WO2013047837A1 - Curable composition - Google Patents

Curable composition Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
curable composition
meth
acrylate
group
polymer
Prior art date
Application number
PCT/JP2012/075245
Other languages
French (fr)
Japanese (ja)
Inventor
村山　之彦
Original Assignee
積水フーラー株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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
Publication of WO2013047837A1 publication Critical patent/WO2013047837A1/en

Links

Classifications

    • 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.

Landscapes

  • 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

[Abstract] The present invention provides a curable composition capable of forming a cured article that exhibits excellent adhesion and weather resistance properties. This curable composition is characterized by containing: a polyoxyalkylene polymer (A) containing a trimethoxysilyl group; a (meth)acrylate polymer (B) containing a hydrolyzable silyl group; and silica. Such a curable composition cures because of moisture in the air or moisture contained in the article subjected to deposition thereof, and forms a cured article having excellent adhesion properties to various substrates. In addition, a cured article formed from this curable composition is capable not only of exhibiting excellent flexibility and extendibility, but also of maintaining this excellent flexibility and extendibility over a long period of time.

Description

硬化性組成物Curable composition
　本発明は、優れた接着性及び耐候性を有する硬化性組成物に関する。 The present invention relates to a curable composition having excellent adhesion and weather resistance.
　従来から、架橋可能な加水分解性シリル基を有する重合体を主成分として含有する硬化性組成物が知られている。硬化性組成物は、塗料、コーティング剤、接着剤、感圧接着剤、シーラント及びシーリング材などとして様々な用途に用いられている。 Conventionally, 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.
　硬化性組成物は、雰囲気又は被着体に含まれている湿気により、重合体が有している架橋可能な加水分解性シリル基が加水分解してシラノール基を形成した後、シラノール基同士が脱水縮合してシロキサン結合を形成することによって硬化し、これにより接着力に優れた硬化物を与える。 In the curable composition, 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 | cures by dehydrating condensation and forming a siloxane bond, and this gives the hardened | cured material excellent in the adhesive force.
　例えば、特許文献１では、架橋可能な加水分解性シリル基を有するポリオキシアルキレン系重合体を用いることにより、短時間で硬化することが可能であり、透明性に優れた硬化物を形成することが可能である硬化性組成物が開示されている。 For example, in 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.
特開２００８－２８０４３５号公報JP 2008-280435 A
　しかしながら、特許文献１の硬化性組成物では、短時間で硬化することができるものの接着性が低く、得られる硬化物の各種基材に対する接着力が十分ではないという問題があった。 However, 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.
　さらに、特許文献１の硬化性組成物では、これを硬化させてなる硬化物の耐候性が低いという問題があった。すなわち、特許文献１の硬化性組成物の硬化物は、光、熱、雨水などの外部環境から影響を受けることにより、経時的に柔軟性を失って硬くなると共に脆くなり、最終的にひび割れや接着力の低下などの劣化を生じる問題があった。このような硬化性組成物により形成された硬化物の劣化は、被着体としてガラスなどの透明材料からなる基材を用いた場合には、被着体を透過する光によって促進される。したがって、特許文献１の硬化性組成物には、耐候性の向上が望まれている。 Furthermore, 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.
　したがって、本発明は、接着性に優れていると共に、耐候性に優れた硬化物を形成することが可能な硬化性組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a curable composition capable of forming a cured product having excellent adhesion and weather resistance.
　本発明の硬化性組成物は、トリメトキシシリル基を含有するポリオキシアルキレン系重合体（Ａ）、加水分解性シリル基を含有する（メタ）アクリレート系重合体（Ｂ）、及びシリカを含有することを特徴とする。 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.
　［ポリオキシアルキレン系重合体（Ａ）］
　トリメトキシシリル基（－Ｓｉ（ＯＣＨ3）3）を含有するポリオキシアルキレン系重合体（Ａ）は、主鎖が、一般式：－（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が好ましく挙げられる。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と共に、柔軟性及び伸び性が向上されることによって優れた耐候性を有している硬化物を形成することができる。 [Polyoxyalkylene polymer (A)]
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.
　ポリオキシアルキレン系重合体（Ａ）の主鎖骨格としては、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシブチレン、ポリオキシテトラメチレン、ポリオキシエチレン－ポリオキシプロピレン共重合体、及びポリオキシプロピレン－ポリオキシブチレン共重合体などが挙げられる。なかでも、ポリオキシプロピレンが好ましい。ポリオキシプロピレンによれば、硬化性組成物の接着性を向上させることができるだけでなく、さらに硬化性組成物を硬化させて得られる硬化物に優れた柔軟性及び伸び性を付与し、硬化物の耐候性を向上させることもできる。 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.
　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の他に、ウレタン結合をさらに有していることが好ましい。ウレタン結合は、ポリオキシアルキレン系重合体（Ａ）に極性を付与することができ、これにより硬化性組成物の接着性を向上させることも可能となる。 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.
　ポリオキシアルキレン系重合体（Ａ）は、ポリオキシアルキレン鎖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ことが好ましい。トリメトキシシリル基の近傍にウレタン結合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、硬化性組成物の接着性のさらなる向上が図れる。 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.
　ポリオキシアルキレン鎖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するポリオキシアルキレン系重合体（Ａ）は、例えば、ポリオキシアルキレン鎖の両末端にヒドロキシル基を有するプレポリマーと、トリメトキシシリル基及びイソシアネート基を有する化合物とを反応させることにより得られる。 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.
　ポリオキシアルキレン鎖の両末端にヒドロキシル基を有するプレポリマーとしては、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリオキシブチレングリコール、ポリオキシテトラメチレングリコール、ポリオキシエチレン－ポリオキシプロピレングリコール、及びポリオキシプロピレン－ポリオキシブチレングリコールなどが挙げられる。 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.
　トリメトキシシリル基及びイソシアネート基を有する化合物としては、１－イソシアネートメチルトリメトキシシラン、２－イソシアネートエチルトリメトキシシラン、３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートブチルトリメトキシシラン、３－イソシアネートペンチルトリメトキシシラン、及び１－イソシアネートプロピルトリメトキシシランなどが挙げられる。 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.
　ポリオキシアルキレン鎖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するポリオキシアルキレン系重合体（Ａ）を合成するには、ポリオキシアルキレン鎖の両末端にヒドロキシ基を有するプレポリマーと、トリメトキシシリル基及びイソシアネート基を有する化合物とを混合して混合物を得、この混合物を撹拌して上記プレポリマーのヒドロキシ基と、上記化合物のイソシアネート基とを反応させてウレタン結合を形成させることにより行うことができる。また、上記混合物を加熱しながら撹拌することにより、反応を促進させることができる。 In order to synthesize a polyoxyalkylene polymer (A) having a trimethoxysilyl group via a urethane bond at both ends of the polyoxyalkylene chain, 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 | stimulated by stirring the said mixture, heating.
　ポリオキシアルキレン系重合体（Ａ）の数平均分子量は、３，０００～５０，０００が好ましく、１０，０００～２０，０００がより好ましい。ポリオキシアルキレン系重合体（Ａ）の数平均分子量が大き過ぎると、得られる硬化性組成物の粘度が高くなり、上記硬化性組成物の塗工性などが低下する虞れがある。また、ポリオキシアルキレン系重合体（Ａ）の数平均分子量が小さ過ぎると、得られる硬化性組成物の硬化物が脆くなり、硬化物の機械的強度、伸び性、及び柔軟性が低下する虞れがある。 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.
　なお、本発明において、ポリオキシアルキレン系重合体（Ａ）の数平均分子量はＧＰＣ（ゲルパーミエーションクロマトグラフィー）法によって測定されたポリスチレン換算した値である。具体的には、ポリオキシアルキレン系重合体（Ａ）６～７ｍｇを採取し、採取したポリオキシアルキレン系重合体（Ａ）を試験管に供給した上で、試験管に０．０５重量％のＢＨＴ（ジブチルヒドロキシトルエン）を含むｏ－ＤＣＢ（オルトジクロロベンゼン）溶液を加えてポリオキシアルキレン系重合体（Ａ）の濃度が１ｍｇ／ｍＬとなるように希釈して希釈液を作製する。 In the present invention, 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.
