JP2005290168A - Curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition using a polyoxyalkylene-based polymer having a hydrolyzable silicon-containing group, excellent in weather resistance and further having good workability. <P>SOLUTION: The curable composition comprises a polymer (A) having an alkylene oxide monomer unit on the main chain and having at least one hydrolyzable silicon-containing group per molecule and polymer fine particles (B), dispersed in the polymer (A), in which a polymer (b) having an alkylene skeleton on the main chain can be three-dimensionally crosslinked and/or is three-dimensionally crosslinked. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group.

  Polymers having hydrolyzable silicon-containing groups are used in curable compositions for applications such as sealants and adhesives because of their excellent curability at room temperature and ease of compounding design. In particular, a polymer having a polyoxyalkylene-based main chain (hereinafter, also simply referred to as “polyoxyalkylene-based polymer”) is excellent in curability, adhesiveness, safety, non-contamination, and the like. , Sealing agents, potting agents, elastic adhesives, coating materials, lining materials, adhesives and the like. Among these, as a sealing material, it is used for both room temperature moisture hardening type one component form and room temperature moisture hardening type two component form.

  However, the composition using the polyoxyalkylene-based polymer having a hydrolyzable silicon-containing group described above is superior in adhesiveness and non-staining properties compared to the polyisobutylene-based and silicone-based sealing material compositions. However, it has a problem that the weather resistance is inferior, and there is room for improvement particularly as a sealing material for construction.

  Accordingly, an object of the present invention is to provide a curable composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group, which has excellent weather resistance and further improved workability.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a specific polymer can be three-dimensionally crosslinked and / or a polyoxyalkylene polymer having a hydrolyzable silicon-containing group. It was found that when fine particles were dispersed, a curable composition having excellent weather resistance and good workability was obtained, and the present invention was completed.
That is, this invention provides the curable composition shown to the following (1)-(15).

(1) containing a polymer and fine polymer particles dispersed in the polymer,
The polymer is a polymer (A) having an alkylene oxide monomer unit in the main chain and having at least one hydrolyzable silicon-containing group per molecule,
The curable composition, wherein the polymer fine particles are polymer fine particles (B) in which the polymer (b) having an alkylene skeleton in the main chain can and / or three-dimensionally crosslink.

  (2) The polymer fine particles (B) can be three-dimensionally cross-linked by the reaction of the functional group of the polymer (b) having a crosslinkable functional group (B) and / or the polymer fine particles (B). The curable composition as described in said (1).

  (3) The curable composition according to (1) or (2), further comprising a curing catalyst (C) of the polymer (A).

  (4) The curable composition according to any one of (1) to (3), further comprising a compatibilizer (D).

  (5) The curable composition according to any one of (1) to (4), wherein the alkylene skeleton of the polymer (b) is composed of an isobutylene monomer unit.

  (6) The curable composition according to any one of (1) to (4), wherein the alkylene skeleton of the polymer (b) is composed of an ethylene / α-olefin / non-conjugated polyene monomer unit.

  (7) The polymer (b) has a hydrolyzable silicon-containing group, and the polymer fine particles (B) can and / or are three-dimensionally crosslinked by hydrolysis of the polymer (b). The curable composition according to any one of (1) to (6).

  (8) The polymer (b) has an alkenyl group, and the polymer fine particles (B) can be three-dimensionally crosslinked by a hydrosilylation reaction between the polymer (b) and a compound having a hydrosilyl group, and / or The curable composition according to any one of (1) to (6) above.

  (9) The curable composition according to any one of (1) to (8), wherein the polymer fine particles (B) have a hydrolyzable silicon-containing group.

  (10) The above (9), wherein all or part of the hydrolyzable silicon-containing group of the polymer fine particle (B) is introduced into the polymer fine particle (B) by reaction with a silane coupling agent. The curable composition according to 1.

  (11) The curable composition according to (10), wherein the silane coupling agent is aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof.

  (12) The curable composition according to the above (10) or (11), wherein the amount of the silane coupling agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A).

  (13) The curable composition according to any one of (1) to (12), which contains 1 to 100 parts by mass of the polymer fine particles (B) with respect to 100 parts by mass of the polymer (A).

  (14) The curable composition according to any one of (3) to (13), which contains 0.1 to 20 parts by mass of the curing catalyst (C) with respect to 100 parts by mass of the polymer (A). Stuff.

