JP2005290270A - Curable composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-curable composition which gives a cured product having excellent antistaticity and whose surface is thereby hardly stained with dusts and the like, and to provide a sealing material and an adhesive which each uses the curable composition. <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 an alkyl, an aryl, an aralkyl, or a triorganosiloxy, provided that, when two or more R<SP>1</SP>groups and two or more R<SP>2</SP>groups exist, the groups are each 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, 1, 2, to 3; (b) is 0, 1 or 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 that is cured by moisture, and more specifically, is configured using a vinyl polymer containing a hydrolyzable silyl group that can be cross-linked. The present invention relates to a curable composition that gives an excellent cured product, and a sealing material and an adhesive using the curable composition.

  Conventionally, a vinyl polymer having an alkoxysilyl group is known to be crosslinked by moisture in the atmosphere to give a cured product excellent in durability, weather resistance, transparency and adhesiveness (for example, the following patents) Literature 1, Patent Literature 2, Patent Literature 3). Therefore, the curable composition having the vinyl polymer is widely used for applications such as paints, coating agents, adhesives, pressure-sensitive adhesives, sealants, and sealants.

  By the way, the sealing material and the cured adhesive material located in the portion exposed to the outside air often have an exposed portion that is contaminated by moisture or dust drifting in the atmosphere, thereby impairing the appearance. Therefore, conventionally, a method of adding a photocurable compound described in Patent Document 4 below, an oxygen reactive compound described in Patent Document 5, or the like has been used. Further, as described in Patent Document 6 below, a curable composition using a polyfluoro group-containing acrylic polymer has also been proposed.

  However, these compounds are not firmly bonded to the alkoxysilyl group-containing vinyl polymer via a covalent bond. Accordingly, the surface of the cured product may be contaminated under the influence of the atmosphere, or these compounds may bleed out over time.

  Further, Patent Document 7 below discloses a coating composition containing an organosiloxane component, but here, mention is made of a covalent bond to a hydrolyzable silyl group-containing vinyl polymer. It has not been.

JP 57-179210 A JP-A-4-202585 JP 11-43512 A JP-A-5-65400 Japanese Patent Laid-Open No. 3-160053 JP 2000-366320 A JP 2002-309174 A

  An object of the present invention is to provide a curable composition using an alkoxysilyl group-containing vinyl polymer that is crosslinked and cured by moisture in the atmosphere in view of the above-described state of the art, and the cured product has an antistatic property. Accordingly, it is an object of the present invention to provide a curable composition whose surface is hardly contaminated by dust and the like, and a sealing material and an adhesive using the curable composition.

The present invention contains a vinyl polymer (a) having a structure derived from an ammonium salt (b) having a crosslinkable silyl group represented by the formula (1) at the terminal and having a polymerizable functional group as a copolymerization component. Is a curable composition.
_{^{- [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 still another specific aspect of the curable composition according to the present invention, the ammonium salt (b) having a polymerizable functional group is a (meth) acrylic group-containing ammonium salt.
In still another specific aspect of the curable composition according to the present invention, in addition to the vinyl polymer (a), a polyether polymer (c) having a hydrolyzable silyl group capable of crosslinking is further blended. Has been.

In the curable composition constituted according to the present invention, a layered silicate is preferably further blended.
The sealing material and the adhesive according to the present invention are each characterized by comprising a curable composition constituted according to the present invention.

Details of the present invention will be described below.
(Vinyl polymer (a))
The curable composition of the present invention contains a vinyl polymer (a) having the terminal formula (1).
_{^{- [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 silyl group of formula (1) at the terminal is not particularly limited. For example, the above-described method is performed using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst. By polymerizing a vinyl monomer, a vinyl polymer having a terminal structure represented by formula (2) is produced, and the halogen of formula (2) is converted to a crosslinkable silyl group-containing substituent represented by formula (1). A method 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 above formula (2) into the crosslinkable silyl group-containing substituent represented by the formula (1) is not particularly limited. For example, a compound having an alkenyl group and a crosslinkable silyl group, a silyl group, A method of reacting a compound having a stabilized carbanion, a compound having a polymerizable alkenyl group and another alkenyl group, an organometallic compound having an alkenyl group, a carboxylic acid metal salt having an alkenyl group, an alkenyl group and a stabilized carbanion For example, a method in which a halogen compound represented by formula (2) is substituted with an alkenyl group and then a hydrosilane having a crosslinkable silyl group is reacted with the alkenyl group.