　溶解濾過装置を用いて１４５℃にて回転速度２５ｒｐｍにて１時間に亘って上記希釈液を振とうさせてポリオキシアルキレン系重合体（Ａ）をＢＨＴのｏ－ＤＣＢ溶液に溶解させて測定試料とする。この測定試料を用いてＧＰＣ法によってポリオキシアルキレン系重合体（Ａ）の数平均分子量を測定することができる。 Using a dissolution filtration apparatus, shake the dilution liquid at 145 ° C. for 1 hour at a rotational speed of 25 rpm to dissolve the polyoxyalkylene polymer (A) in the BHT o-DCB solution, and then measure the sample. And The number average molecular weight of the polyoxyalkylene polymer (A) can be measured by the GPC method using this measurement sample.
　ポリオキシアルキレン系重合体（Ａ）における数平均分子量は、例えば、下記測定装置及び測定条件にて測定することができる。
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℃ 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 Mobile phase: o-DCB 1.0 mL / min Sample concentration: 1 mg / mL
Detector: Bryce refractometer Standard material: Polystyrene (Molecular weight: 500 to 8420000, manufactured by TOSOH)
Elution conditions: 145 ° C
SEC temperature: 145 ° C
　なお、後述する（メタ）アクリレート系重合体（Ｂ）の重量平均分子量の測定も上記と同じ方法を用いて行うことができる。 In addition, 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.
　ポリオキシアルキレン系重合体（Ａ）の２５℃における粘度は、１０００～３００００ｍＰａ・ｓが好ましく、４０００～２５０００ｍＰａ・ｓがより好ましく、５０００～１５０００ｍＰａ・ｓが特に好ましい。ポリオキシアルキレン系重合体（Ａ）の粘度が高過ぎると、得られる硬化性組成物の粘度が高くなり、上記硬化性組成物の塗工性などが低下する虞れがある。また、ポリオキシアルキレン系重合体（Ａ）の粘度が低過ぎると、硬化性組成物の硬化物が脆くなり、硬化物の機械的強度や伸び性が低下する虞れがある。 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. Moreover, when the viscosity of a polyoxyalkylene type polymer (A) is too low, the hardened | cured material of a curable composition will become weak, and there exists a possibility that the mechanical strength and elongation property of hardened | cured material may fall.
　なお、本発明において、ポリオキシアルキレン系重合体（Ａ）の２５℃における粘度の測定は、ＪＩＳ　Ｋ１５５７に準拠した方法により測定することができる。 In the present invention, the viscosity of the polyoxyalkylene polymer (A) at 25 ° C. can be measured by a method based on JIS K1557.
　トリメトキシシリル基を含有するポリオキシアルキレン系重合体（Ａ）は、市販されているものを用いることができる。例えば、主鎖骨格がポリオキシプロピレンであり、主鎖骨格の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としては、旭硝子株式会社製　エクセスターＡ２５５１が挙げられる。また、主鎖骨格がポリオキシプロピレンであり、主鎖骨格の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としては、バイエル社製　Ｄｅｓｍｏｓｅａｌ（登録商標）ＸＰ２７４９が挙げられる。 A commercially available polyoxyalkylene polymer (A) containing a trimethoxysilyl group can be used. For example, as 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. In addition, 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. Is mentioned.
　［（メタ）アクリレート系重合体（Ｂ）］
　（メタ）アクリレート系重合体（Ｂ）におけ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なる基である。（メタ）アクリレート系重合体（Ｂ）を、上述したポリオキシアルキレン系重合体（Ａ）と組み合わせて用いることにより、接着力に優れ且つ耐候性が向上された硬化物を形成することができる硬化性組成物を提供することができる。 [(Meth) acrylate polymer (B)]
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. By using the (meth) acrylate polymer (B) in combination with the polyoxyalkylene polymer (A) described above, curing that can form a cured product having excellent adhesion and improved weather resistance. Sex compositions can be provided.
　加水分解性シリル基の加水分解性基としては、特に限定されず、例えば、水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などが挙げられる。 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.
　加水分解性シリル基としては、硬化性組成物の接着性を向上させることができることから、アルコキシシリル基が好ましい。アルコキシシリル基としては、トリメトキシシリル基、トリエトキシシリル基、トリイソプロポキシシリル基、及びトリフェノキシシリル基などのトリアルコキシシリル基；ジメトキシメチルシリル基、及びジエトキシメチルシリル基などのジメトキシシリル基；並びに、メトキシジメトキシシリル基、及びエトキシジメチルシリル基などのモノアルコキシシリル基が挙げられる。なかでも、トリアルコキシシリル基がより好ましく、トリメトキシシリル基が特に好ましい。 As the hydrolyzable silyl group, an alkoxysilyl group is preferable because the adhesiveness of the curable composition can be improved. Examples of 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. Among these, a trialkoxysilyl group is more preferable, and a trimethoxysilyl group is particularly preferable.
　（メタ）アクリレート系重合体（Ｂ）の主鎖骨格としては、（メタ）アクリレート系モノマーをラジカル重合して得られる（メタ）アクリレート系重合体が挙げられる。なお、（メタ）アクリレートは、メタクリレート又はアクリレートを意味する。 The main chain skeleton of the (meth) acrylate polymer (B) includes a (meth) acrylate polymer obtained by radical polymerization of a (meth) acrylate monomer. In addition, (meth) acrylate means a methacrylate or an acrylate.
　（メタ）アクリレート系重合体（Ｂ）の主鎖を構成する（メタ）アクリレート系モノマーとして、具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、エポキシ（メタ）アクリレート、ポリエステル（メタ）アクリレート、ウレタン（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、５－ヒドロキシペンチル（メタ）アクリレート、６－ヒドロキシヘキシル（メタ）アクリレート、３－ヒドロキシ－３－メチルブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、２－［アクリロイルオキシ］エチル－２－ヒドロキシエチルフタル酸、及び２－［アクリロイルオキシ］エチル－２－ヒドロキシプロピルフタル酸などが挙げられる。これらの（メタ）アクリレート系モノマーは、単独で用いられても二種以上が併用されてもよい。 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, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl ( (Meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, glycidyl (meth) Chryrate, tetrahydrofurfuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) ) Acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropy (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meta ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- [acryloyloxy] ethyl-2-hydroxyethylphthalic acid, 2- [acryloyloxy] ethyl-2-hydroxypropylphthalic acid, etc. . These (meth) acrylate monomers may be used alone or in combination of two or more.
