JP2005126673A - Curable composition, sealing material and adhesive - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition which comprises an organic polymer bearing a crosslinkable hydrolyzable silyl group, does not cause phase separation and gives a stable cured film hardly causing bleeding out of additives after cure, a sealing material and an adhesive. <P>SOLUTION: The curable composition comprises the organic polymer (a) bearing at least a crosslinkable hydrolyzable silyl group and an organic polymer (b) having a difference in the SP value of at most 7×10<SP>-4</SP>(J/m<SP>3</SP>)<SP>0.5</SP>from the organic polymer (a). Preferably, the curable composition further contains a layered silicate. The sealing material comprises the curable composition. The adhesive comprises the curable composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a curable composition, a sealing material, and an adhesive that are crosslinked and cured by moisture in an atmosphere, and more particularly, a curable composition capable of obtaining a stable cured film without phase separation, and the curable composition. The present invention relates to a sealing material and an adhesive using the composition.

  Conventionally, various curable compositions using vinyl polymers having a crosslinkable hydrolyzable silyl group have been proposed (see, for example, Patent Document 1). Curable compositions using these vinyl polymers are crosslinked by moisture in the atmosphere, and give a cured product excellent in durability, weather resistance, transparency and adhesiveness. Therefore, the curable composition is widely used in various applications such as paints, coating materials, sealants, sealants, adhesives, pressure-sensitive adhesives, and primers.

  As a vinyl polymer having a crosslinkable hydrolyzable silyl group, for example, if a composition containing an alkoxysilyl group-containing vinyl polymer is liquefied to increase the coating workability, the molecular weight is lowered. There is a need. However, when the molecular weight of the vinyl polymer is lowered, physical properties such as elongation of a cured product after curing may be lowered.

  For this purpose, various methods have been proposed in which a vinyl polymer having a hydrolyzable silyl group is used while ensuring the physical properties of the cured product, and a compound for reducing the viscosity is added to make the composition liquid. ing. For example, in order to reduce the viscosity of the composition to obtain a favorable viscosity, it has been proposed to contain a polymer plasticizer as a liquid oligomer such as polyester or polyether (see, for example, Patent Document 2).

JP 57-179210 A JP 55-31874 A

  However, when a liquid oligomer having a different monomer composition is used as a compound for reducing the viscosity in an organic polymer containing a hydrolyzable silyl group, the composition causes phase separation or the liquid oligomer is removed from the cured product. In some cases, bleed out and stickiness occur, and the original performance may not be exhibited.

  The object of the present invention is a curable composition using an organic polymer containing a crosslinkable hydrolyzable silyl group in view of the above-described state of the art, and the composition does not phase-separate and is cured. It is an object of the present invention to provide a curable composition, a sealing material, and an adhesive which are capable of obtaining a stable cured film that hardly causes bleeding out of the additive.

In order to achieve the above object, the invention according to claim 1 is characterized in that the SP value difference between the organic polymer (a) containing at least a crosslinkable hydrolyzable silyl group and the organic polymer (a) is 7 ×. There is provided a curable composition comprising an organic polymer (b) that is 10 ⁻⁴ (J / m ³ ) ^0.5 or less.

  Moreover, invention of Claim 2 provides the curable composition of Claim 1 which further contains a layered silicate.

  Moreover, invention of Claim 3 provides the sealing material which consists of a curable composition of Claim 1 or 2.

  Moreover, invention of Claim 4 provides the adhesive agent which consists of a curable composition of Claim 1 or 2.

Details of the present invention will be described below.
In the curable composition of the present invention, the SP value difference between the organic polymer (a) containing at least a crosslinkable hydrolyzable silyl group and the organic polymer (a) is 7 × 10 −4 (J / m ³ ) and an organic polymer (b) that is ^0.5 or less.

(Organic polymer (a))
The organic polymer used in the present invention has at least one hydrolyzable silyl group that can be crosslinked by forming a siloxane bond. This siloxane bond is, for example, a hydroxyl group or hydrolyzable group bonded to a silicon atom. It is formed by.

