester 765
  • silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, Neostan U-130 manufactured by Nitto Kasei Co., Ltd.
  • adherend As the adherend, a lauan plywood, a vinyl chloride plate, and a stainless 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
  • the curable composition was applied onto an aluminum plate so as to have a width of 20 mm and a thickness of 2 mm, and cured by leaving it to stand in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% for 2 weeks to obtain a cured product. . Then, the cured product is irradiated with ultraviolet rays (wavelength: 295 nm to 450 nm) with an irradiation intensity of 100 mW / cm 2 , and irradiation using a UV tester (Isuperki UV Tester manufactured by Iwasaki Electric Co., Ltd.).
  • the curable composition of the present invention can be used in various applications such as adhesives, sealants, paints, coating agents, pressure sensitive adhesives, sealants and the like.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne une composition durcissable capable de former un article durci qui manifeste d'excellentes propriétés d'adhérence et de résistance aux intempéries. Cette composition durcissable est caractérisée en ce qu'elle contient : un polymère de polyoxyalkylène (A) contenant un groupe triméthoxysilyle; un polymère de (méth)acrylate (B) contenant un groupe silyle hydrolysable; et de la silice. Cette composition durcissable durcit sous l'action de l'humidité de l'air ou de l'humidité contenue dans l'article soumis au dépôt de ladite composition, et forme un article durci ayant d'excellentes propriétés d'adhérence à divers substrats. De plus, un article durci formé à partir de cette composition durcissable est capable non seulement de manifester une excellente flexibilité et extensibilité, mais aussi de conserver cette excellente flexibilité et extensibilité sur une longue période de temps.
PCT/JP2012/075245 2011-09-30 2012-09-28 Composition durcissable WO2013047837A1 (fr)

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JP2011-217425 2011-09-30

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175358A1 (fr) * 2013-04-24 2014-10-30 積水フーラー株式会社 Composition durcissable et structure de joint fabriquée à partir de la composition
JPWO2015129903A1 (ja) * 2014-02-25 2017-03-30 住友化学株式会社 粒状接着剤
CN109609053A (zh) * 2018-12-19 2019-04-12 广西华纳新材料科技有限公司 一种石材建筑密封胶用纳米碳酸钙及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002155200A (ja) * 2000-11-22 2002-05-28 Konishi Co Ltd 耐候性樹脂組成物
JP2006291021A (ja) * 2005-04-11 2006-10-26 Kaneka Corp 硬化性組成物の塗工方法、被着体の貼り合せ方法
WO2006112340A1 (fr) * 2005-04-15 2006-10-26 Kaneka Corporation Composition durcissable et article durci d’une transparence excellente
JP2007137955A (ja) * 2005-11-15 2007-06-07 Kaneka Corp 硬化性組成物
WO2007094275A1 (fr) * 2006-02-16 2007-08-23 Kaneka Corporation Composition durcissable
WO2008020600A1 (fr) * 2006-08-16 2008-02-21 Asahi Glass Company, Limited Composition de polymère
JP2010155894A (ja) * 2008-12-26 2010-07-15 Asahi Glass Co Ltd 硬化性組成物
JP2011021107A (ja) * 2009-07-16 2011-02-03 Sekisui Fuller Co Ltd 硬化性組成物、接着剤及びシーリング材

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002155200A (ja) * 2000-11-22 2002-05-28 Konishi Co Ltd 耐候性樹脂組成物
JP2006291021A (ja) * 2005-04-11 2006-10-26 Kaneka Corp 硬化性組成物の塗工方法、被着体の貼り合せ方法
WO2006112340A1 (fr) * 2005-04-15 2006-10-26 Kaneka Corporation Composition durcissable et article durci d’une transparence excellente
JP2007137955A (ja) * 2005-11-15 2007-06-07 Kaneka Corp 硬化性組成物
WO2007094275A1 (fr) * 2006-02-16 2007-08-23 Kaneka Corporation Composition durcissable
WO2008020600A1 (fr) * 2006-08-16 2008-02-21 Asahi Glass Company, Limited Composition de polymère
JP2010155894A (ja) * 2008-12-26 2010-07-15 Asahi Glass Co Ltd 硬化性組成物
JP2011021107A (ja) * 2009-07-16 2011-02-03 Sekisui Fuller Co Ltd 硬化性組成物、接着剤及びシーリング材

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175358A1 (fr) * 2013-04-24 2014-10-30 積水フーラー株式会社 Composition durcissable et structure de joint fabriquée à partir de la composition
JP5698422B1 (ja) * 2013-04-24 2015-04-08 積水フーラー株式会社 硬化性組成物及びこれを用いてなる目地構造
JPWO2015129903A1 (ja) * 2014-02-25 2017-03-30 住友化学株式会社 粒状接着剤
CN109609053A (zh) * 2018-12-19 2019-04-12 广西华纳新材料科技有限公司 一种石材建筑密封胶用纳米碳酸钙及其制备方法
CN109609053B (zh) * 2018-12-19 2020-09-08 广西华纳新材料科技有限公司 一种石材建筑密封胶用纳米碳酸钙的制备方法

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