　（メタ）アクリレート系重合体（Ｂ）において、他のモノマーを共重合することも可能である。このようなモノマーとしては、例えば、スチレン、インデン、α－メチルスチレン、ｐ－メチルスチレン、ｐ－クロロスチレン、ｐ－クロロメチルスチレン、ｐ－メトキシスチレン、ｐ－ｔｅｒｔ－ブトキシスチレン、ジビニルベンゼンなどのスチレン誘導体、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプロン酸ビニル、安息香酸ビニル、珪皮酸ビニルなどのビニルエステル基を持つ化合物、無水マレイン酸、Ｎ－ビニルピロリドン、Ｎ－ビニルモルフォリン、（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－ベンジルマレイミド、ｎ－プロピルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、ｔｅｒｔ－アミルビニルエーテル、シクロヘキシルビニルエーテル、２－エチルヘキシルビニルエーテル、ドデシルビニルエーテル、オクタデシルビニルエーテル、２－クロロエチルビニルエーテル、エチレングリコールブチルビニルエーテル、トリエチレングリコールメチルビニルエーテル、安息香酸（４－ビニロキシ）ブチル、エチレングリコールジビニルエーテル、ジエチレングリコールジビニルエーテル、トリエチレングリコールジビニルエーテル、テトラエチレングリコールジビニルエーテル、ブタン－１，４－ジオール－ジビニルエーテル、ヘキサン－１，６－ジオール－ジビニルエーテル、シクロヘキサン－１，４－ジメタノール－ジビニルエーテル、イソフタル酸ジ（４－ビニロキシ）ブチル、グルタル酸ジ（４－ビニロキシ）ブチル、コハク酸ジ（４－ビニロキシ）ブチルトリメチロールプロパントリビニルエーテル、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、６－ヒドロキシヘキシルビニルエーテル、シクロヘキサン－１，４－ジメタノールモノビニルエーテル、ジエチレングリコールモノビニルエーテル、３－アミノプロピルビニルエーテル、２－（Ｎ，Ｎ－ジエチルアミノ）エチルビニルエーテル、ウレタンビニルエーテル、ポリエステルビニルエーテルなどのビニロキシ基を持つ化合物などを挙げることができる。これらのモノマーは、単独で用いられても二種以上が併用されてもよい。 In the (meth) acrylate polymer (B), other monomers can be copolymerized. Examples of such monomers include styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, 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 vinyl ether, triethylene glycol methyl vinyl ether, benzoic acid (4-vinyloxy) butyl, ethylene glycol Divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol-divinyl ether, cyclohexane-1,4-dimethanol Divinyl ether, di (4-vinyloxy) butyl isophthalate, glutar Di (4-vinyloxy) butyl acid, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol Examples thereof include compounds having a vinyloxy group such as monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, and polyester vinyl ether. These monomers may be used alone or in combination of two or more.
　（メタ）アクリレート系重合体（Ｂ）の主鎖骨格は、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が好ましく、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ことがより好ましい。主鎖骨格が上記共重合体からなる（メタ）アクリレート系重合体（Ｂ）によれば、硬化性組成物の接着性をより向上させることができる。 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.
　（メタ）アクリレート系重合体（Ｂ）の重合方法としては、特に限定されず、公知の方法を用いることができ、例えば、フリーラジカル重合法、アニオン重合法、カチオン重合法、ＵＶラジカル重合法、リビングアニオン重合法、リビングカチオン重合法、リビングラジカル重合法などの各種重合法が挙げられる。 The polymerization method of the (meth) acrylate polymer (B) is not particularly limited, and a known method can be used. For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, Various polymerization methods such as a living anionic polymerization method, a living cation polymerization method, and a living radical polymerization method may be mentioned.
　（メタ）アクリレート系重合体（Ｂ）への加水分解性シリル基の導入方法としては、特に限定されず、例えば、分子中に不飽和基を導入した（メタ）アクリレート系重合体に、加水分解性シリル基を有するヒドロシランを作用させてヒドロシリル化する方法などを利用することができる。 The method for introducing the hydrolyzable silyl group into the (meth) acrylate polymer (B) is not particularly limited. For example, 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.
　（メタ）アクリレート系重合体（Ｂ）の重量平均分子量は、２，０００～５０，０００が好ましく、２，５００～１５，０００がより好ましく、２，５００～５，０００が特に好ましい。（メタ）アクリレート系重合体（Ｂ）の重量平均分子量が大き過ぎると、硬化性組成物の接着性が低下する虞れがある。また、（メタ）アクリレート系重合体（Ｂ）の重量平均分子量が低過ぎると、硬化性組成物の硬化物が脆くなり、硬化物の機械的強度、伸び性や耐候性が低下する虞れがある。また、（メタ）アクリレート系重合体（Ｂ）の重量平均分子量が小さ過ぎると、硬化性組成物の接着性が低下する虞れもある。 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.
　硬化性組成物中における（メタ）アクリレート系重合体（Ｂ）の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、５～１００重量部が好ましく、１０～７０重量部がより好ましく、３０～５０重量部が特に好ましい。硬化性組成物中における（メタ）アクリレート系重合体（Ｂ）の含有量が低過ぎると、硬化性組成物の接着性を十分に向上できない虞れがある。また、硬化性組成物中における（メタ）アクリレート系重合体（Ｂ）の含有量が高過ぎると、得られる硬化性組成物の硬化物が脆くなり、硬化物の機械的強度、伸び性、及び柔軟性が低下する虞れがある。 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 | cured material of the obtained curable composition will become weak, mechanical strength of a hardened | cured material, extensibility, and There is a possibility that the flexibility is lowered.
　［シリカ］
　本発明の硬化性組成物は、シリカを含有していることによって、柔軟性及び伸び性が向上されることにより、優れた耐候性を有している硬化物を形成することができる。 [silica]
The curable composition of this invention can form the hardened | cured material which has the outstanding weather resistance by a softness | flexibility and elongation property improving by containing a silica.
　シリカとしては、疎水性シリカ及び親水性シリカが挙げられるが、疎水性シリカが好ましく挙げられる。 Silica includes hydrophobic silica and hydrophilic silica, with hydrophobic silica being preferred.
　疎水性シリカとしては、メチル基、ジメチル基及びトリメチル基などの疎水性基を含有するシラン化合物によって表面処理されてなるシリカが挙げられる。 Examples of the hydrophobic silica 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.
　疎水性基を含有するシラン化合物としては、メチル基及びハロゲン原子を含有するシラン化合物が好ましく挙げられる。ハロゲン原子としては、例えば、塩素原子及び臭素原子などが挙げられる。そして、メチル基及びハロゲン原子を含有するシラン化合物として、具体的には、ジメチルジクロロシラン、トリメチルクロロシラン、メチルトリクロロシラン、ベンジルジメチルクロロシラン、ブロモメチルジメチルクロロシランが挙げられる。なかでも、ジメチルジクロロシランが好ましい。 Preferred examples of the silane compound containing a hydrophobic group include silane compounds containing a methyl group and a halogen atom. Examples of 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.
　通常、シリカは、その表面にシラノール基を有している。そして、このようなシリカ表面をメチル基及びハロゲン原子を含有するシラン化合物で表面処理することによって、シリカ表面に存在するシラノール基とシラン化合物が有しているハロゲン原子とが反応して、シリカ表面にメチル基が導入されることによって、疎水性シリカが得られる。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。 Usually, 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.
　メチル基及びハロゲン原子を含有するシラン化合物によって表面処理されてなる疎水性シリカによれば、より優れた耐候性を有している硬化物を形成することができる硬化性組成物を提供することができる。 According to 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.
　なお、疎水性基を含有するシラン化合物によってシリカの表面処理を行う方法としては、公知の方法が用いられる。例えば、疎水性基を含有するシラン化合物とシリカとを混合する方法や、疎水性基を含有するシラン化合物を含む溶液をシリカの表面に塗布又は噴霧する方法などが用いられる。 In addition, a well-known method is used as a method of performing the surface treatment of silica with a silane compound containing a hydrophobic group. For example, 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.
　シリカの平均一次粒子径は、５～３０ｎｍが好ましく、１０～２０ｎｍがより好ましい。平均一次粒子径が５ｎｍ未満であるシリカでは、凝集し易く分散性が低いために、シリカを添加したことによって充分な効果が得られない虞れがある。また、シリカの平均一次粒子径が３０ｎｍを超えると、得られる硬化性組成物の粘度が高くなり過ぎたり、硬化性組成物のチキソ性が低下する虞れがある。 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. Moreover, when 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.
　なお、本発明において、シリカの平均一次粒子径の測定は、次の要領に従って行うことができる。シリカを透過型電子顕微鏡により５万倍～１０万倍の倍率で撮影し、得られた撮影像より１０個以上、特に１００個以上のシリカの一次粒子径を測定して、得られた値を相加平均することにシリカの平均一次粒子径を算出することができる。なお、シリカの一次粒子径とは、シリカの一次粒子を包囲し得る最小径の真円の直径を意味する。 In the present invention, 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.
　シリカのＢＥＴ比表面積は、５０～３００ｍ2／ｇが好ましく、１００～２００ｍ2／ｇがより好ましい。ＢＥＴ比表面積が５０ｍ2／ｇ未満であるシリカでは、得られる硬化性組成物の粘度が高くなり過ぎたり、硬化性組成物のチキソ性が低下する虞れがある。また、ＢＥＴ比表面積が３００ｍ2／ｇを超えるシリカでは、分散性が低いために、シリカを添加したことによって充分な効果が得られない虞れがある。 BET specific surface area of silica is preferably 50 ~ 300m 2 / g, more preferably 100 ~ 200m 2 / g. In 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. In addition, 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.
　なお、本発明において、シリカのＢＥＴ比表面積の測定は、ＤＩＮ　６６１３１に準拠した方法により行うことができる。 In the present invention, the BET specific surface area of silica can be measured by a method based on DIN 66131.
　硬化性組成物中におけるシリカの含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、１０～１００重量部が好ましく、１０～５０重量部がより好ましい。硬化性組成物中におけるシリカの含有量が低過ぎると、シリカを添加したことによって充分な効果が得られない虞れがある。また、硬化性組成物中におけるシリカの含有量が高過ぎると、得られる硬化性組成物の粘度が高くなり過ぎたり、硬化性組成物のチキソ性が低下するする虞れがある。 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.