  (15) The curable composition according to any one of (4) to (14) above, containing 0.1 to 10 parts by mass of a compatibilizer (D) with respect to 100 parts by mass of the polymer (A). Stuff.

  As will be described below, according to the present invention, there is provided a curable composition using a polyoxyalkylene polymer having a hydrolyzable silicon-containing group, which is excellent in weather resistance and workability. It is useful because it can.

The present invention is described in detail below.
The curable composition of the present invention contains a polymer and fine polymer particles dispersed in the polymer, the polymer contains an alkylene oxide monomer unit in the main chain, and a hydrolyzable silicon-containing group. Is a polymer (A) having at least one per molecule, and the polymer fine particles (B) can be three-dimensionally crosslinked and / or polymer fine particles (B) having an alkylene skeleton in the main chain (B) Is a curable composition.
The curable composition of the present invention substantially becomes a mixed dispersion of the polymer (A) and the polymer fine particles (B), and the polymer (A It is preferable to contain a curing catalyst (C) of the above polymer (A), and not a copolymer or blend of resin components), and if necessary, a compatibilizer (D). May be.
Next, the polymer (A), the polymer fine particles (B), and the curing catalyst (C) and the compatibilizer (D) that can be optionally used will be described in detail.

<Polymer (A)>
The polymer (A) used in the present invention is a polymer having a main chain containing an alkylene oxide monomer unit and at least one hydrolyzable silicon-containing group per molecule. In the present invention, the hydrolyzable silicon-containing group may be present at the terminal in the molecule of the polymer, may be present in the side chain, or may be present in both.

Examples of the alkylene oxide monomer unit contained in the polymer (A) include —CH ₂ CH ₂ O—, —CH ₂ CH (CH ₃ ) O—, —CH ₂ CH (C ₂ H ₅ ) O—. _{, -CH (CH 3) CH 2} O -, - CH (C 2 H 5) CH 2 O -, - expressed CH ₂ CH ₂ CH ₂ O- or -CH ₂ CH ₂ CH ₂ CH ₂ O- in Repeat units are mentioned.
The main chain of the polymer (A) may consist of only one of these repeating units or may consist of two or more.
The main chain of a polymer (A) may be used independently and may use 2 or more types together.

  The hydrolyzable silicon-containing group has a hydroxyl group and / or hydrolyzable group bonded to a silicon atom, and causes a condensation reaction by using a catalyst or the like in the presence of moisture or a cross-linking agent, if necessary. A silicon-containing group that can be cross-linked by forming a bond. Examples thereof include an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidosilyl group. Specifically, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, an amidosilyl group and the like exemplified by the following formula are preferably used.

Among these, an alkoxysilyl group is preferable because it is easy to handle.
Although the alkoxy group couple | bonded with the silicon atom of an alkoxy silyl group is not specifically limited, Since acquisition of a raw material is easy, a methoxy group, an ethoxy group, or a propoxy group is mentioned suitably.
The group other than the alkoxy group bonded to the silicon atom of the alkoxysilyl group is not particularly limited. For example, a hydrogen atom or an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group An alkenyl group or an arylalkyl group is preferable.

  The polymer (A) is preferably bifunctional or more, that is, alkoxysilanes having two or more alkoxysilyl groups in the molecule, and 3 to 20 functional alkoxysilanes are more preferable because the raw materials are easily available. .

  The molecular weight of such a polymer (A) is not particularly limited, but a polymer having a high viscosity and may be difficult to handle. Therefore, the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC). Is preferably 50,000 or less.

  A polymer (A) may be used independently and may use 2 or more types together.

  The polymer (A) can be produced by a known method.

Known polyoxyalkylene polymers containing such hydrolyzable silicon-containing groups can be used.
For example, Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55- Nos. 123620, 55-125121, 55-131022, 55-135135, 55-137129, and JP-A-3-72527 can be used. Further, as commercially available products, for example, MSP S203, S303, S810 and S943 manufactured by Kaneka Chemical Co., Ltd., EXCESTAR ES-S2410, ES-S2420, ES-S3430 and ES-S3630 manufactured by Asahi Glass Co., Ltd. can be used. .

<Polymer fine particles (B)>
The polymer fine particles (B) used in the present invention are polymer fine particles in which the polymer (b) having an alkylene skeleton in the main chain can be three-dimensionally cross-linked and / or formed in the polymer (A) described above. Are distributed.
Below, a polymer (b) is demonstrated.

