JP2005290269A - Curable composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-curable composition which has elasticity, a stain-preventing property, yellowing resistance and transparency, to provide a sealing material, and to provide an adhesive. <P>SOLUTION: This curable composition comprises 100 pts. wt. of a vinylic polymer having cross-linkable silyl groups represented by formula (1): -[Si(R<SP>1</SP>)<SB>2-b</SB>(Y)<SB>b</SB>O]<SB>m</SB>-Si(R<SP>2</SP>)<SB>3-a</SB>(Y)<SB>a</SB>[R<SP>1</SP>and R<SP>2</SP>are each a 1 to 20C alkyl, a 6 to 20C aryl, a 7 to 20C aralkyl, or a triorganosiloxy group represented by formula : (R')<SB>3</SB>Si- (R' is a 1 to 20C monovalent hydrocarbon group, provided that three R' groups may be identical or different); Y is OH or a hydrolyzable group, provided that, when two or more Y groups exit, the Y groups are identical or different; (a) is 0 to 3; (b) is 0 to 2; (m) is an integer of 0 to 19, where (a)+(m)(b)≥1], at the terminals, and 5 to 40 pts.wt. of an air-curable and/or photo-curable compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition, a sealing material, and an adhesive, and more specifically, curability that gives a cured product that has little yellowing with time and is cured by moisture in the atmosphere, and has excellent durability and elasticity. The present invention relates to a composition, and a sealing material and an adhesive comprising the composition.

  Vinyl polymers having an alkoxysilyl group are disclosed, for example, in Patent Documents 1 to 3 below. The vinyl polymer having an alkoxysilyl group is crosslinked by moisture in the atmosphere, and gives a cured product excellent in durability, weather resistance, transparency and adhesiveness. Therefore, alkoxysilyl group-containing vinyl polymers are used in a wide range of applications such as paints, coating agents, adhesives, pressure sensitive adhesives, sealants, and sealants.

  When the adhesive or sealing material containing the vinyl polymer is used in an exposed portion, the cured product may be deteriorated by ultraviolet rays or rainwater caused by sunlight, and the weather resistance may be lowered. Conventionally, in order to improve weather resistance, an ultraviolet absorber and an antioxidant have been added to the sealing material and the adhesive. However, depending on the type of vinyl polymer, the ultraviolet absorber and the antioxidant may bleed out from the cured product over time, and the weather resistance may decrease.

  On the other hand, Patent Document 4 below discloses a configuration in which an ultraviolet absorber is copolymerized with the main chain of a hydrolyzable silyl group-containing vinyl polymer in order to improve weather resistance. However, the hydrolyzable silyl group-containing vinyl polymer in which an ultraviolet absorber is copolymerized in the main chain described in Patent Document 4 has a problem that the cured product turns yellow over time.

JP 57-179210 A JP-A-4-202585 JP 11-43512 A JP 7-26155 A

  An object of the present invention is to provide a curable composition that eliminates the above-mentioned drawbacks of the prior art, cures little by time and is cured by moisture in the atmosphere, and a sealing material and an adhesive comprising the curable composition. There is to do.

The curable composition according to the present invention includes a vinyl polymer (a) having a crosslinkable hydrolyzable silyl group represented by the general formula (1), a reducing functional group, an ultraviolet absorbing functional group, and light. It is a curable composition containing the (meth) acrylic acid ester-type polymer (b) which has at least 1 of a stable functional group.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

In the curable composition according to the present invention, the vinyl polymer (a) having a crosslinkable hydrolyzable silyl group represented by the general formula (1) at the terminal has a reducing functional group, an ultraviolet absorbing functional group, and light. A curable composition having at least one stable functional group.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

  In a specific aspect of the curable composition according to the present invention, the light-stable functional group is a hindered amine functional group.

In the curable composition concerning this invention, Preferably, the hardening accelerator which consists of organometallic compounds is further contained.
The curable composition according to the present invention preferably further contains a layered silicate.

In still another specific aspect of the curable composition according to the present invention, a polyether polymer (c) having a hydrolyzable silyl group is further included.
The sealing material and the adhesive according to the present invention are characterized by comprising a curable composition constituted according to the present invention.

Details of the present invention will be described below.
The curable composition of the present invention contains a vinyl polymer (a) having the general formula (1) at its terminal.
_{^{- [Si (R 3) 2}} -b (Y) b O] m -Si (R 4) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)

  The hydrolyzable group represented by Y is not particularly limited, and examples thereof include an alkoxy group such as hydrogen, a halogen atom, a methoxy group, and an ethoxy group, an acyl oxide group, a ketoximate group, an amino group, an amide group, and an acid amide group. An aminooxy group, a mercapto group, an alkenyl oxide group and the like are preferable examples, and an alkoxy group that is easy to handle and does not generate harmful by-products during the reaction is particularly preferable. The hydroxyl group and hydrolyzable group can be bonded to one silicon atom in the range of 1 to 3, and the total number of hydroxyl groups and hydrolyzable groups in the formula (1), that is, a + mb is 1 to 1 A range of 5 is preferred. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.

  The vinyl polymer portion constituting the vinyl polymer may be a polymer obtained by polymerizing a vinyl monomer. For example, polyethylene, polypropylene, polyisobutylene, poly (meth) acrylate, polystyrene, poly Examples thereof include vinyl chloride, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyvinyl ether. Moreover, the copolymer which has these vinyl polymer parts may be sufficient. A poly (meth) acrylate having a number average molecular weight of 10,000 or more and a copolymer thereof having a good balance between cohesive strength and adhesiveness are preferable. Here, (meth) acryl is an expression collectively showing methacryl and acryl.