In addition, when producing a vinyl polymer having a crosslinkable silyl group at the end of formula (1), an organic halide having a crosslinkable silyl group is used as an initiator, and a halogen is contained at one end. After synthesizing a polymer having a crosslinkable silyl group at one end, a polymer having a crosslinkable silyl group at both ends may be prepared by reacting with halogen and glycol, diamine, dicarboxylic acid, etc. After synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end,
Halogen may be converted to a crosslinkable silyl group by the above reaction. Alternatively, after synthesizing a polymer having a halogen at one end and a crosslinkable silyl group at the other end, the halogen may be converted to an alkenyl group by the above-described reaction, and then further converted to a crosslinkable silyl group. good.

Further, when producing a vinyl polymer having a terminal crosslinkable 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 a method of converting to a crosslinkable silyl group by the above method.

(Ammonium salt having a polymerizable functional group (b))
In the present invention, the vinyl polymer (a) has a structure derived from an ammonium salt (b) having a polymerizable functional group as a copolymer component in order to suppress the antistatic property of the cured product.

Although it does not specifically limit as said polymerizable functional group, For example, a (meth) acryloyl group etc. can be mentioned.
The ammonium salt having a polymerizable functional group can be a salt having various counter anions such as chloride, bromide, iodide, acetate salt or sulfate salt.

  As the ammonium salt having a polymerizable functional group, for example, a tetraalkylammonium salt having a polymerizable functional group such as a (meth) acryloyl group is preferably used.

  Specific examples of the ammonium salt having a polymerizable functional group include N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ammonium chloride, N, N, N-trimethyl-N. -(2-methacryloyloxyethyl) ammonium chloride, diallyldimethylammonium chloride, N, N, N-trimethyl-N- (2-hydroxy-3-methacryloyloxypropyl) ammonium acetate, 3-methacrylamideamidopropyl-trimethylammonium chloride, 3-methacrylamidopropyl-trimethylammonium methyl sulfate, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium p-toluene sulfate, N, N, -dimethyl-N-ethyl-N- ( 2-methacryloyloxyethyl) ammonium ethyl sulfate and the like.

    The vinyl polymer (a) having a structure derived from the ammonium salt (b) having a polymerizable functional group as a copolymer component is, for example, a vinyl having a terminal structure represented by the formula (2) by polymerizing a vinyl monomer. When producing a polymer, it is obtained by copolymerizing the ammonium salt (b) having a polymerizable functional group.

  The copolymerization ratio of the ammonium salt (b) having a polymerizable functional group is 0.1 to 20% by weight, more preferably 0.5 to 15% by weight in 100% by weight of the vinyl polymer (a). It is desirable to be in the range. If the amount is 0.1% by weight, the effect of improving the antistatic property may not be sufficiently obtained. If the amount exceeds 20% by weight, volume expansion may occur due to moisture absorption.

(Polyether polymer (c))
In the curable composition concerning this invention, Preferably, the polyether polymer (c) which has a hydrolyzable silyl group which can be bridge | crosslinked is further mix | 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 organic 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) and the polyether polymer (c) are used in combination, the blending ratio is 100 parts by weight of the vinyl polymer (a), and the polyether polymer (c). Is preferably added at a ratio of 0.1 to 100 parts by weight, more preferably 0.5 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 polyether polymer (c) 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.

(Layered silicate)
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 with respect to 100 parts by weight of the base resin. More preferably, it is 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight. 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.