　［可塑剤］
　本発明の硬化性組成物は、可塑剤をさらに含んでいることが好ましい。可塑剤によれば、硬化性組成物の硬化物の柔軟性及び伸び性を向上させ、結果として硬化物の耐候性を向上させることができる。 [Plasticizer]
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.
　可塑剤としては、フタル酸ジメチル、フタル酸ジエチル、フタル酸ジブチル、フタル酸ジイソブチル、フタル酸ジノルマルヘキシル、フタル酸ビス（２－エチルヘキシル）、フタル酸ジノルマルオクチル、フタル酸ジイソノニル、フタル酸ジノニル、フタル酸ジイソデシル、フタル酸ジイソウンデシル、及びフタル酸ビスブチルベンジルなどのフタル酸エステル；アジピン酸ジオクチル、セバシン酸ジオクチル、セバシン酸ジブチル、及びコハク酸イソデシルなどの非芳香族二塩基酸エステル；オレイン酸ブチル、及びアセチルリシノール酸メチルなどの脂肪族エステル；ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、及びペンタエリスリトールエステルなどのポリアルキレングリコールのエステル；並びにトリクレジルホスフェート、及びトリブチルホスフェートなどのリン酸エステルなどが挙げられる。これらの可塑剤は、単独で用いられても二種以上が併用されてもよい。 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 ester; Tricresyl phosphate, and phosphoric acid esters such as tributyl phosphate and the like to. These plasticizers may be used alone or in combination of two or more.
　なかでも、可塑剤としては、フタル酸エステルが好ましく用いられ、フタル酸ジイソデシルがより好ましい。これらの可塑剤によれば、硬化性組成物の硬化物の耐候性をより向上させることができる。 Among these, as the 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.
　硬化性組成物中における可塑剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、１０～１００重量部が好ましく、２０～７０重量部がより好ましい。硬化性組成物中における可塑剤の含有量が低過ぎると、得られる硬化性組成物の粘度が高くなり、上記硬化性組成物の塗工性などが低下する虞れがある。また、硬化性組成物中における可塑剤の含有量が高過ぎると、硬化性組成物の硬化物表面に可塑剤が滲み出して、硬化物の耐候性を低下させる虞れがある。 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). When 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 | paintability of the said curable composition may fall. Moreover, when content of the plasticizer in a curable composition is too high, there exists a possibility that a plasticizer may ooze out on the hardened | cured material surface of a curable composition, and may reduce the weather resistance of hardened | cured material.
　［アミノシランカップリング剤］
　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含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、硬化性組成物の接着性をより向上させることができる。 [Aminosilane coupling agent]
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. When 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.
　アミノシランカップリング剤として、具体的には、３－アミノプロピルトリメトキシシラン、３－アミノプロピルメチルジメトキシシラン、３－アミノプロピルトリエトキシシラン、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、Ｎ－（２－アミノエチル）－３－アミノプロピルトリエトキシシラン、Ｎ，Ｎ’－ビス－〔３－（トリメトキシシリル）プロピル〕エチレンジアミン、Ｎ，Ｎ’－ビス－〔３－（トリエトキシシリル）プロピル〕エチレンジアミン、Ｎ，Ｎ’－ビス－〔３－（メチルジメトキシシリル）プロピル〕エチレンジアミン、Ｎ，Ｎ’－ビス－〔３－（トリメトキシシリル）プロピル〕ヘキサメチレンジアミン、Ｎ，Ｎ’－ビス－〔３－（トリエトキシシリル）プロピル〕ヘキサメチレンジアミン等が挙げられる。これらのアミノシランカップリング剤は、単独で用いられても二種以上が併用されてもよい。 Specific examples of aminosilane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (tri Ethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N '-Bis- [3- (triethoxysilyl) propyl] hexamethylenediamine Etc. The. These aminosilane coupling agents may be used alone or in combination of two or more.
　なかでも、アミノシランカップリング剤としては、３－アミノプロピルトリメトキシシラン、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、及びＮ－（２－アミノエチル）－３－アミノプロピルトリエトキシシランが好ましく挙げられ、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がより好ましく挙げられる。これらのアミノシランカップリング剤によれば、（メタ）アクリレート系重合体（Ｂ）との相乗効果が得られ易く、硬化性組成物の接着性をより向上させることができる。 Among these, 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.
　硬化性組成物中におけるアミノシランカップリング剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．５～１０重量部が好ましく、１～５重量部がより好ましい。硬化性組成物中におけるアミノシランカップリング剤の含有量が低過ぎると、硬化性組成物の接着性を充分に向上できない虞れがある。また、硬化性組成物中におけるアミノシランカップリング剤の含有量が高過ぎると、硬化性組成物の硬化速度が高くなり過ぎ、硬化性組成物の貯蔵安定性や取扱性が低下する虞れがある。 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. .
　［脱水剤］
　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。 [Dehydrating agent]
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.
　脱水剤としては、ビニルトリメトキシシラン、ジメチルジメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、テトラメトキシシラン、フェニルトリメトキシシラン、及びジフェニルジメトキシシランなどのシラン化合物；並びにオルトギ酸メチル、オルトギ酸エチル、オルト酢酸メチル、及びオルト酢酸エチル等のエステル化合物などを挙げることができる。これらの脱水剤は、単独で用いられても二種以上が併用されてもよい。なかでも、ビニルトリメトキシシランが好ましい。 Examples of 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. These dehydrating agents may be used alone or in combination of two or more. Of these, vinyltrimethoxysilane is preferable.
　硬化性組成物中における脱水剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．５～２０重量部が好ましく、１～１０重量部がより好ましく、１～５重量部が特に好ましい。硬化性組成物中における脱水剤の含有量が低過ぎると、脱水剤により得られる効果が十分ではない虞れがある。また、硬化性組成物中における脱水剤の含有量が高過ぎると、硬化性組成物の硬化性が低下する虞れがある。 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 | hardenability of a curable composition may fall.
　［耐候安定剤］
　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、及び光安定化剤が好ましく挙げられる。これらの耐候安定剤を用いることによって、硬化性組成物の硬化物の耐候性を向上させることができる。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。 [Weatherproof stabilizer]
The curable composition of the present invention preferably further contains a weathering stabilizer. Preferred examples of the weather resistance 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.
　酸化防止剤としては、ヒンダードフェノール系酸化防止剤、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、及びポリフェノール系酸化防止剤などが挙げられる。なかでも、ヒンダードフェノール系酸化防止剤が好ましい。ヒンダードフェノール系酸化防止剤として、具体的には、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℃）、オクタデシル－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５２℃）、及びＮ，Ｎ′－ヘキサン－１，６－ジイルビス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオンアミド）]（融点１５８℃）などが挙げられる。また、ヒンダードフェノール系酸化防止剤としては、ＢＡＳＦ社製　ＩＲＧＡＮＯＸ（登録商標）１１３５（融点５℃）などの市販品を用いることもできる。 Examples of the antioxidant 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 | fusing point 5 degreeC) by BASF, can also be used.
　硬化性組成物中における酸化防止剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．１～２０重量部が好ましく、０．３～１０重量部がより好ましく、０．５～５重量部が特に好ましい。 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.
　紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤などが挙げられる。なかでも、ベンゾトリアゾール系紫外線吸収剤が好ましい。ベンゾトリアゾール系紫外線吸収剤として、具体的には、２－（２Ｈ－ベンゾトリアゾール－２－イル）－ｐ－クレゾール（融点１３０℃）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－６－ビス（１－メチル－１－フェニルエチル）フェノール（融点１３９℃）、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℃）、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４，６－ジ－ｔｅｒｔ－ペンチルフェノール（融点８４℃）、及び２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール（融点１０４℃）などが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤としては、ＢＡＳＦ社製　ＴＩＮＵＶＩＮ（登録商標）３８４－２（融点１０℃以下）などの市販品を用いることもできる。 Examples of UV absorbers 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 (melting point 104 ° C.) and the like. As the benzotriazole-based ultraviolet absorber, commercially available products such as TINUVIN (registered trademark) 384-2 (melting point: 10 ° C. or lower) manufactured by BASF Corporation may be used.