Examples of the monomer for obtaining poly (meth) acrylate and its copolymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, 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) acrylate, tetrahydro Rufuryl (meth) acrylate, hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene 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 acrylate, Polyester acrylate, urethane acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropy (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, 2-[(meth) acryloyloxy] ethyl 2-hydroxyethylphthalic acid, 2- [ (Meth) acryloyloxy] ethyl 2-hydroxypropylphthalic acid,
[Compound 1]
_{CH 2 = CH-C (O} ) O-CH 2 CH 2 O-
_{[C (O) CH 2 CH} 2 CH 2 CH 2 CH 2 O] n-H
(N = 1-10)
[Compound 2]
_{CH 2 = C (CH 3)} -C (O) O-CH 2 CH 2 O-
_{[C (O) CH 2 CH} 2 CH 2 CH 2 CH 2 O] n-H
(N = 1-10)
[Compound 3]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-H
(N = 1-12)
[Compound 4]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n-H
(N = 1-12)
[Compound 5]
_{CH 2 = CH-C (O} ) O- [CH 2 CH (CH 3) O] n-H
(N = 1-12)
[Compound 6]
_{CH 2 = C (CH 3)} -C (O) O- [CH 2 CH (CH 3) O] n-H
(N = 1-12)
[Compound 7]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n-
_{[CH 2 CH (CH 3)} O] m-H
(M, n = 1-12)
[Compound 8]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-
_{[CH 2 CH (CH 3)} O] m-H
(M, n = 1-12)
[Compound 9]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n-
(CH ₂ CH ₂ CH ₂ CH ₂ O) mH
(M, n = 1-12)
[Compound 10]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-
(CH ₂ CH ₂ CH ₂ CH ₂ O) mH
(M, n = 1-12)
[Compound 11]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-CH 3
(N = 1-10)
[Compound 12]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n-CH 3
(N = 1-30)
[Compound 13]
_{CH 2 = CH-C (O} ) O- [CH 2 CH (CH 3) O] n-CH 3
(N = 1-10)
[Compound 14]
_{CH 2 = C (CH 3)} -C (O) O- [CH 2 CH (CH 3) O] n-CH 3
(N = 1-10)
[Compound 15]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n-
_{[CH 2 CH (CH 3)} O] m-H
(M, n = 1-10)
[Compound 16]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-
_{[CH 2 CH (CH 3)} O] m-H
(M, n = 1-10)
[Compound 17]
_{CH 2 = CH-C (O} ) O- [CH 2 CH (CH 3) O] n
—C (O) —CH═CH ₂
(N = 1-20)
[Compound 18]
_{CH 2 = C (CH 3)} -C (O) O- [CH 2 CH (CH 3) O] n
_{-C (O) -C (CH 3} ) = CH 2
(N = 1-20)
[Compound 19]
_{CH 2 = CH-C (O} ) O- (CH 2 CH 2 O) n-C (O) -CH = CH 2
(N = 1-20)
[Compound 20]
_{CH 2 = C (CH 3)} -C (O) O- (CH 2 CH 2 O) n
_{-C (O) -C (CH 3} ) = CH 2
(N = 1 to 20).

  Examples of other vinyl monomers include styrene derivatives such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, and divinylbenzene; For example, compounds having a vinyl ester group such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (meta ) Acrylonitrile, (meth) acrylamide, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide, n-propylvinylether, n-butylvinylether, isobutylvinylether, ter -Butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene glycol butyl vinyl ether, tritylene 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, glu Di (4-vinyloxy) butyl tartrate, di (4-vinyloxy) butyl trimethylolpropane trivinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-di succinate Mention may be made of compounds having a vinyloxy group such as methanol-monovinyl ether, diethylene glycol monovinyl ether 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) ethyl vinyl ether, urethane vinyl ether, polyester vinyl ether and the like.

The method for producing a vinyl polymer having a crosslinkable hydrolyzable silyl group of formula (1) at the end is not particularly limited. For example, an organic halide or a sulfonyl halide compound is used as an initiator, a transition metal complex. Is used as a catalyst to produce a vinyl polymer having a terminal structure represented by formula (2), and the halogen of formula (2) is a crosslinkable hydrolyzable represented by formula (1). The method of converting into a silyl group containing substituent is mentioned.
-C (R ³ ) (R ⁴ ) (X) (2)
(In the formula, R ^3, R ⁴ represents a group bonded to an ethylenically unsaturated group of a vinyl monomer. In addition, X represents chlorine, bromine, or halogen atom iodine,.)
It is.

  The method for converting the halogen of the formula (2) into the crosslinkable hydrolyzable silyl group-containing substituent represented by the formula (1) is not particularly limited. For example, the hydrolyzable silyl group crosslinkable with an alkenyl group. A compound having a silyl group and a compound having a stabilized carbanion, a compound having a polymerizable alkenyl group and another alkenyl group, an organometallic compound having an alkenyl group, and a carboxylic acid metal salt having an alkenyl group , A method in which a compound having an alkenyl group and a stabilized carbanion is reacted to substitute the halogen of formula (2) with an alkenyl group, and then a hydrosilane having a hydrolyzable silyl group capable of crosslinking is reacted with the alkenyl group Is mentioned.