  The main chain of the organic polymer having at least one hydrolyzable silyl group capable of crosslinking by forming a siloxane bond is not particularly limited. Examples thereof include a polymer, a polyester-based polymer, a polycarbonate-based polymer, a polyolefin-based polymer, and the like, and preferably a vinyl-based polymer and / or a polyether-based polymer. That is, the main chain may have one or both of a vinyl polymer portion and a polyether polymer portion. These may be used alone or in combination of two or more.

  Examples of hydrolyzable groups bonded to silicon atoms include hydrogen, halogen atoms, alkoxy groups, acyl oxide groups, ketoximate groups, amino groups, amide groups, acid amide groups, aminooxy groups, mercapto groups, alkenyl oxide groups, and the like. Is a preferred example.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, a tert-butoxy group, a phenoxy group, and a benzyloxy group. Examples of the alkoxysilyl group to which the alkoxy group is bonded include, for example, a trialkoxysilyl group such as a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a triphenoxysilyl group; a dimethoxymethylsilyl group, a diethoxymethylsilyl group And dialkoxysilyl groups such as methoxydimethylsilyl group and ethoxydimethylsilyl group. These may be used alone or in combination of two or more.

  As the hydrolyzable silyl group, an alkoxysilyl group such as a methoxysilyl group or an ethoxysilyl group is preferably used because no harmful by-product is formed after the reaction.

(Vinyl polymer)
The vinyl polymer used in the present invention is particularly limited except that the main chain consists essentially of a vinyl polymer, has a crosslinkable hydrolyzable silyl group, and excludes the telechelic acrylic polymer. It is not a thing. The crosslinkable hydrolyzable silyl group is preferably a functional group in which 1 to 3 alkoxy groups are bonded to a silicon atom, that is, an alkoxysilyl group.

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 acetal, and polyvinyl ether. Moreover, the copolymer which has these vinyl-type polymer parts may be sufficient. Preferably, poly (meth) acrylate having a number average molecular weight of 5,000 to 200,000 and a copolymer thereof having a good balance between cohesive strength and adhesiveness are preferable. Here, (meth) acrylate means methacrylate or acrylate.

  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
(M, n = 1-12)
[Compound 8]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 1-12)
[Compound 9]
CH2 = C (CH3) -C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(M, n = 1-12)
[Compound 10]
CH2 = CH-C (O) O- (CH2CH2O) n-
(CH2CH2CH2CH2O) mH
(M, n = 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
(M, n = 1-10)
[Compound 16]
CH2 = CH-C (O) O- (CH2CH2O) n-
[CH2CH (CH3) O] m-H
(M, n = 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 = 1-20)
Etc.

  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.

  A known method can be used for producing the vinyl polymer. For example, a free radical polymerization method, an anionic polymerization method, a cationic polymerization method, a UV radical polymerization method, a living anion polymerization method, a living cation polymerization method, a living radical polymerization method, etc. can be used, and depending on the polymerizable reaction of the monomer A polymerization method may be appropriately selected.

  As a method for introducing a crosslinkable hydrolyzable silyl group, a method of initiating polymerization using an initiator having a crosslinkable hydrolyzable silyl group, or a chain transfer agent having a crosslinkable hydrolyzable silyl group is used. And a method of introducing a silyl group simultaneously with polymerization by a method using a copolymerizable monomer having a hydrolyzable silyl group capable of crosslinking (for example, JP-A-54-123192, JP-A-57-179210, JP-A-59-78220, JP-A-60-23405) and methods for synthesizing vinyl polymers having alkenyl groups and then introducing alkoxysilyl groups by hydrosilylation (for example, JP-A-59-78220). JP 54-40893, JP 11-80571). The production method of the vinyl polymer constituting the present invention can use any of the known production techniques as described above without any problem as long as the vinyl polymer is obtained.

