JP2005290276A - Curable composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition giving a cured product which has excellent insecticidal, antifungal, and algaecidal properties and the like and can maintain a good appearance over a long period, and to provide a sealing material and an adhesive each using the curable composition. <P>SOLUTION: This curable composition comprises (a) 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 represented by formula : (R')<SB>3</SB>Si- (R' is a 1 to 20C monovalent hydrocarbon group); Y is OH or a hydrolyzable group; (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 (b) at least one appearance-retaining agent selected from the group consisting of organism-repelling agents, algaecides and antifungal agents. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition using a hydrolyzable silyl group-containing polymer that is crosslinked by moisture in an atmosphere and gives a cured product having excellent durability. More specifically, the present invention has a long-term appearance. The present invention relates to a curable composition that provides a cured product that can be maintained, a sealing material using the curable composition, and an adhesive.

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

  In order to make the composition containing the alkoxysilyl group-containing vinyl polymer into a liquid composition so that the coating operation is easy and that the cured product after curing has rubber elasticity, As the combination, a (meth) acrylic acid ester polymer is preferably used.

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

  The curable composition prepared using the vinyl polymer having an alkoxysilyl group is cured in an atmosphere in the air to give a cured product. By the way, when the curable composition is used as an adhesive or a sealing material, and left in the air after curing, there is a problem that insects, molds, algae, etc. are attached and the appearance is deteriorated. In particular, in a high humidity environment such as Japan, mold, algae, insects or the like that deteriorate the appearance as described above tend to adhere to the surface of the cured product.

  An object of the present invention is to provide a curable composition using a vinyl polymer having a crosslinkable hydrolyzable silyl group in view of the above-described conventional state of the art. An object of the present invention is to provide a curable composition that is excellent in anti-algae properties and the like and that provides a cured product that can maintain a good appearance for a long period of time, and a sealing material and an adhesive using the curable composition.

The curable composition according to the present invention is selected from the group consisting of a vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) and a biological repellent, an algae and an antifungal agent. And a curable composition comprising at least one appearance-retaining agent (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.)

  In still another specific aspect of the curable composition according to the present invention, a polyether polymer (d) having at least a crosslinkable hydrolyzable silyl group is 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 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 part constituting the vinyl polymer may be a polymer obtained by polymerizing a vinyl monomer, such as polyethylene, polypropylene, polyisobutylene, poly (meth) acrylate, polystyrene, Examples thereof include polyvinyl chloride, polyvinylidene chloride, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, and polyvinyl ether. Moreover, the copolymer which has these vinyl-type 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]
CH2 = CH-C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 2]
CH2 = C (CH3) -C (O) O-CH2CH2O-
[C (O) CH2CH2CH2CH2CH2O] n-H
(N = 1-10)
[Compound 3]
CH2 = CH-C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 4]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-H
(N = 1-12)
[Compound 5]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 6]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-H
(N = 1-12)
[Compound 7]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 8]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-12)
(M = 1-12)
[Compound 9]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 10]
CH2 = CH-C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(N = 1-12)
(M = 1-12)
[Compound 11]
CH2 = CH-C (O) O- (CH2CH2O) n-CH3
(N = 1-10)
[Compound 12]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-CH3
(N = 1-30)
[Compound 13]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 14]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n-CH3
(N = 1-10)
[Compound 15]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 16]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(N = 1-10)
(M = 1-10)
[Compound 17]
CH2 = CH-C (O) O- [CH2CH (CH3) O] n
-C (O) -CH = CH2
(N = 1-20)
[Compound 18]
CH2 = C (CH3) -C (O) O- [CH2CH (CH3) O] n
-C (O) -C (CH3) = CH2
(N = 1-20)
[Compound 19]
CH2 = CH-C (O) O- (CH2CH2O) n-C (O) -CH = CH2
(N = 1-20)
[Compound 20]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n
-C (O) -C (CH3) = CH2
(N = 1 to 20).

  Examples of other vinyl monomers include styrene such as styrene, indene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, and the like. Derivatives; for example, compounds having vinyl ester groups such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate, vinyl cinnamate; maleic anhydride, N-vinylpyrrolidone, N-vinylmorpholine, (Meth) 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.

(Appearance retention agent (b))
In the curable composition concerning this invention, in order to maintain the external appearance of hardened | cured material, at least 1 sort (s) selected from the group which consists of a biological repellent, an algae control agent, and a fungicide is mix | blended.

  The biological repellent is not particularly limited, and for example, an appropriate drug having an action of preventing insects such as an ant preventive can be used. Examples of such biological repellents include dried red pepper powder, red pepper extract, horseradish extract, cypress extract, and shibumi components of moths. It is possible to suppress the adhesion of filth and the proximity and adhesion of these living organisms to the cured product surface.