Further, when producing a vinyl polymer having a crosslinkable hydrolyzable silyl group at the terminal of the formula (1), an organic halide having a crosslinkable hydrolyzable silyl group is used as an initiator, After synthesizing a polymer with a hydrolyzable silyl group that has a halogen at one end and a crosslinkable hydrolyzable silyl group at the other end, it can react with halogen, glycol, diamine, dicarboxylic acid, etc. A polymer having a silyl group may be prepared, or after synthesizing a polymer having a hydrolyzable silyl group having a halogen at one end and a crosslinkable at the other end,
Halogen may be converted to a hydrolyzable silyl group capable of crosslinking by the above reaction. Alternatively, after synthesizing a polymer having a hydrolyzable silyl group having a halogen at one end and a crosslinkable at the other end, the halogen can be converted into an alkenyl group by the above-described reaction, and then further hydrolyzable by hydrolysis. May be converted to a functional silyl group.

In producing a vinyl polymer having a terminal crosslinkable hydrolyzable silyl group of formula (1),
After synthesizing a polymer having a halogen at one end and an alkenyl group at the other end using an organic halide having an alkenyl group as an initiator, the halogen is converted to an alkenyl group, And the like, and the like.

  The (meth) acrylic acid ester polymer (b) according to the present invention is a (meth) acrylic acid ester polymer having at least one of a reducing functional group, an ultraviolet absorbing functional group, and a photostable functional group. In obtaining such a (meth) acrylic acid ester polymer (b), the above-mentioned (meth) acrylic acid ester monomer, a reducing functional group, an ultraviolet absorbing functional group, a light-stable functional group are used. What is necessary is just to radical-polymerize the following copolymerizable monomer which has at least 1 of group and can be copolymerized with a (meth) acrylic acid ester-type monomer.

  The copolymerizable monomer having at least one of the reducing, ultraviolet absorbing functional group and light-stable functional group is, for example, (meth) acrylic acid or poly (meth) acrylic acid ester and (meth) acryloyloxy Esterification, amidation, urethane of a compound obtained by reacting ethyl isocyanate with a compound having a hydroxyl group or amino group having active hydrogen and a reducing functional group, a UV-absorbing functional group and / or a photostable functional group Or by urea reaction. Moreover, as a commercially available compound, the product number: RUVA-93 [(2- (2'-hydroxy-5'-methacryloyloxyethylphenyl) -2H-benzotriazole made from Otsuka Chemical Co., Ltd. which has an ultraviolet absorptive functional group, for example. )] And the like.

  As another method for obtaining the (meth) acrylic acid ester polymer (b), (meth) acrylic acid or poly (meth) acrylic acid ester is copolymerized with (meth) acryloyloxyethyl isocyanate. A method of esterifying, amidating, urethanizing or ureating a hydroxyl group or amino group having active hydrogen and a compound having at least one of a reducing functional group, an ultraviolet absorbing functional group and a photostable group. Can be mentioned.

Examples of the compound used for the esterification, amidation, urethanization or urealation reaction include the following compounds.
For example, as a compound having a reducing functional group, triethylene glycol bis (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol bis (3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate), pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), 2,2-thio-ethylene Bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), N, N′-hexamethylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), And tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate.

  Examples of the compound having an ultraviolet absorbing functional group include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl) -2H. -Benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-(( Xyl) oxy) phenol, 2-ethoxy-2′-ethyl-oxalic acid bisanilide, 2-hydroxy-4-n-octyloxyoxybenzophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- And phenyl-propan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, and the like.

  Examples of the compound having a photostable functional group include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 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), N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis (N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino) -6-chloro-1.3.5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (2 , 5-Di-tert-butyl-4-hydride Roxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t-butylphenyl-3,5-di-t-butyl Examples include -4-hydroxybenzoate.

  Preferably, a hindered amine functional group is used as the light-stable functional group, whereby yellowing of the cured product due to ultraviolet rays or the like can be more reliably suppressed.

  The vinyl polymer (a) having at least one of the reducing functional group, ultraviolet absorbing functional group, and photostable functional group is a vinyl having a terminal structure represented by the formula (2) by polymerizing a vinyl monomer. Copolymerizes a monomer that has at least one of a reducing functional group, an ultraviolet-absorbing functional group, and a light-stable functional group and can be copolymerized with a (meth) acrylic acid ester monomer. After the copolymerization of (meth) acryloyloxyethyl isocyanic acid, a hydroxyl group or amino group having active hydrogen and at least one of a reducing functional group, an ultraviolet absorbing functional group and a photostable group Examples of the method include esterification, amidation, urethanization, or urea reaction with a compound having the same.

  In the curable composition according to the present invention, the vinyl polymer (a) and the (meth) acrylic acid ester polymer (b) are included, preferably, 100 parts by weight of vinyl (a). The (meth) acrylic acid ester polymer (b) is blended at a ratio of 10 to 1000 parts by weight. When the blending ratio of the (meth) acrylic acid ester polymer (a) is less than 10 parts by weight, the effect of improving the weather resistance may not be sufficient, and when it exceeds 1000 parts by weight, the reducing functional group and the ultraviolet absorbing functional group. And because of the cohesive strength of the photostable functional group, it may no longer exhibit elasticity.