　硬化性組成物中における紫外線吸収剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．１～２０重量部が好ましく、０．１～１０重量部がより好ましく、０．５～５重量部が特に好ましい。 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.
　光安定剤としては、ヒンダードアミン系光安定剤などが挙げられる。具体的には、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート及びメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートの混合物（融点１０℃以下）、ジブチルアミン・１，３，５－トリアジン・Ｎ，Ｎ’－ビス（２，２，６，６－テトラメチル－４－ピペリジル－１，６－ヘキサメチレンジアミンとＮ－（２，２，６，６－テトラメチル－４－ピペリジル）ブチルアミンとの重縮合物（融点１３５℃）、ポリ［｛６－（１，１，３，３－テトラメチルブチル）アミノ－１，３，５－トリアジン－２，４－ジイル｝｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６－テトラメチル－４－ピペリジル）イミノ｝］（融点１１８℃）、コハク酸ジメチルと４－ヒドロキシ－２，２，６，６－テトラメチル－１－ピペリジンエタノールの重縮合物（融点６３℃）などが挙げられる。 Examples of 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. or less ), Dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2, Polycondensate with 6,6-tetramethyl-4-piperidyl) butylamine (melting point 135 ° C.), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine -2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (melting point 118 ° C), dimethyl succinate Such as polycondensates of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (mp 63 ° C.) and the like.
　硬化性組成物中における光安定剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．５～２０重量部が好ましく、１～１０重量部がより好ましく、１～５重量部が特に好ましい。 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.
　耐候安定剤の融点は、１０℃以下が好ましく、－２０～５℃がより好ましい。融点が１０℃以下である耐候安定剤によれば、硬化性組成物の硬化物の耐候性をさらに向上させることができる。 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.
　なお、複数種の耐候安定剤を用いる場合、耐候安定剤の融点とはそれぞれの耐候安定剤の融点を意味する。本発明において、耐候安定剤の融点は、ＪＩＳ　Ｋ００６４（１９２２年）に準拠した目視法により測定された値とする。 In addition, when using several types of weather stabilizers, the melting point of the weather stabilizer means the melting point of each weather stabilizer. In the present invention, the melting point of the weather stabilizer is a value measured by a visual method according to JIS K0064 (1922).
　融点が１０℃以下の耐候安定剤を用いる場合、硬化性組成物は融点が１０℃以下の耐候安定剤と、融点が１０℃を超える耐候安定剤とを含んでいても、硬化性組成物の硬化物の耐候性を向上することができる。しかしながら、硬化性組成物は、融点が１０℃以下の耐候安定剤のみを含んでいることが好ましい。 When a weathering stabilizer having a melting point of 10 ° C. or less is used, 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. However, it is preferable that the curable composition contains only a weathering stabilizer having a melting point of 10 ° C. or lower.
　本発明の硬化性組成物は、上述した成分の他にも、チキソ性付与剤、顔料、染料、及び沈降防止剤などの他の添加剤、並びに溶剤などを含んでいてもよい。他の添加剤や溶媒は、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。 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.
　チキソ性付与剤は、硬化性組成物にチキソトロピー性を発現せることができるものであればよい。チキソ性付与剤としては、水添ひまし油、脂肪酸ビスアマイド、ヒュームドシリカなどが好ましく挙げられる。 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.
　硬化性組成物中におけるチキソ性付与剤の含有量は、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、０．１～２００重量部が好ましく、１～１５０重量部がより好ましい。硬化性組成物中におけるチキソ性付与剤の含有量が少ないと、硬化性組成物にチキソトロピー性を付与することができない虞れがある。また、硬化性組成物中におけるチキソ性付与剤の含有量が多いと、硬化性組成物の粘度が高くなり、硬化性組成物の取扱性が低下する虞れがある。 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.
　［シラノール縮合触媒］
　本発明の硬化性組成物では、上述したポリオキシアルキレン系重合体（Ａ）、（メタ）アクリレート系重合体（Ｂ）、及びシリカを組み合わせて用いることにより、シラノール縮合触媒の使用を省略することができる。 [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.
　シラノール縮合触媒とは、ポリオキシアルキレン系重合体（Ａ）が有するジアルコキシシリル基や（メタ）アクリレート系重合体（Ｂ）が有する加水分解性シリル基が加水分解することなどにより形成された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。硬化性組成物がシラノール縮合触媒を含有していると、硬化性組成物の硬化物の劣化を促進させ、硬化物が柔軟性や伸び性を失って脆くなり、結果として、硬化物にひび割れの発生や接着力の低下が生じる虞れがある。したがって、本発明の硬化性組成物は、シラノール縮合触媒を含有していないことが好ましい。 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. When the curable composition contains a silanol condensation catalyst, the cured product of the curable composition is accelerated to deteriorate, and the cured product loses flexibility and extensibility and becomes brittle. As a result, the cured product is cracked. There is a possibility that the generation and the adhesive strength may be reduced. Therefore, it is preferable that the curable composition of the present invention does not contain a silanol condensation catalyst.
　シラノール縮合触媒としては、ジブチル錫ジラウレート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫フタレート、ビス（ジブチル錫ラウリン酸）オキサイド、ジブチル錫ビス（アセチルアセトナート）、ジブチル錫ビス（モノエステルマレート）、オクチル酸錫、ジブチル錫オクトエート、ジオクチル錫オキサイド、ジブチル錫ビス（トリエトキシシリケート）、ジオクチル錫ジラウレート、ビス（ジブチル錫ビストリエトキシシリケート）オキサイド、ジブチル錫オキシビスエトキシシリケート、及び１，１，３，３－テトラブチル－１，３－ジラウリルオキシカルボニル－ジスタノキサンなどの有機錫系化合物；テトラ－ｎ－ブトキシチタネート、及びテトライソプロポキシチタネートなどの有機チタン系化合物；１，５，７－トリアザビシクロ［４．４．０］デカー５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカー５－エン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、６－ジブチルアミノ－１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、１，５－ジアザビシクロ［４．３．０］ノナー５－エンなどのシクロアミジン系化合物；ジブチルアミン－２－エチルヘキソエートなどが挙げられる。また、他の酸性触媒や塩基性触媒もシラノール縮合触媒として用いることができる。 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 tetraisopropoxy titanate; , 5,7-triazabicyclo [4.4.0] deca5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene, 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] noner 5 -Cycloamidine compounds such as ene; dibutylamine-2-ethylhexoate and the like. Other acidic catalysts and basic catalysts can also be used as the silanol condensation catalyst.
　硬化性組成物中におけるシラノール縮合触媒の含有量は、重合体（Ａ）１００重量部に対して、０．００１重量部未満、特に０重量部とする。 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.
　本発明の硬化性組成物の製造は、トリメトキシシリル基を含有するポリオキシアルキレン系重合体（Ａ）、加水分解性シリル基を含有する（メタ）アクリレート系重合体（Ｂ）、シリカ、並びに必要に応じて、耐候安定剤、他の添加剤、及び溶剤をそれぞれ所定の重量比となるように混合する方法により行うことができる。混合は減圧下で行うことが好ましい。 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.
　本発明の硬化性組成物は、空気中の湿気や、被着体に含まれている湿気によって迅速に硬化し、各種基材に対して優れた接着力を有している硬化物を形成する。また、本発明の硬化性組成物により形成された硬化物は、柔軟性及び伸び性に優れているだけでなく、このような優れた柔軟性及び伸び性を長期間に亘って維持することができる。したがって、硬化性組成物の硬化物が光、熱、雨水などの外部環境に長期間に亘って曝されたとしても、硬化物がひび割れや接着力の低下などの劣化を生じることがなく、優れた耐候性を発揮することができる。さらに、本発明の硬化性組成物及びその硬化物は透明性にも優れている。 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.
　したがって、本発明の硬化性組成物は、接着剤、シーリング材、塗料、コーティング剤、感圧接着剤、シーラントなどの様々な用途に用いることができ、特にガラスなどの透明材料からなる透明基材を被着体とする用途に好適に用いられる。 Therefore, 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.