Examples of the chain transfer agent or copolymerizable monomer for introducing a crosslinkable hydrolyzable silyl group include mercaptomethyltrimethylsilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyldimethoxymethylsilane. Alkoxysilane having a functional group with high chain transfer; N- (3-acryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropylmethyldimethoxy Silane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethylbis (trimethylsiloxy) silane, allyltriethoxysilane, allyltrimethoxysilane, 3-allylaminopropylto Methoxysilane, 3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Methacryloyloxypropenyltrimethoxysilane, vinylmethyldiacetoxysilane, vinyltriacetoxysilane, vinyldimethylmethoxysilane, vinyldimethylethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vintriisopropoxysilane , Vinyltriphenoxysilane, vinyldimethylisopentenyloxysilane, vinyldimethyl- -((2-ethoxyethoxy) ethoxy) silane, vinyltris (1-methylvinyloxy) silane, vinyltris (2-methoxyethoxy) silane, phenylvinyldiethoxysilane, diphenylvinylethoxysilane, 6-triethoxysilyl-2- Examples thereof include alkoxysilanes having a polymerizable unsaturated group such as norbornene, octa-7-enyltrimethoxysilane, and styrylethyltrimethoxysilane.

  The blending amount of the chain transfer agent or copolymerizable monomer for introducing the hydrolyzable silyl group is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the vinyl polymerizable monomer. Preferably, it is 0.1 to 5 parts by weight.

  In the present invention, in order to make yellowing of the cured product difficult to occur, the vinyl polymer is preferably obtained by a radical polymerization method using a peroxide as a polymerization initiator. Examples of the peroxide used as the polymerization initiator include benzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, parachlorobenzoyl peroxide, di (3, 5, Diacyl peroxides such as 5-trimethylhexanoyl) peroxide; diisopropyl purge carbonate, di-sec-butyl purge carbonate, di-2-ethylhexyl purge carbonate, di-1-methylheptyl purge carbonate, di-3-methoxybutyl purge Peroxydicarbonates such as carbonate and dicyclohexyl purge carbonate; tert-butyl perbenzoate, tert-butyl peracetate, tert-butyl per-2- Peroxyesters such as tilhexanoate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl diperadipate, cumyl perneodecanoate; ketones such as methyl ethyl ketone peroxide and cyclohexanone peroxide Peroxides; dialkyl such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane Peroxides; hydroperoxides such as cumene hydroxy peroxide and tert-butyl hydroperoxide.

  As for the said peroxide, only 1 type may be used and 2 or more types may be used together. Further, the peroxide may be added at once or may be added sequentially over a plurality of times.

As another method of introducing the hydrolyzable silyl group, there is a method of synthesizing a polymer having a functional group and then introducing the hydrolyzable silyl group using the functional group. This method is preferable because it is easy to reliably introduce a hydrolyzable silyl group as represented by the formula (1) to the end of the polymer.
-C (R ¹ ) (R ² ) (X) (1)
(In the formula, R ^1, R ² represents a group bonded to an ethylenically unsaturated group of a vinyl monomer. In addition, X represents chlorine, bromine, or halogen atom iodine,.)

  As a method for introducing the hydrolyzable silyl group, for example, an organic halide or a sulfonyl halide compound is used as an initiator, and the vinyl monomer is polymerized using a transition metal complex as a catalyst. And a method of producing a polymer having a halogen at the terminal and converting the halogen of the formula (1) into a hydrolyzable silyl group. In this case, a polymer having halogen at both ends can be obtained by using an initiator having two halogens that serve as polymerization initiation base points.

  The method for converting the halogen of the above formula (1) into a hydrolyzable silyl group is not particularly limited. For example, a compound having an alkenyl group and a hydrolyzable silyl group, a compound having a silyl group and a stabilized carbanion, etc. 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, a compound having an alkenyl group and a stabilized carbanion, and the like. Examples include a method in which a halogen of formula (1) is substituted with an alkenyl group, and then a hydrosilane having a hydrolyzable silyl group is reacted with the alkenyl group.

Further, when producing a polymer having a terminal of formula (1), an organic halide having a hydrolyzable silyl group is used as an initiator, and a halogen is present at one end and a hydrolyzable at the other end. After synthesizing a polymer having a silyl group, a polymer having hydrolyzable silyl groups at both ends may be prepared by reacting with halogen and glycol, diamine, dicarboxylic acid or the like. After synthesizing a polymer having a hydrolyzable silyl group at the other end,
Halogen may be converted to a hydrolyzable silyl group by the above reaction. Alternatively, after synthesizing a polymer having a halogen at one end and a hydrolyzable silyl group at the other end, the halogen is converted to an alkenyl group by the reaction described above, and then further converted to a hydrolyzable silyl group. May be.