(viscosity)
In order to use the curable composition of the present invention as a liquid or paste composition, the viscosity at 25 ° C. of either the vinyl polymer (a) or the (meth) acrylic acid ester polymer (b). Is preferably 10 to 500,000 cps. When both are less than 10 cps, a liquid composition having excellent handleability is obtained, but it may be difficult to impart thixotropy by adjusting the viscosity. When both viscosities exceed 500,000 cps, cold flow properties may be exhibited, but application may be difficult and the composition may be difficult to handle. Therefore, when the curable composition of the present invention is used as a liquid or paste, the above viscosity range is preferable. From the viewpoint of ease of handling, more preferably, any viscosity is 100 to 50000 cps, more preferably 1000 to 30000 cps. Moreover, the viscosity range with favorable coating property in the curable composition of this invention is 50-500000 cps, Preferably, it is 100-100000 cps.

  In order to use the curable composition of the present invention as a liquid or pasty composition excellent in elongation of the cured product and difficult to string, a vinyl polymer (a) or a (meth) acrylic acid ester polymer The number average molecular weight (polystyrene equivalent molecular weight determined from GPC) in any of (b) is desirably 5,000 to 100,000. When the number average molecular weight of both is less than 5000, the liquid composition is easy to handle, but the cured product may not be sufficiently stretched. When both molecular weights exceed 100,000, it is possible to easily obtain a composition excellent in elongation properties of the cured product, but there are cases where it becomes a liquid composition in which stringing easily occurs.

  Therefore, in order to increase the elongation of the cured product and to obtain a liquid or paste-like composition that is difficult to string, the above number average molecular weight range is preferable. In order to obtain a liquid that is excellent in elongation of the cured product and is difficult to be stringed, more preferably, any number average molecular weight is 1000 to 30000, and more preferably 5000 to 30000.

(Curing accelerator)
In the curable composition which concerns on this invention, in order to raise a cure rate, you may add the hardening accelerator which consists of an organometallic compound.

  Examples of the organic metal compound that can be preferably used include an organic metal compound obtained by substituting a metal element such as germanium, tin, lead, boron, aluminum, gallium, indium, titanium, and zirconium with an organic group. For example, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), tin octylate, dibutyl Tin compounds such as tin octoate and dioctyl tin oxide, and titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate can be used, and these can be used alone or in combination of two or more.

  The blending ratio of the curing accelerator is preferably 100 parts by weight in total of the vinyl polymer (a) and the (meth) acrylic acid ester polymer (b), and the vinyl polymer (a) is a reducing functional group. In the case of having at least one of an ultraviolet grade functional group and a photostable functional group, the amount is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the vinyl polymer. If it is less than 0.01 parts by weight, the effect of promoting curing is not sufficient, and if it exceeds 10 parts by weight, curing may become too fast, and it may be difficult to obtain a uniform cured film.

(Layered silicate)
In the curable composition concerning this invention, in order to improve a weather resistance, a layered silicate may be mix | blended.

  The layered silicate preferably used in the present invention means a silicate mineral having exchangeable cations between layers. The layered silicate used in the present invention is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite, vermiculite, halloysite, and swelling mica. It is done. Among these, montmorillonite and swellable mica are preferable. The layered silicate may be a natural product or a synthetic product, and one or more of these may be used.

  As the layered silicate, it is more preferable to use smectites or swelling mica having a large shape anisotropy effect defined by the following formula from the viewpoint of improving the mechanical strength and gas barrier property of the curable composition. In addition, the crystal | crystallization surface (A) and crystal | crystallization end surface (B) of layered silicate are typically shown in FIG.

  Shape anisotropy effect = area of crystal surface (A) / area of crystal end face (B)

  As shown in FIG. 2, the exchangeable cations existing between the layers of the layered silicate are ions such as sodium and calcium on the crystal surface, and these ions have ion exchange properties with a cationic substance. Therefore, various substances having a cationic property can be trapped (intercalated) between the layers of the layered silicate.

  Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, It is preferable that it is 50-200 milliequivalent / 100g. If it is less than 50 milliequivalents / 100 g, the amount of the cationic surfactant that can be trapped (intercalated) between the crystal layers by ion exchange decreases, so the layers may not be sufficiently nonpolarized. On the other hand, when it exceeds 200 milliequivalents / 100 g, the bonding force between the layers of the layered silicate becomes strong, and it may be difficult to increase the distance between the crystal flakes constituting each layer of the layered silicate.

  The layered silicate is blended in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of the base resin. When the amount is less than 0.1 part by weight, the effect of improving the weather resistance of the cured product and flame retardancy is hardly exhibited, and when the amount exceeds 10 parts by weight, the viscosity of the curable composition is increased and workability and productivity are reduced. There is.

The base resin is
The total of the vinyl polymer (a) and the (meth) acrylic acid ester polymer (b), or the vinyl polymer (a) is at least a reducing functional group, an ultraviolet-grade functional group and a photostable functional group. When it has one, it is the sum total of the vinyl polymer and the later-described polyether polymer (c) added if necessary.

  The layered silicate preferably has an average interlayer distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more and dispersed including those existing in 5 layers or less. When the average interlayer distance is 3 nm or more and the dispersion is 5 layers or less, it is advantageous for the weather resistance and flame retardancy performance of the curable composition.

  In the present specification, the average interlayer distance of the layered silicate is an average interlayer distance when the fine flaky crystal is used as a layer, and is obtained by X-ray diffraction peak and transmission electron microscope photography, that is, wide-angle X It can be calculated by a line diffraction measurement method. The state where the layers are cleaved to 3 nm or more and dispersed including those existing in 5 layers or less means that a part or all of the layered silicate laminate is dispersed, This is because the interaction between layers is weakened.