  Further, the above algae and fungicide are not particularly limited, and examples thereof include 2-n-octyl-4-isothiazolin-3-one and 5-dichloro-2-n-octyl-4-isothiazolin-3-one. , 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazolin-3-one, and the like; 3- (3,4-dichlorophenyl) -1,1-dimethylurea ( DCMU), 3- (3,4-dichlorophenyl) -1-methyl-1-methoxyurea, 3- (3,4-dichlorophenyl) -1- (2-methylcyclohexyl) urea, 3-phenyl-1- (2 -Urea systems such as methylcyclohexyl) urea and 3- (phenyldimethylmethyl) -1- (4-methylphenyl) urea; 2-chloro-4,6-bis (ethylamino) -1,3 5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylthio-4,6-bis (ethylamino) -S-triazine, 2-methylthio-4- Ethylamino-6-isopropylamino-S-triazine, 2-methylthio-4,6-bis (isopropylamino) -S-triazine, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-S-triazine , N′-t-butyl-N-cyclopropyl-6- (methylthio) -1,3,5-triazine-2,4-diamine and other triazines; tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetraisopropyl Thiuram disulfide, dipyrrolizol thiuram disulfide, polyethylene thiuram Thiuram disulfide series such as sulfide; benzimidazole series such as 2- (4-thiazyl) benzimitazole, 2- (carbomethoxyamino) benzimidazole; 2,3,5,6-tetrachloro-4- (methyl) Pyridine) such as sulfonyl) pyridine; zinc pyrithione such as zinc-2-pyritinthiol-1-oxide; thiazole such as 2- (4-thiocyanomethylthio) benzothiazole; organohalogen, organometallic, haloalkylthio Type, phenylphenol-type algae or fungicide.

  Only 1 type may be used for the said biological repellent, an algae control agent, and a fungicide, and these may be used together. Further, a plurality of biological repellents, algaeproofing agents and antifungal agents may be used.

  Preferably, it is desirable to use an antifungal agent having a high antifungal effect such as an isothiazoline or urea type in combination with an algal control agent such as a triazine or a pyridine.

  If the amount of the biological repellent, the algae and / or the fungicide is too small, the effect of maintaining the appearance may not be sufficient. If the amount is too large, the weather resistance will be lowered, and the discoloration may occur due to secular change. May occur. Therefore, it is preferable that the appearance retention agent (b) is blended in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight with respect to 100 parts by weight of the base resin. The base resin refers to the vinyl polymer (a) described above, or the total of the vinyl polymer (a) and the later-described polyether polymer (d).

  In addition, when only one type of appearance retention agent is used, the addition ratio of the appearance retention agent (b) may be within the above range, and plural types of appearance retention agents ( When b) is added, the total of the plurality of types of appearance retention agents (b) may be added within the above range.

  Furthermore, the curable composition of the present invention can suppress bleed-out of the appearance retainer by further blending a layered silicate described later, so that the appearance retention effect of the curable composition can be maintained for a long time. Can keep.

(Layered silicate (c))
In the curable composition which concerns on this invention, Preferably, layered silicate (c) is further mix | blended. By blending the layered silicate, bleed out from the cured product of the above-described appearance-retaining agent (b) can be suppressed, and thereby the action of the appearance-retaining agent (b) can be maintained over a long period of time. it can.

  Further, the surface of the layered silicate has an anionic property, and the appearance-retaining agent (b) hardly bleeds out on the outer surface of the cured product having a low polarity due to ionic interaction with the appearance-retaining agent (b). Thus, the effect of the addition of the appearance retaining agent (b) is maintained for a long time.

  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) or the vinyl polymer (a1) and the polyether polymer (d) added as 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. Quaternary ammonium salts are known to have a catalytic action on the crosslinking reaction of the above polyether polymers, and are dispersed in the base resin together with the layered silicate to improve the dispersibility and accelerate the curing rate. It is also possible to make it.

  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.

(Polyether polymer)
In the curable composition according to the present invention, the vinyl polymer (a) preferably has a crosslinkable hydrolyzable silyl group when the main chain is essentially composed of a vinyl polymer. It is preferable that an ether polymer is further blended.

By adding a 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) and the polyether polymer are used in combination, the blending ratio is preferably 0.1 to 200 parts by weight of the polyether polymer with respect to 100 parts by weight of the vinyl polymer (a). More preferably, it is 0.5 to 100 parts by weight.

  When the blending ratio of the polyether polymer is less than 0.1 parts by weight, the effect of improving adhesiveness may be reduced, and when it exceeds 200 parts by weight, the weather resistance may be lowered and the effect of improving adhesiveness may be obtained. It is not so expensive.