  In addition, when producing a polymer having a terminal of formula (1), an organic halide having an alkenyl group is used as an initiator, and a polymer having a halogen at one end and an alkenyl group at the other end And a method of converting the alkenyl group to a hydrolyzable silyl group by the above-described method after the halogen is converted to an alkenyl group.

(Polyether polymer)
Examples of the polyether polymer 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) acrylate. 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 and the polyether polymer are used in combination, the blending ratio is 100 parts by weight of the vinyl polymer.
It is preferable to add the polyether polymer at a ratio of 0.1 to 200 parts by weight, and more preferably 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 may not be so high.

The polyether-based polymer essentially has a main chain of the general formula [— (R—O) n
-And R in the formula 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 is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at the terminal with a hydrosilane compound represented by the following formula (2) in the presence of a group VIII transition metal.

Wherein R ³ 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.

  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.

(Organic polymer (b))
The curable composition concerning this invention contains the organic polymer (b) whose SP value difference with the said organic polymer (a) is 7 * 10 < ^-4 > (J / m < ³ >) ^0.5 or less. The SP value is a solubility parameter.

As the SP value, a value obtained by the Hoy method is used. When the SP value difference between the organic polymer (a) and the organic polymer (b) is 7 × 10 ⁻⁴ (J / m ³ ) ^0.5 or less, the organic polymer (a) and the organic polymer (b ), The composition undergoes phase separation, or a bleed-out hardly occurs from the cured product, so that a stable cured film is obtained, and the original performance is easily exhibited.

The organic polymer (b) has an SP value difference of 7 × 10 ⁻⁴ (J / m ³ ) ^{0.5 from the} organic polymerization (a).
It will not specifically limit if it is the organic polymer used as the following. Examples of the main chain of the organic polymer (b) include a vinyl polymer, a polyether polymer, a polyester polymer, a polycarbonate polymer, a polyolefin polymer, and preferably a vinyl polymer. And / or a polyether polymer. That is, the main chain may have one or both of a vinyl polymer portion and a polyether polymer portion.

  The organic polymer (b) is preferably an oligomer having a number average molecular weight of 500 to 10,000 in order to reduce the viscosity of the curable composition and improve the coating workability. When the number average molecular weight is less than 500, the cohesive force is low and the elasticity of the cured product may be lowered, or the tackiness may remain. When the number average molecular weight exceeds 10,000, it may be difficult to lower the viscosity.

  The vinyl polymer part constituting the vinyl polymer may be a polymer obtained by polymerizing a vinyl monomer used in the vinyl polymer, such as poly (meth) acrylate and its copolymer. Coalescence is preferred.

  The method for producing the vinyl polymer can be the same as the method for producing the vinyl polymer described above, and a crosslinkable hydrolyzable silyl group may or may not be introduced.

  The blending ratio of the organic polymer (b) is preferably 20 to 200 parts by weight, more preferably 50 to 150 parts by weight with respect to 100 parts by weight of the organic polymer (a). If the amount is less than 20 parts by weight, it may be difficult to lower the viscosity. If the amount exceeds 200 parts by weight, a sufficient cured film may no longer be formed even if the organic polymer (a) is crosslinked.

(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 these may be used alone or in combination of two or more.

  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 organic polymer (a). More preferably, it is 0.5 to 50 parts by weight, and particularly preferably 1 to 10 parts by weight. If it is less than 0.1 part by weight, the effects such as improvement in weather resistance and flame retardancy of the cured product are hardly exhibited, and 1
When it exceeds 00 parts by weight, the viscosity of the curable composition may be increased, and workability and productivity may be deteriorated.

  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 organic polymer (a). 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 in 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 organic polymer (a) can be improved by treating with a quaternary ammonium salt. Further, quaternary ammonium salts are known to have a catalytic action on the crosslinking reaction of the organic polymer (a), and dispersibility is improved by dispersing in the organic polymer (a) together with the layered silicate. At the same time, the curing rate can be accelerated.