  Furthermore, when the average interlayer distance of the layered silicate is 6 nm or more, it is particularly advantageous for expressing functions such as flame retardancy, mechanical properties, and heat resistance. If the average interlaminar distance is 6 nm or more, the lamellar silicate crystal flake layers separate into layers, and the interaction of the lamellar silicate weakens so that it can be almost ignored. The dispersion state in progresses in the direction of delamination stabilization. That is, the layered silicate is present in a stabilized state in the curable composition in a state where the layered silicates are separated in a flake form one by one.

  As a dispersion state of the layered silicate, it is preferable that the flaky crystals of the layered silicate are highly dispersed in the base resin. More specifically, it is preferable that 10% by weight or more of the layered silicate is dispersed in a state where it is present in 5 layers or less, more preferably, 20% by weight or more of the layered silicate is 5 layers or less. It is desirable to exist in a state. Furthermore, if the number of laminated flaky crystals is 5 or less, the effect of the addition of the layered silicate can be obtained satisfactorily, but if it is 3 or less, it is more preferable, and it is dispersed in a single layer. More desirable.

  The layered silicate of the present invention is preferably a layered silicate treated with a quaternary ammonium salt. This is because the dispersibility of the layered silicate in the base resin can be improved by treating with a quaternary ammonium salt. Further, quaternary ammonium salts are known to have a catalytic action for the crosslinking reaction of the (meth) acrylic acid ester polymer (b), and are dispersed by dispersing them in the base resin together with the layered silicate. It is also possible to accelerate the curing speed with improvement of the above.

  Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, and N-polyoxyethylene. -N-lauryl-N, N-dimethylammonium salt and the like can be mentioned, and these quaternary ammonium salts may be used alone or in combination of two or more. Among them, a quaternary alkyl ammonium ion salt having an alkyl chain having 6 or more carbon atoms or a polyoxyalkylene chain is preferable because good dispersibility can be obtained.

  Various stirrers can be used to disperse the layered silicate, but if it is difficult to disperse, it may be easy to obtain a desired dispersion state by dispersing using a high shearing device such as a three roll.

  In the curable composition according to the present invention, a polyether polymer (c) having a main chain essentially composed of a polyether polymer and having a crosslinkable hydrolyzable silyl group may be blended. Examples of the polyether polymer (c) include those in which the main chain consists essentially of a polyether polymer, and polymers in which the main chain consists of polyether and (meth) acrylic acid ester. By blending this polyether polymer, the water resistance of the cured product can be increased, and the rubber elasticity when a sealing material is formed can be increased. When the vinyl polymer (a), the (meth) acrylic acid ester polymer (b), and the polyether polymer (c) are used in combination, the blending ratio of the vinyl polymer (a), It is preferable to add the polyether polymer (c) at a ratio of 0.1 to 100 parts by weight with respect to a total of 100 parts by weight of the (meth) acrylic acid ester polymer (b), more preferably 0.8. 5 to 100 parts by weight.

  When the blending ratio of the polyether polymer (c) is less than 0.1 parts by weight, the effect of improving the adhesiveness may be reduced, and when it exceeds 200 parts by weight, the weather resistance may be lowered and the adhesiveness may be decreased. The improvement effect may not be so high.

  The polyether polymer (c) essentially represents a general formula [— (R—O) n—, wherein R represents an alkylene group having 1 to 4 carbon atoms. ] A polymer containing a hydrolyzable silyl group which can be cross-linked at the terminal.

  The polymer is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at a terminal with a hydrosilane compound represented by the following chemical formula (3) in the presence of a group VIII transition metal.

Wherein R ⁵ is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2, X is a halogen atom, an alkoxy group, an acyloxy group, and Means an atom or group selected from a ketoximate group.)
Examples of the polyalkylene oxide that is the main chain of the polymer include polyethylene oxide, polypropylene oxide, polybutylene oxide, etc., but the cured product of the room temperature curable composition is excellent in water resistance and as a sealing material. Polypropylene oxide is preferable because it can ensure elasticity.

  As the crosslinkable hydrolyzable silyl group, those which do not generate harmful by-products after the reaction are preferable, and examples thereof include alkoxysilyl groups such as methoxysilyl group and ethoxysilyl group.

  If the number average molecular weight of the polyether polymer (c) is small, the cured product will not be sufficiently stretched, the followability to the ground will be reduced, and if it is large, the viscosity before curing will be high, and the workability of the blending process will be increased. Deteriorate. Therefore, the number average molecular weight is preferably 4,000 to 30,000, more preferably 10,000 to 30,000, and the molecular weight distribution is preferably 1.6 or less.

  Examples of the polyether polymer (c) include the trade name “MS polymer” (manufactured by Kaneka Chemical Co., Ltd.), MS polymer S-203, S-303, etc. As Sakai Chemical Industry Co., Ltd.), Silyl SAT-200, SAT-350, SAT-400, and trade name "Exester" (manufactured by Asahi Glass Co., Ltd.), Exester ESS-3620, ESS-3430, ESS-2420, ESS -2410 and the like are commercially available.

(Ultraviolet absorber and light stabilizer)
In order to further improve the weather resistance, it is preferable to add various ultraviolet absorbers and light stabilizers to the curable composition of the present invention. Furthermore, when the structure of the ultraviolet absorber or light stabilizer added is similar to the ultraviolet absorbing functional group or light stable functional group in the curable composition of the present invention, these interact. As a result, the bleed-out speed of the ultraviolet absorber or light stabilizer added later is suppressed. In addition, since the layered silicate acts so as to suppress the bleeding out of various ultraviolet absorbers and light stabilizers in combination with the layered silicate, these are retained in the cured product for a long period of time.