In addition, the said base resin is the sum total of the said vinyl polymer (a) and the polyether polymer (c) added as needed.
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 vinyl polymer, and disperse in the base resin together with the layered silicate to improve the dispersibility and accelerate the curing rate. It is also possible.

  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.

(Ultraviolet absorber and light stabilizer)
The curable composition of the present invention preferably contains various ultraviolet absorbers and light stabilizers in order to improve the weather resistance. This is because the layered silicate acts so as to suppress bleed-out of various ultraviolet absorbers and light stabilizers in combination with the layered silicate, so that these are retained in the cured product for a long time.

  Examples of the UV absorber include known UV absorbers such as benzotriazole and benzophenone, and among them, a benzotriazole UV absorber is preferable because of its 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.

  It is considered that the weather resistance effect by the combined use with the layered silicate is mainly due to the bleed-out prevention effect of the light stabilizer. That is, it is considered that the layered silicate interacts 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 additives)
In the curable composition of the present invention, unless the effect is hindered from the object of the present invention, a curing accelerator for the vinyl polymer (a), a viscosity modifier for adjusting the viscosity characteristics of the composition, a thixotropic agent, a tensile property Add physical property modifiers, extenders, reinforcing agents, plasticizers, colorants, flame retardants, antioxidants, anti-sagging agents, anti-aging agents, solvents, fragrances, pigments, dyes, dehydrating agents, etc. Also good.

  As the curing accelerator for the vinyl polymer (a), for example, an organometallic compound can be used. As an organic metal compound that can be suitably used, 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 can be given. 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, titanate compounds such as tetra-n-butoxy titanate and tetraisopropoxy titanate, and these can be used alone or in combination of two or more.

  The viscosity modifier is selected, for example, from a polymer compound having good compatibility with the vinyl polymer (a), and is appropriately selected from compounds to be blended. 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 a high affinity for the vinyl polymer (a).

  Examples of physical property modifiers that improve tensile properties include various silane coupling agents such as vinyltrimethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and phenyltrimethoxy. Silane, 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] ethylene Amines, 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 exhibit 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 glycerin 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.

(Adhesive and sealing material)
The curable composition according to the present invention is suitably used as a sealing material or an adhesive. The curable composition according to the present invention is quickly cured by moisture in the atmosphere, gives a cured product having flexibility and develops good adhesive strength, as will be apparent from the examples described later, but further cured. Since the object is excellent in antistatic property, adhesion of dust and the like is difficult to occur. Therefore, the curable composition according to the present invention is suitably used for a sealing material or an adhesive used for a portion exposed to the outside.

The curable composition according to the present invention contains a vinyl polymer (a) containing at least a crosslinkable silyl group, and is quickly cured by moisture in the atmosphere to give a cured product with high flexibility. In particular, since the ammonium salt (b) having a polymerizable functional group is copolymerized as a copolymerization monomer, the cured product has excellent antistatic properties, and therefore excellent antifouling properties.
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.

  Therefore, the curable composition according to the present invention is suitably used as a sealing material or an adhesive used in a portion exposed to the outside in the outdoors, etc., and enhances the appearance of the joint portion or the seal portion over a long period of time. Is possible.

  Examples of the present invention and comparative examples will be described below. The present invention is not limited to the following examples.

(Example 1)
(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. N-butyl acrylate (447 g, 3.9 mol), 1.3 g of N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride and diethyl-2,5-dibromoadipate (15.7 g) 43.6 mmol), and the mixture was stirred with heating 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. 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), potassium salt of 4-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.

  100 g of the vinyl polymer obtained above, 50 g of polypropylene glycol (Wako Pure Chemical Industries, molecular weight 3000), 13 g of fatty acid surface-treated calcium carbonate, 26 g of heavy calcium carbonate, and 2 g of a curing accelerator (dibutyltin dilaurate) are added, The mixture was mixed with a sealed stirrer until uniform, and then degassed under reduced pressure for 10 minutes to obtain a white paste-like curable composition.