  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 bleeding 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 period of time.

Examples of the ultraviolet absorber include known ultraviolet absorbers such as benzotriazole and benzophenone, and among them, a benzotriazole ultraviolet absorber is preferable because of its high ultraviolet absorption performance. When blending the ultraviolet absorber, 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight is blended with respect to 100 parts by weight of the organic polymer (a). preferable. If the amount is less than 0.1 parts by weight, the effect of improving weather resistance may be insufficient. If the amount exceeds 20 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 chemical formula (3) in the molecule are particularly effective when used in combination with a layered silicate. Examples of such hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidine) sebacate and 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 of the combined use of the light stabilizer 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 layered silicate interacts with the light stabilizer in the composition to prevent the light stabilizer from escaping from the system.

  When the light stabilizer is blended, 0.1 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight is blended with respect to 100 parts by weight of the organic polymer (a). . If the amount is less than 0.1 parts 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 organic polymer (a), a viscosity modifier for adjusting the viscosity characteristics of the composition, a thixotropic agent, tensile properties, etc. Physical property modifiers, extenders, reinforcing agents, plasticizers, colorants, flame retardants, UV absorbers, light stabilizers, antioxidants, anti-sagging agents, anti-aging agents, solvents, fragrances, pigments, dyes, A dehydrating agent or the like may be added.

  As the curing accelerator for the organic 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 may be used alone or in combination of two or more.

  As a viscosity modifier, it selects from the high molecular compound with a compatibility with an organic polymer (a), for example, and is suitably selected from the compound mix | 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. For selection of the thixotropic agent, it is desirable to have a surface having a high affinity for the organic 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 kinds 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. 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 include fatty acid dibasic acid esters and polypropylene glycols, and these may be used alone or in combination of two or more.

(Sealing material and adhesive)
Since the sealing material and the adhesive according to the present invention are configured using the curable composition of the present invention described above, the composition does not phase-separate, and the bleedout of the cured additive hardly occurs and is stable. A cured coating is obtained.

Since the curable composition of the present invention has the above-described configuration, the composition is not phase-separated, and a curable composition that does not easily bleed out the cured additive is obtained. When the layered silicate is further included, the weather resistance of the cured product becomes more excellent.
In addition, since the sealing material and the adhesive of the present invention are configured using the above-described curable composition of the present invention, the composition does not phase-separate, and the bleedout of the cured additive hardly occurs and is stable. It became possible to obtain a cured film.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.

(Preparation of organic polymer (a1))
In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 100 g of ethyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “ KBM-503 ") 0.5 g, 3-mercaptopropyltrimethoxysilane (Shin-Etsu Chemical Co.," KBM-803 ") 0.2 g, lauryl mercaptan (Wako Pure Chemical Industries, Ltd.) 0.25 g and ethyl acetate 100 g Then, dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring. did.

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, after 2, 3 and 4 hours after the initiation of polymerization, di (3,5,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g, and 0.36 g diluted with 1 g of ethyl acetate were sequentially added. I put it in. Seven hours after the first polymerization initiator was charged, the polymerization was terminated by cooling to room temperature. An ethyl acetate solution of an alkoxysilyl group-containing acrylate polymer having a number average molecular weight of about 20,000 (by gel permeation chromatography, molecular weight in terms of polystyrene) was obtained. The average number of silyl functional groups was 1.5.
The SP value determined by the Hoy method was 102 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

(Preparation of organic polymer (a2))
In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet, 100 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) , “KBM-503”) 0.5 g, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-803”) 0.2 g, lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) 0.25 g and ethyl acetate 100 g After the dissolved oxygen was removed by bubbling with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas and the mixture was stirred until it reached reflux. The temperature rose.

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, after 2, 3 and 4 hours after the start of polymerization, di (3,5,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g,
And a solution prepared by diluting 0.36 g with 1 g of ethyl acetate were sequentially added. Seven hours after the first polymerization initiator was charged, the polymerization was terminated by cooling to room temperature. An ethyl acetate solution of an alkoxysilyl group-containing acrylate polymer having a number average molecular weight of about 20,000 (by gel permeation chromatography, molecular weight in terms of polystyrene) was obtained. The average number of silyl functional groups was 1.5.
The SP value determined by the Hoy method was 97.7 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

(Preparation of organic polymer (a3))
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 (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. 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.