  Examples of the UV absorber include known UV absorbers such as benzotriazole, benzophenone, and benzoate. Among them, benzotriazole UV absorbers are preferable because of their high UV absorption performance. When the ultraviolet absorber is blended, it is preferably blended in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the base resin. When the amount is less than 0.1 parts by weight, the effect of improving weather resistance may be insufficient. When the amount exceeds 20 parts by weight, problems such as deterioration of the appearance as a sealing material due to coloration occur.

  As the light stabilizer, for example, a hindered amine light stabilizer is used. A hindered amine light stabilizer generally exhibits an excellent effect when used in combination with an ultraviolet absorber. Among the hindered amine light stabilizers (hereinafter referred to as light stabilizers), those having a group having a structure represented by the following general formula (A) in the molecule are particularly effective when used in combination with a layered silicate. Examples of such a hindered amine light stabilizer include, for example, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [{6- (1,1,3,3, -tetramethylbutyl). ) Amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidine) imino} hexamethylene {(2,2,6,6-tetramethyl) -4-piperidine) imino}] and the like. These may be used alone or in combination of two or more.

  The weather resistance effect by the combined use with the (meth) acrylic acid ester polymer (b) of the present invention and the layered silicate is considered to be mainly due to the bleedout prevention effect of the light stabilizer. That is, it is considered that the (meth) acrylic acid ester polymer (b) and the layered silicate interact with the light stabilizer in the composition to prevent the light stabilizer from escaping from the system. . In addition, it is considered that the bleedout of the light stabilizer is suppressed when the layered silicate acts like a plate that inhibits bleedout among the interactions. Among the light stabilizers, those having a group having the structure represented by the following general formula (A) in the molecule are considered to be particularly effective because the H atom bonded to the N atom is involved. .

  When the light stabilizer is blended, it is preferably blended in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the base resin. If the amount is less than 0.1 part by weight, the effect of improving the weather resistance may be insufficient. If the amount exceeds 20 parts by weight, coloring problems may occur and the appearance as a sealing material may be impaired.

(Other ingredients)
In the curable composition according to the present invention, a curing catalyst, a curing co-catalyst, a viscosity modifier, a thixotropic agent, a physical property modifier, an extender, a reinforcing agent, a plasticizer, as long as the object and effect of the present invention are not impaired. Colorants, flame retardants, sagging inhibitors, antioxidants, anti-aging agents, solvents, fragrances, pigments, dyes, dehydrating agents, and the like may be added.

  Examples of the curing catalyst include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, bis (dibutyltin laurate) oxide, dibutyltin bisacetylacetonate, dibutyltin bis (monoester maleate), Tin compounds such as tin octylate, dibutyltin octoate and dioctyltin oxide; titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate; amine salts such as dibutylamine-2-ethylhexoate; and others And acidic catalysts and basic catalysts. Further, in order to adjust the curing rate, divalent organic carboxylate tin having a relatively fast curing rate may be used, and these include tin stearate, stannous octoate, and dioctyl tin compounds. .

  The viscosity modifier is, for example, selected from a polymer compound having a good compatibility with a polymer composed of a repeating unit having a substantially (meth) acrylic acid ester having an alkoxysilyl group as a monomer, and appropriately selected from compounds to be blended Is done. For example, acrylic polymers, methacrylic polymers, polyvinyl alcohol derivatives, polyvinyl acetate, polystyrene derivatives, polyesters, polyethers, polyisobutene, polyolefins, polyalkylene oxides, polyurethanes, polyamides, natural rubber, polybutadiene , Polyisoprene, NBR, SBS, SIS, SEBS, hydrogenated NBR, hydrogenated SBS, hydrogenated SIS, hydrogenated SEBS, and the like. Moreover, these copolymers and functional group modified products can be mentioned, and these may be combined as appropriate.

  The thixotropic agent is appropriately selected from substances whose composition exhibits thixotropic properties. Examples thereof include colloidal silica, polyvinyl pyrrolidone, hydrophobized calcium carbonate, glass balloons, and glass beads. Regarding the selection of the thixotropic agent, it is desirable to have a surface having high affinity with a polymer composed of a repeating unit having a substantially (meth) acrylic acid ester having an alkoxysilyl group as a monomer.

  Examples of physical property modifiers that improve tensile properties include various silane coupling agents such as vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and phenyltrimethoxysilane. Methoxysilane, diphenyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N′-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl ] Echile And diamine, N, N′-bis- [3- (trimethoxysilyl) propyl] hexaethylenediamine, N, N′-bis- [3- (triethoxysilyl) propyl] hexaethylenediamine, and the like. Two or more types may be used in combination.

  As the extender, those which are added to the composition according to the present invention and do not express thixotropic properties can be suitably used. For example, talc, clay, calcium carbonate, magnesium carbonate, anhydrous silicon, hydrous silicon, calcium silicate, Examples thereof include titanium dioxide and carbon black, and these may be used alone or in combination of two or more.

  Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate, phthalate esters such as dioctyl phthalate, fatty acid-basic acid esters such as glycerol monooleate, and dioctyl adipate. Examples thereof include fatty acid dibasic acid esters and polypropylene glycols, and these may be used alone or in combination of two or more.