The obtained curable composition was coated on a polyethylene plate so as to have a film thickness of 2.5 mm, and then cured for 7 days in an environment of 20 ° C. and a relative humidity of 20%. A film was obtained. The rubber properties of the sheet film were evaluated as follows. As a result, the breaking elongation was 490% and the breaking stress was 0.19 N / mm ² .

Evaluation of rubber properties: A rubber-like sheet cured for 7 days in an atmosphere of 20 ° C. and 50% relative humidity was subjected to a tensile test at a crosshead speed of 500 mm / min in a No. 3 dumbbell shape according to JIS K 6301, and ruptured. Elongation (%) and breaking stress (N / mm ² ) were measured.

(Comparative Example 1)
In Example 1, when the vinyl polymer (a) was synthesized, curing was performed in the same manner as in Example 1 except that N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride was not used. A composition was obtained.
The obtained curable composition was evaluated in the same manner as in Example 1.
The breaking elongation of the sheet coating rubber was 580%, and the breaking stress was 0.23 N / mm ² .

(Evaluation of antifouling properties)
Antifouling property was evaluated using a part of each sheet used for evaluating rubber physical properties in the above-described Examples and Comparative Examples. In evaluating the antifouling property, a part of the sheet was exposed outdoors. When exposed outdoors, the sheet was exposed to the south side and inclined by 45 ° with respect to the horizontal plane. The place of exposure was a point about 20 m away from National Route 1 in the site of Sekisui Chemical Co., Ltd. Mizuguchi Factory. The results are shown in Table 1 below.

  In addition, the meaning of the evaluation symbol in the following Table 1 is as follows.

  ◎: No contamination, ○: Slightly contaminated, ×: Very contaminated

(Example 2)
During the preparation of the curable composition, 10 g of layered silicate Somasifu MPE-100 (swelling fluorinated mica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Co-op Chemical), tinuvin 770 (hindered amine light stabilizer, A curable composition was obtained in the same manner as in Example 1 except that 5 g of Ciba Specialty Chemicals Co., Ltd.) and 5 g of Tinuvin 327 (benzotriazole ultraviolet absorber, Ciba Specialty Chemicals Co., Ltd.) were added.

(Measurement of average interlayer distance of layered silicate)
The average interlayer distance of the layered silicate in the curable composition obtained in Example 2 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]
The weather resistance of the curable compositions obtained in Examples 1 and 2 was evaluated by the following method. Each compounded composition was applied to a stainless steel plate of 50 mm × 150 mm (thickness 1 mm) at a thickness of 0.5 mm, allowed to stand for 7 days (168 hours) in an atmosphere of 20 ° C. × 60% RH, and then cured and cured. Irradiation with light was performed for 150 hours and 400 hours under the conditions, the surface state was visually confirmed, and those without cracks were determined as ◯.

-Light irradiation condition Test apparatus: Eye super UV tester (SUV-F11 type), manufactured by Iwasaki Electric Co., Ltd. Irradiation intensity: 100 mW / cm <2>
Limited wavelength: 295 nm to 450 nm
Black panel temperature: 63 ° C
Irradiation distance: 235mm (between light source and sample)
Although the light irradiation evaluation by the eye super UV tester varies depending on the material system and test conditions, it cannot be generally stated. However, it is usually 10 times more severe than the evaluation by the sunshine weatherometer. Has been. The results are shown in Table 2 below.

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 (6)

It contains a vinyl polymer (a) having a structure derived from an ammonium salt (b) having a crosslinkable silyl group represented by the formula (1) at the terminal and having a polymerizable functional group as a copolymerization component. A curable composition characterized by the above.
_{^{- [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 ammonium salt (b) having a polymerizable functional group is a (meth) acrylic group-containing ammonium salt.   The curable composition according to claim 1 or 2, further comprising a polyether polymer (c) having a crosslinkable hydrolyzable silyl group in addition to the vinyl polymer (a).   The curable composition according to any one of claims 1 to 3, further comprising a layered silicate.   A sealing material comprising the curable composition according to claim 1. An adhesive comprising the curable composition according to any one of claims 1 to 4.

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