  A polyether polymer is a polymer whose main chain is essentially a polyether polymer and contains a hydrolyzable silyl group which can be cross-linked at the end, and the main chain is essentially Formula [-(RO) 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 may be a copolymer having a main chain composed of polyether and (meth) acrylic acid ester.
The polyether 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 (d) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and the like, but a cured product of a room temperature curable composition is excellent in water resistance and sealing. Polypropylene oxide is preferable because it can ensure elasticity as a material.

  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-based polymer is small, the elongation of the cured product is not sufficient, the followability to the joint surface is lowered, and if it is large, the viscosity before curing is increased and the workability of the blending process is deteriorated. 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 include, for example, trade name “MS polymer” (manufactured by Kaneka Chemical Co., Ltd.), MS polymer S-203, S-303, etc. As a product), Cyril SAT-200, SAT-350, SAT-400, as trade name "Exester" (Asahi Glass Co., Ltd.), Exester ESS-3620, ESS-3430, ESS-2420, ESS-2410, etc. Is commercially available.

(Ultraviolet absorber and light stabilizer)
The curable composition of the present invention preferably contains various ultraviolet absorbers and / or 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 blending the ultraviolet absorber, 0.5 to 10 parts by weight is preferably blended with respect to 100 parts by weight of the base resin. If the amount is less than 0.5 parts by weight, the effect of improving weather resistance may be insufficient. If the amount exceeds 10 parts by weight, problems such as a loss of 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.

(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 a hardening accelerator of a vinyl polymer (a), an organometallic compound part can be used, for example. 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. About selection of a thixotropic agent, what has a surface with high affinity with respect to a vinyl polymer (a1) is desirable.

  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.

Since the curable composition according to the present invention comprises the vinyl polymer (a) having a crosslinkable silyl group represented by the formula (1) at the terminal and the above-described appearance retention agent (b), moisture in the atmosphere To give a cured product having elasticity. Moreover, since the appearance-retaining agent is added, the adhesion of organisms such as insects and birds or the adhesion of filth by organisms is suppressed, and the adhesion of molds and algae is less likely to occur. Therefore, it is possible to provide a curable composition that can provide a cured product having a good appearance for a long period of time.
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 particular, when layered silicate is blended in the curable composition, the layered silicate suppresses the bleed-out of the above-mentioned appearance retention agent. Therefore, the effect of the appearance retaining agent is exhibited over a long period of time.

  Moreover, when the layered silicate contains an alkylammonium ion, the dispersibility of the layered silicate in the curable composition is enhanced, and the effect of the addition of the layered silicate is further enhanced.

  In the curable composition concerning this invention, since the external appearance property of hardened | cured material is hold | maintained over a long period of time, it becomes possible to provide the curable composition suitable for the sealing material and adhesives used outdoors.

  Hereinafter, the present invention will be described in more detail by giving specific examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(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. 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.

  To 100 g of the vinyl polymer obtained above, 50 g of polypropylene glycol (manufactured by Wako Pure Chemical Industries, molecular weight 3000), 30 g of surface treated calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Viscolite U), heavy calcium carbonate (Shiraishi Calcium Co., Ltd.) Product, Whiteon P30) 70 g, curing accelerator (dibutyltin dilaurate) 2 g, fungicide (2-n-octyl-4-isothiazolin-3-one) 2 g, and mixed with a sealed stirrer until uniform Then, defoaming under reduced pressure for 10 minutes gave a white paste-like curable composition. The obtained curable composition was filled in a joint portion having a width of 10 mm, a length of 30 mm, and a depth of 10 mm, and then cured under an environment of 30 ° C. and a relative humidity of 50%, and the occurrence of mold was visually observed. Even after 6 months, the occurrence of mold was not confirmed.

(Comparative Example 1)
100 g of the vinyl polymer (a) obtained above, 50 g of polypropylene glycol (manufactured by Wako Pure Chemical Industries, molecular weight 3000), 30 g of surface-treated calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., Viscolite U), heavy calcium carbonate (Shiroishi) Calcium White White P30) 70g and curing accelerator (dibutyltin dilaurylate) 2g are added, mixed with a sealed stirrer until uniform, and then defoamed under reduced pressure for 10 minutes to form a white paste-like curable composition Got. The obtained curable composition was filled in a joint of 10 mm wide × 30 mm long × 10 mm deep, then cured under an environment of 30 ° C. and 50% relative humidity, and the occurrence of mold was visually observed. After 6 months, the occurrence of slightly black mold was confirmed.

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 (5)

At least one appearance-retaining agent selected from the group consisting of a vinyl polymer (a) having a crosslinkable silyl group represented by the general formula (1) and a biorepellent, an algae and an antifungal agent A curable composition comprising (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 curable composition according to claim 1, further comprising a layered silicate (c). The curable composition according to claim 1 or 2, further comprising a polyether polymer (d) having at least a crosslinkable hydrolyzable silyl group. 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 3.

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