  The curable composition according to the present invention is cured by reacting with moisture in the atmosphere to give a cured product having rubber elasticity. As is clear from the examples described later, the (meth) acrylic acid ester polymer comprising the above-mentioned specific repeating unit and obtained by a free radical polymerization method using a peroxide as a polymerization initiator is mainly used. Since it is a component, it is excellent in the weather resistance of the cured product and hardly causes yellowing. Therefore, by using the curable composition according to the present invention, it is possible to provide a sealing material and an adhesive that are excellent in weather resistance and whose color state hardly changes with time.

The curable composition according to the present invention comprises at least one of a vinyl polymer (a) having a crosslinkable hydrolyzable silyl group at its terminal, a reducing functional group, an ultraviolet absorbing functional group, and a photostable functional group. (Meth) acrylic acid ester-based polymer (b) having a curable composition is quickly cured by moisture in the atmosphere, and is only excellent in elasticity, durability, and adhesiveness. In addition, the weather resistance of the cured product can be effectively increased.
In particular, the crosslinkable silyl group-containing vinyl polymer (a) of the present invention has a crosslinkable silyl group at the terminal as described above, so that it has a crosslinkable silyl group in the side chain. The cured product exhibits excellent elongation and elasticity despite its low viscosity before curing and easy handling with little stringing.

In the curable composition according to the present invention, the vinyl polymer (a) having a crosslinkable hydrolyzable silyl group at the end includes at least a reducing functional group, an ultraviolet absorbing functional group, and a photostable functional group. Because it has one, the curable composition is quickly cured by moisture in the atmosphere, and not only is excellent in elasticity, durability and adhesiveness, but also effectively increases the weather resistance of the cured product be able to.
As described above, since weather resistance stability over a long period of time can be effectively obtained, it becomes possible to provide a sealing material, adhesive or coating agent excellent in weather resistance according to the present invention.

  Hereinafter, the present invention will be described in more detail by describing specific examples of the present invention. The present invention is not limited to the following examples.

(Preparation of vinyl polymer (a))
A 1 L three-necked round bottom flask equipped with a reflux tube was charged with cuprous bromide (6.25 g, 156 mmol), acetonitrile (50 mL), and pentamethyldiethylenetriamine (9.1 mL) and replaced with nitrogen gas. Acrylic acid-n-butyl (500 mL, 447 g, 3.9 mol) and diethyl-2,5-dibromoadipate (15.7 g, 43.6 mmol) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. Volatiles were distilled off under reduced pressure to obtain 350 g of poly (acrylic acid-n-butyl) having a halogen at the terminal (polymerization yield: 87%). The number average molecular weight of the polymer was 10700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.15.

Next, in a 2 L three-necked round bottom flask equipped with a reflux tube, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (350 g), synthesized in Production Example 2 4 -A potassium salt of pentenoic acid (22.3 g, 161 mmol) and dimethylacetamide (350 mL) were charged and reacted at 70 ° C for 4 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer was dried over Na ₂ SO ₄ and the polymer was isolated by removing the volatiles under reduced pressure. An equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer and stirred at 100 ° C. for 4 hours to obtain poly (butyl acrylate) having an alkenyl group at the terminal. According to ¹ H-NMR analysis, 1.82 alkenyl groups were introduced per oligomer-1 molecule.

Next, the polymer (150 g), dimethoxymethylhydrosilane (18 mL, 145 mmol), dimethyl orthoformate (2.6 mL, 24.2 mmol), and a platinum catalyst were charged into a 200 mL pressure-resistant glass reaction vessel. However, the amount of platinum catalyst used was 2 × 10 ⁻⁴ equivalent in terms of molar ratio to the alkenyl group of the polymer. The reaction mixture was heated at 100 ° C. for 4 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a silyl group at the terminal. According to ¹ H-NMR analysis, 1.46 silyl groups were introduced per oligomer-1 molecule.

(Preparation of (meth) acrylic acid ester polymer (b1))
4. In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 95 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) and methacryloyloxyethyl isocyanate (made by Showa Denko) 0 g, 5.0 g of lauryl mercaptan (Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate were added and mixed. After the dissolved oxygen was removed by bubbling the monomer mixed solution with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas, and the temperature was increased to reach reflux while stirring.

  After refluxing, a solution obtained by diluting 0.024 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane as a polymerization initiator with 1 g of ethyl acetate was added to the polymerization system. After 1 hour, a solution prepared by diluting 0.036 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate was added. Further, 2, 3, and 4 hours after the start of polymerization, a solution prepared by diluting 0.048 g, 0.12 g, and 0.36 g of di (3,5,5-trimethylhexanoyl) peroxide with 1 g of ethyl acetate was added. did. Seven hours after the first polymerization initiator was charged, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (Ciba Specialty Chemicals, IRGANOX 1010) 2 g, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole (Ciba Specialty Chemicals, TINUVIN 327) 2 g, bis (2,2,6,6-tetramethyl-4-piperidyl ) 2 g of sebacate (Ciba Specialty Chemicals, TINUVIN 770) was added, and after further reaction for 3 hours, the reaction was terminated by cooling to room temperature. (Meth) acrylic acid ester-based weight containing a reducing functional group having a number average molecular weight of about 3000 (gel permeation chromatography, molecular weight in terms of polystyrene), an ultraviolet-absorbing functional group, and a photostable functional group Combined (a) was obtained.