(Preparation of organic polymer (b1))
In a 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, 100 g of n-butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate After the dissolved oxygen was removed by bubbling with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas and the mixture was stirred until it reached reflux. The temperature rose.

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, after 2, 3 and 4 hours after the start of polymerization, di (3,5,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g,
And a solution prepared by diluting 0.36 g with 1 g of ethyl acetate were sequentially added. Seven hours after the first polymerization initiator was charged, the polymerization was terminated by cooling to room temperature. An ethyl acetate solution of an acrylate polymer which is an oligomer having a number average molecular weight of 5000 (molecular weight by gel permeation chromatography, the molecular weight is converted to polystyrene) was obtained. The SP value determined by the Hoy method was 97.7 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

(Preparation of organic polymer (b2))
In a 0.5 L separable flask equipped with a stirrer, cooler, thermometer and nitrogen gas inlet, 100 g of 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate After the dissolved oxygen was removed by bubbling with nitrogen gas for 20 minutes, the inside of the separable flask system was replaced with nitrogen gas and the mixture was stirred until it reached reflux. The temperature rose.

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 initiation of polymerization, di (3,5,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g, and 0.36 g were sequentially diluted with 1 g of ethyl acetate. I put it in. Seven hours after the first polymerization initiator was charged, the polymerization was terminated by cooling to room temperature. An ethyl acetate solution of an acrylate polymer which is an oligomer having a number average molecular weight of 5000 (molecular weight by gel permeation chromatography, the molecular weight is converted to polystyrene) was obtained.
The SP value obtained by the Hoy method was 92.2 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

(Preparation of organic polymer (b3))
A 0.5 L separable flask equipped with a stirrer, a cooler, a thermometer, and a nitrogen gas inlet is charged with 100 g of dodecyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 3 g of lauryl mercaptan (manufactured by Wako Pure Chemical Industries, Ltd.) and 100 g of ethyl acetate. Then, dissolved oxygen was removed by bubbling the obtained monomer mixed solution with nitrogen gas for 20 minutes, and then the inside of the separable flask system was replaced with nitrogen gas, and the temperature was raised until the reflux was reached while stirring. did.

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, after 2, 3 and 4 hours after the start of polymerization, di (3,5,5-trimethylhexanoyl) peroxide 0.048 g, 0.12 g,
And a solution prepared by diluting 0.36 g with 1 g of ethyl acetate were sequentially added. Seven hours after the first polymerization initiator was charged, the polymerization was terminated by cooling to room temperature. An ethyl acetate solution of an acrylate polymer which is an oligomer having a number average molecular weight of 5000 (molecular weight by gel permeation chromatography, the molecular weight is converted to polystyrene) was obtained.
The SP value determined by the Hoy method was 91.5 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

(Example 1)
80 g of the organic polymer (b1) ethyl acetate solution was added to 120 g of the ethyl acetate solution of the organic polymer (a1) obtained above, and the ethyl acetate was removed by an evaporator to obtain a viscous composition. Thereafter, 80 g of heavy calcium carbonate (manufactured by Shiraishi Calcium, “Whiteon P30”), 20 g of fatty acid-treated calcium carbonate (manufactured by Shiraishi Calcium, “Viscolite U”) and curing acceleration 3 g of an agent (dibutyltin dilaurate) was added and mixed with a sealed stirrer until uniform. Thereafter, it was degassed under reduced pressure for 10 minutes to obtain a white paste-like curable composition.
The SP value difference determined by the Hoy method was 4.3 × 10 ⁻⁴ (J / m ³ ) ^0.5 .

[Adhesive strength]
The obtained curable composition was applied to the end of a pentite N steel plate (150 mm × 30 mm × 2 mm) so that the coating was 0.3 mm in an area of 25 mm × 25 mm, and a slate (150 mm × 30 mm × 8 mm) was applied. The samples were bonded so that the tensile shear adhesive force could be measured, and cooled to 25 ° C. after 7 days at 50 ° C. and 50% relative humidity. Thereafter, the tensile shear adhesive strength was measured at a test speed of 5 mm / min according to JIS K 6852. The results are shown in Table 1.