　以下に実施例を挙げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。 Hereinafter, the embodiments of the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
　（実施例１～１６、比較例１～３）
　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（Ａ）（２５℃における粘度５，０００ｍＰａ・ｓ、バイエル社製　Ｄｅｓｍｏｓｅａｌ（登録商標）ＸＰ２７４９）、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からなり且つトリメトキシシリル基を有している（メタ）アクリレート系重合体（Ｂ）（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）、ジメチルジクロロシランで表面処理されてなる疎水性シリカ（平均一次粒子径１６ｎｍ、ＢＥＴ比表面積１１０ｍ2／ｇ、エボニックデグサ社製　ＡＥＲＯＳＩＬ　Ｒ９７２）、可塑剤（フタル酸ジイソデシル）、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（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）、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）、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）、ヒンダードアミン系光安定剤（ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート及びメチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートの混合物、融点１０℃以下、豊国製油株式会社製　ＨＳエステル７６５）、及びシラノール縮合触媒（１，１，３，３－テトラブチル－１，３－ジラウリルオキシカルボニル－ジスタノキサン、日東化成株式会社製　ネオスタンＵ－１３０）をそれぞれ表１及び２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。 (Examples 1 to 16, Comparative Examples 1 to 3)
Polyoxyalkylene polymer (A) having a main chain skeleton of polyoxypropylene and having a trimethoxysilyl group at the end of the main chain skeleton via a urethane bond (viscosity at 25 ° C., 5,000 mPa · s Desmosal (registered trademark) XP2749, manufactured by Bayer AG), a (meth) acrylate polymer (B) in which the main chain skeleton is a copolymer of ethyl acrylate and n-butyl acrylate and has a trimethoxysilyl group Alfon US-6170 manufactured by Toagosei Co., Ltd., weight average molecular weight 2,800), hydrophobic silica surface-treated with dimethyldichlorosilane (average primary particle size 16 nm, BET specific surface area 110 m 2 / g, AEROSIL manufactured by Evonik Degussa) R972), plasticizer (diisodecyl phthalate), aminosilane Pulling agent (1) (N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), aminosilane coupling agent (2) (3-aminopropyltrimethoxysilane, Shin-Etsu Chemical KBM-903), dehydrating agent (vinyltrimethoxysilane, Shin-Etsu Chemical KBM-1003), hindered phenol antioxidant (1) (pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], melting point 118 ° C., IRGANOX (registered trademark) 1010) manufactured by BASF, benzotriazole ultraviolet absorber (1) (2- [5-chloro (2H) -Benzotriazol-2-yl] -4-methyl-6- (tert-butyl) pheno , 139 ° C., TINUVIN (registered trademark) 326 manufactured by BASF), benzotriazole ultraviolet absorber (2) (melting point: 10 ° C. or lower, TINUVIN (registered trademark) 384-2 manufactured by BASF), 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) and silanol condensation catalyst (1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distannoxane, Neostan U-130 manufactured by Nitto Kasei Co., Ltd.) are shown in Tables 1 and 2, respectively. By mixing until uniform in a sealed stirrer while reducing the pressure so that the blending amount shown in A curable composition was prepared.
　（評価）
　硬化性組成物の接着性及び耐候性を下記手順に従って評価した。結果をまとめて表１及び２に示す。 (Evaluation)
The adhesiveness and weather resistance of the curable composition were evaluated according to the following procedures. The results are summarized in Tables 1 and 2.
　（接着性）
　被着体として、ラワン合板、塩化ビニル板、及びステンレス板を用意した。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（bad）」とし、硬化物が全て界面破壊したものを「不良（bad）」とした。 (Adhesiveness)
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. In Table 1, when exfoliating the cured product from the adherend, all the cured product was agglomerated and destroyed, indicating "excellent", and the cured product had a part where the agglomerated fracture and a part where the interface was destroyed Was evaluated as “bad”, and all the cured products were broken at the interface, and “bad”.
　なお、硬化物の凝集破壊とは、被着体から硬化物を剥離する際に、硬化物が破壊した状態を意味する。また、硬化物の界面破壊とは、被着体から硬化物を剥離する際に、被着体と硬化物との界面で剥離した状態を意味する。硬化性組成物の硬化物の接着力が高いほど凝集破壊を生じ、硬化性組成物の硬化物の接着力が低いほど界面破壊を生じる。 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. Moreover, the interface destruction of hardened | cured material means the state which peeled in the interface of a to-be-adhered body and hardened | cured material when peeling hardened | cured material from a to-be-adhered body. The higher the adhesive strength of the cured product of the curable composition, the more the cohesive failure occurs, and the lower the adhesive strength of the cured product of the curable composition, the more the interface failure occurs.
　（耐候性）
　硬化性組成物を、アルミ板上に、幅２０ｍｍ、厚み２ｍｍとなるように塗布し、温度２３℃、相対湿度５０％の雰囲気下に２週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、硬化物に、ＵＶ試験機（岩崎電機株式会社製　アイスーパーＵＶテスター）を用いて、ブラックパネル温度を６３℃とし、紫外線（波長：２９５ｎｍ～４５０ｎｍ）を照射強度１００ｍＷ／ｃｍ2、及び照射距離：２４０ｍｍ（光源と硬化物間）の照射条件にて６時間に亘って連続して照射した後、硬化物を暗黒下に２時間放置し、且つ紫外線照射開始から５．９時間後に３０秒間水シャワーを行う操作を１サイクルとし、このサイクルを繰り返し、紫外線照射時間が合計で５０時間、１００時間、２００時間、及び３００時間となった時点での硬化物の表面状態を目視により観察した。なお、表１において、目視によって硬化物表面にクラックの発生が全く認められなかったものを「優（excellent）」とし、目視によって硬化物表面にクラックの発生が認められたが、クラックの長さが０．１ｍｍ以下であったものを「良（good）」とし、目視によって硬化物表面に長さが０．１ｍｍを超えるクラックの発生が認められたものを「不良（bad）」とした。 (Weatherability)
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.). Distance: Continuous irradiation for 6 hours under irradiation conditions of 240 mm (between the light source and the cured product), then the cured product is left in the dark for 2 hours, and 5.9 hours after the start of UV irradiation for 30 seconds. The operation of performing a water shower was defined as one cycle, and this cycle was repeated, and the surface state of the cured product was visually observed when the ultraviolet irradiation time reached 50 hours, 100 hours, 200 hours, and 300 hours in total. In Table 1, “excellent” means that no crack was observed on the surface of the cured product by visual inspection, and cracks were observed on the surface of the cured product by visual inspection. In which cracks with a length exceeding 0.1 mm were visually observed on the surface of the cured product were evaluated as “bad”.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本発明の硬化性組成物は、接着剤、シーリング材、塗料、コーティング剤、感圧接着剤、シーラントなどの様々な用途に用いることができる。 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.