(Example 1, Comparative Example 1)
After mixing the vinyl polymer (a) obtained above and the (meth) acrylic ester polymer (b1) so that the ratio of the polymers is as shown in Table 1, the rotary evaporator is used. The solvent was removed using it to obtain a resin composition. To 100 parts by weight of the obtained resin composition, 80 parts by weight of heavy calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten P-30) and fatty acid-treated calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Viscolite U) 20 parts by weight, 10 parts by weight of titanium oxide (manufactured by Wako Pure Chemical Industries, Ltd.), and 2 parts by weight of a curing accelerator (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dilaurate) are added and uniformed with a sealed stirrer. And then defoaming under reduced pressure for 10 minutes to obtain a white paste-like curable composition. The curable composition thus obtained was subjected to a weather resistance test and a tensile test in the following manner. The results are shown in Table 1.

(Weatherability)
The curable composition was applied to a 50 mm × 1 mm thick stainless steel plate with a thickness of 0.5 mm, cured for 7 days in an atmosphere of 20 ° C. and 50% relative humidity, and then subjected to a weather resistance acceleration test under the following conditions. The state was confirmed visually. The time when the crack was observed was defined as the weather resistance time.

Weathering accelerated test conditions:
Test device, Iwasaki Electric Co., Ltd. eye super UV tester (SUV-F11 type)
Irradiation intensity, 100 mW / cm ²
Limited wavelength, 295 nm, 450 nm
Irradiation distance 235mm (between light source and sample)
Black panel temperature, 63 ° C

(Tensile test)
The curable composition was coated on a polyethylene plate so as to have a coating thickness of 2 mm, and after curing for 7 days in an atmosphere of 20 ° C. and a relative humidity of 50%, the resulting rubbery sheet was applied to JIS K 6301. Similarly, a tensile test was performed with a No. 3 dumbbell shape at a crosshead speed of 500 mm / min, and the elongation at break (%) and the stress at break (N / mm ² ) were measured.

(Comparative Example 2)
The vinyl polymer (a), (meth) acrylic acid ester polymer (b2), IRGANOX-1010, TINUVIN-327, and TINUVIN-770 obtained above were blended in the proportions shown in Table 1 and sealed. The mixture was mixed with a stirrer until uniform, and then degassed under reduced pressure for 10 minutes to obtain a white paste-like curable composition. Evaluation similar to Example 1 was performed about the obtained curable composition. The results are shown in Table 1.

Example 4
In the preparation of the curable composition in Example 1, 10 g of swellable fluorinated mica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Co-op Chemical Co., Ltd., TINUVIN 770 (hindered amine type) A curable composition was prepared in the same manner as in Example 1 except that 5 g of a light stabilizer (manufactured by Ciba Specialty Chemicals) and 5 g of tinuvin 327 (benzotriazole-based UV absorber, Ciba Specialty Chemicals) were added. Obtained.

(Measurement of average interlayer distance of layered silicate)
The average interlayer distance of the layered silicate in the curable composition obtained in Example 4 was measured as follows.

  Using a X-ray diffraction measurement device (RINT1100, manufactured by Rigaku Corporation), 2θ of the diffraction peak obtained by diffraction of the layered surface of the layered silicate is measured, and the (001) surface of the layered silicate using the following black diffraction equation The interval was calculated. The following d was defined as the average interlayer distance, and the average interlayer distance was well dispersed as 3 nm or more.

λ = 2 dsin θ
In the formula, λ (nm) = 0.154, d (nm) plane spacing of stratified silicate, θ (degree) is a diffraction angle.

[Confirmation of dispersion state of layered silicate]
The dispersion state of the layered silicate in the cured product was observed with a transmission electron microscope (TEM, “JEM-1200EX II” manufactured by JEOL Ltd.), and was present in 5 layers or less.

Weather resistance evaluation [Evaluation]
As a result of evaluating the weather resistance of the curable composition obtained in Example 4 in the same manner as in Example 1, cracks did not occur even when 500 hours had elapsed.

The schematic diagram for demonstrating the crystal | crystallization surface (A) and crystal | crystallization end surface (B) of the flaky crystal | crystallization of a layered silicate. The schematic diagram for demonstrating the exchangeable cation between the layers of layered silicate.

Claims (8)

A vinyl polymer (a) having a crosslinkable hydrolyzable silyl group represented by the general formula (1) as a terminal, and at least one of a reducing functional group, an ultraviolet absorbing functional group and a photostable functional group; A curable composition comprising the (meth) acrylic acid ester polymer (b).
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.) The vinyl polymer (a) terminated with a crosslinkable hydrolyzable silyl group represented by the general formula (1) has at least one of a reducing functional group, an ultraviolet absorbing functional group and a photostable functional group. A curable composition characterized by that.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In the formula, R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ Si— ( R ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different, and represents a triorganosiloxy group represented by R ¹ Alternatively, when two or more R ² are present, they may be the same or different, Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they are the same. A may be 0 or 1, 2, or 3, and b may be 0, 1, or 2. m is an integer of 0 to 19, provided that a + mb ≧ 1 to be satisfied.)   The curable composition according to claim 1, wherein the light-stable functional group is a hindered amine functional group.   The curable composition according to any one of claims 1 to 3, further comprising a curing accelerator composed of an organometallic compound.   The curable composition according to any one of claims 1 to 4, further comprising a layered silicate.   The curable composition according to any one of claims 1 to 5, further comprising a polyether polymer (c) having a hydrolyzable silyl group.   The sealing material which consists of a curable composition in any one of Claims 1-6. An adhesive comprising the curable composition according to any one of claims 1 to 6.

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