[Rubber properties]
The obtained curable composition was coated on a polyethylene plate so as to have a thickness of 2 mm, and cured for 7 days in an atmosphere of 20 ° C. and a relative humidity of 50% to obtain a rubbery sheet. The obtained rubber sheet was subjected to a tensile test in a No. 3 dumbbell shape at a crosshead speed of 500 mm / min in accordance with JIS K 6301 to obtain a breaking elongation (%) and a breaking stress (N / mm ² ). The results are shown in Table 1.

[Bleed]
A laminated sheet obtained by laminating one surface of the rubber sheet with a polyethylene film was cured in an oven at 60 ° C. for 14 days, and then the polyethylene film was peeled off from the rubber sheet obtained from the curable composition of the present invention. The surface was evaluated by visual observation and tentacles. As a result, the bleed was observed for shine and oil sense by bleed, both visually and tactilely. The results are shown in Table 1.

(Example 2)
In Example 1, a curable composition was used in the same manner as in Example 1 except that the organic polymer (a2) and the organic polymer (b3) were used instead of the organic polymer (a1) and the organic polymer (b1). Evaluation similar to Example 1 was performed about the obtained curable composition obtained. The results are shown in Table 1.

(Example 3)
In Example 1, a curable composition was obtained in the same manner as in Example 1 except that the organic polymer (a3) was used instead of the organic polymer (a1). The obtained curable composition was carried out. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, a curable composition was obtained in the same manner as in Example 1 except that the organic polymer (b2) was used instead of the organic polymer (b1). The obtained curable composition was carried out. Evaluation similar to Example 1 was performed. The results are shown in Table 1.

From Table 1, the curable composition in which the SP value difference between the organic polymer (a) and the organic polymer (b) is 7 × 10 ⁻⁴ (J / m ³ ) ^0.5 or less is good without bleeding. I know that there is.

Example 4
In preparing the curable composition of Example 1, 10 g of layered silicate “Somasif MPE-100” (swelling fluorinated mica organically treated with polyoxypropylene diethyl quaternary ammonium salt, manufactured by Coop Chemical Co., Ltd.), “Tinubin 770 Except that 5 g of “hindered amine light stabilizer, manufactured by Ciba Specialty Chemicals” and 5 g of “Tinubin 327” (benzotriazole UV absorber, manufactured by Ciba Specialty Chemicals) were added, the same as in Example 1. A curable composition was obtained.

(Measurement of average interlayer distance of layered silicate)
The average interlayer distance of the layered silicate in the curable composition obtained in Example 3 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) is the surface spacing of the layered silicate, and θ (degree) is the 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)
The weather resistance of the curable compositions obtained in Examples 1 and 3 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. Under the conditions, light irradiation was performed for 150 hours and 400 hours, and the surface state was visually confirmed. The case where there were no cracks was judged as ◯, and the case where some cracks occurred was judged as Δ. The results are shown in Table 2 below.

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)
(Note that the light irradiation evaluation by the eye super UV tester varies depending on the material system and test conditions, so it cannot be said unconditionally. However, it is usually about 10 times as severe as that of the sunshine weatherometer. It is said that)

  From Table 2, it can be seen that those with the addition of layered silicate have better weather resistance.

  ADVANTAGE OF THE INVENTION According to this invention, the curable composition from which the bleed-out of the additive after hardening cannot produce easily and a stable cured film is obtained can be provided. Furthermore, the said curable composition can be widely used for various uses, such as a coating material, a coating material, a sealant, a sealing material, an adhesive agent, a pressure sensitive adhesive agent, a primer.

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 (4)

Organic weight having an SP value difference of 7 × 10 ⁻⁴ (J / m ³ ) ^0.5 or less between the organic polymer (a) containing at least a crosslinkable hydrolyzable silyl group and the organic polymer (a) A curable composition comprising a combination (b). The curable composition according to claim 1, further comprising a layered silicate. A sealing material comprising the curable composition according to claim 1. An adhesive comprising the curable composition according to claim 1 or 2.

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