Claims (7)

  1. 　トリメトキシシリル基を含有するポリオキシアルキレン系重合体（Ａ）と、加水分解性シリル基を含有する（メタ）アクリレート系重合体（Ｂ）と、シリカとを含有することを特徴とする硬化性組成物。 Curability characterized by containing a polyoxyalkylene polymer (A) containing a trimethoxysilyl group, a (meth) acrylate polymer (B) containing a hydrolyzable silyl group, and silica. Composition.
  2. 　（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。 2. The curable composition according to claim 1, wherein the main chain skeleton of the (meth) acrylate polymer (B) is a copolymer of ethyl (meth) acrylate and n-butyl (meth) acrylate. .
  3. 　（メタ）アクリレート系重合体（Ｂ）を、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、５～１００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。 2. The curable composition according to claim 1, comprising 5 to 100 parts by weight of the (meth) acrylate polymer (B) with respect to 100 parts by weight of the polyoxyalkylene polymer (A). .
  4. 　シリカを、ポリオキシアルキレン系重合体（Ａ）１００重量部に対して、１０～１００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。 The curable composition according to claim 1, wherein the silica is contained in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the polyoxyalkylene polymer (A).
  5. 　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。 The curable composition according to claim 1, further comprising an aminosilane coupling agent.
  6. 　酸化防止剤、光安定剤、及び紫外線吸収剤よりなる群から選択される少なくとも一種からなり且つ融点が１０℃以下である耐候安定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。 2. The curability according to claim 1, comprising a weathering stabilizer comprising at least one selected from the group consisting of an antioxidant, a light stabilizer, and an ultraviolet absorber and having a melting point of 10 ° C. or less. Composition.
  7. 　シラノール縮合触媒を含有していないことを特徴とする請求項１に記載の硬化性組成物。 The curable composition according to claim 1, which does not contain a silanol condensation catalyst.
PCT/JP2012/075245 2011-09-30 2012-09-28 Curable composition WO2013047837A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-217425 2011-09-30
JP2011217425 2011-09-30

Publications (1)

Publication Number Publication Date
WO2013047837A1 true WO2013047837A1 (en) 2013-04-04

Family

ID=47995861

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/075245 WO2013047837A1 (en) 2011-09-30 2012-09-28 Curable composition

Country Status (1)

Country Link
WO (1) WO2013047837A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175358A1 (en) * 2013-04-24 2014-10-30 積水フーラー株式会社 Curable composition, and joint structure produced using same
JPWO2015129903A1 (en) * 2014-02-25 2017-03-30 住友化学株式会社 Granular adhesive
CN109609053A (en) * 2018-12-19 2019-04-12 广西华纳新材料科技有限公司 A kind of masonry work sealant nanometer calcium carbonate and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002155200A (en) * 2000-11-22 2002-05-28 Konishi Co Ltd Weatherproof resin composition
WO2006112340A1 (en) * 2005-04-15 2006-10-26 Kaneka Corporation Curable composition and cured article excellent in transparency
JP2006291021A (en) * 2005-04-11 2006-10-26 Kaneka Corp Method of applying curable composition and method of pasting adherend
JP2007137955A (en) * 2005-11-15 2007-06-07 Kaneka Corp Curable composition
WO2007094275A1 (en) * 2006-02-16 2007-08-23 Kaneka Corporation Curable composition
WO2008020600A1 (en) * 2006-08-16 2008-02-21 Asahi Glass Company, Limited Polymer composition
JP2010155894A (en) * 2008-12-26 2010-07-15 Asahi Glass Co Ltd Curable composition
JP2011021107A (en) * 2009-07-16 2011-02-03 Sekisui Fuller Co Ltd Curable composition, adhesive and sealing material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002155200A (en) * 2000-11-22 2002-05-28 Konishi Co Ltd Weatherproof resin composition
JP2006291021A (en) * 2005-04-11 2006-10-26 Kaneka Corp Method of applying curable composition and method of pasting adherend
WO2006112340A1 (en) * 2005-04-15 2006-10-26 Kaneka Corporation Curable composition and cured article excellent in transparency
JP2007137955A (en) * 2005-11-15 2007-06-07 Kaneka Corp Curable composition
WO2007094275A1 (en) * 2006-02-16 2007-08-23 Kaneka Corporation Curable composition
WO2008020600A1 (en) * 2006-08-16 2008-02-21 Asahi Glass Company, Limited Polymer composition
JP2010155894A (en) * 2008-12-26 2010-07-15 Asahi Glass Co Ltd Curable composition
JP2011021107A (en) * 2009-07-16 2011-02-03 Sekisui Fuller Co Ltd Curable composition, adhesive and sealing material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014175358A1 (en) * 2013-04-24 2014-10-30 積水フーラー株式会社 Curable composition, and joint structure produced using same
JP5698422B1 (en) * 2013-04-24 2015-04-08 積水フーラー株式会社 Curable composition and joint structure using the same
JPWO2015129903A1 (en) * 2014-02-25 2017-03-30 住友化学株式会社 Granular adhesive
CN109609053A (en) * 2018-12-19 2019-04-12 广西华纳新材料科技有限公司 A kind of masonry work sealant nanometer calcium carbonate and preparation method thereof
CN109609053B (en) * 2018-12-19 2020-09-08 广西华纳新材料科技有限公司 Preparation method of nano calcium carbonate for stone building sealant

Similar Documents

Publication Publication Date Title
JP5636141B1 (en) Adhesive composition
JP5698422B1 (en) Curable composition and joint structure using the same
JP7231605B2 (en) One-component curable composition for working joints
JP6541480B2 (en) Curable composition
JP6254422B2 (en) Curable composition and joint structure using the same
JP5791824B2 (en) Curable composition
JP7073167B2 (en) Curable composition
JP6214442B2 (en) Curable composition
JP6325333B2 (en) Curable composition and joint structure using the same
JP6279874B2 (en) Curable composition
WO2013047837A1 (en) Curable composition
WO2013047823A1 (en) Curable composition
JP6654179B2 (en) Curable composition and joint structure using the same
JP6998579B2 (en) Curable composition
JP6598499B2 (en) Adhesive composition
JP7038985B2 (en) Curable composition and joint structure using it
JP7377512B2 (en) Curable composition and method for producing the same
JP6544988B2 (en) Curable composition
JP7335578B2 (en) Curable composition
JP2022083438A (en) Curable composition
JP2022192038A (en) Curable composition
JP2023007423A (en) Curable composition for spray coating
JP2021183657A (en) Curable composition
JP2023117676A (en) Sealing material composition
JP2021102765A (en) Moisture-curable composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12837001

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112 (1) EPC, EPO FORM 1205A DATED 06.06.14.

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 12837001

Country of ref document: EP

Kind code of ref document: A1