<Polymer (b)>
The polymer (b) is a polymer having an alkylene skeleton in the main chain, and preferably has a crosslinkable functional group.

  The main chain of the polymer (b) is not particularly limited as long as it has an alkylene skeleton, but it has an alkylene skeleton composed of isobutylene monomer units or ethylene / α-olefin / non-conjugated polyene monomer units. It is preferable. Moreover, it is preferable that the ratio of these monomer units exceeds 50 mass%, and it is more preferable that it is 70 mass% or more.

  Here, the alkylene skeleton composed of isobutylene monomer units is specifically formed substantially from polyisobutylene (PIB).

  The alkylene skeleton composed of ethylene / α-olefin / non-conjugated polyene monomer unit is a rubber-like ternary produced by random copolymerization of ethylene, α-olefin and non-conjugated polyene. It is formed of a copolymer (EPDM). This EPDM is also called ethylene propylene terpolymer (EPT).

  Here, the α-olefin is preferably an α-olefin having 3 to 20 carbon atoms, and specific examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene 1-eicosene and the like. These may be used alone or in combination of two or more. Among these, α-olefins having 3 to 10 carbon atoms, particularly propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable.

  The ratio (molar ratio) of ethylene and α-olefin in the copolymer (EPDM) is 60/40 to 80/20, preferably 62/38 to 79/21, expressed as ethylene / α-olefin. Especially preferably, it exists in the range of 65 / 35-78 / 22. If it is this range, the copolymer which shows favorable rubber elasticity will be obtained.

  Specific examples of the non-conjugated polyene include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, Chain non-conjugated dienes such as 4,5-diethyl-1,4-hexadiene and 7-methyl-1,6-octadiene; methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 -Isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4 Pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- ( 3-methyl-5-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- ( 7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5 Cyclic non-conjugated dienes such as ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene; 2,3-diisopropylidene-5-norbornene, 2 -Trienes such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene; These may be used alone or in combination of two or more.

  When the content of non-conjugated polyene in the copolymer (EPDM) is expressed in terms of iodine value, the iodine value is 10 to 50, preferably 15 to 40, more preferably 18 to 35, and particularly preferably 20 to 30. Is desirable. When the iodine value is within this range, an appropriate effective network chain density can be obtained, so that the compression set is small and the environmental degradation resistance is good.

  Such a copolymer (EPDM) may be used alone or in combination of two or more, and a modified product thereof may also be used. This copolymer (EPDM) can be easily produced by a method described in “Polymer Production Process” (published by Industrial Research Council, Inc., pages 309 to 330).

  The polymer (b) having such a main chain is preferably a polymer having a hydrolyzable silicon-containing group or alkenyl group as a crosslinkable functional group.

When the polymer (b) has a hydrolyzable silicon-containing group, the number of hydrolyzable silicon-containing groups is at least one per molecule. Further, the bonding position of the hydrolyzable silicon-containing group may be any of the main chain terminal, the main chain, and the side chain (including the graft body), but the main chain terminal is preferable. More preferably, it is only the chain end.
Here, the hydrolyzable silicon-containing group as a crosslinkable functional group is the same as that described for the polymer (A).

The method for introducing a hydrolyzable silicon-containing group into the main chain of the polymer (b) is not particularly limited, and examples thereof include a method described in JP-A-9-208622.
Specifically, after polymerizing monomers mainly composed of isobutylene or ethylene / α-olefin / non-conjugated polyene, a polymerization terminator such as 1,9-decadiene, allylmethylsilane, allyl halide is added. And a method of producing a polymer having an alkenyl group obtained by reacting with a hydrosilane having a hydrolyzable silicon-containing group by a hydrosilylation reaction.
Here, a hydrosilane having a hydrolyzable silicon-containing group has at least one silicon group bonded to a hydroxyl group or a hydrolyzable group in the molecule, and has at least one Si-H group in the molecule. The compound is not particularly limited, and specific examples thereof include trichlorosilane, methyldichlorosilane, dimethylchlorosilane, phenyldichlorosilane, trimethylsiloxymethylchlorosilane, 1,1,3,3-tetra Halogenated silanes such as methyl-1-bromodisiloxane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethylsiloxymethylmethoxysilane, trimethylsiloxydiethoxysilane Class: methyldiacetoxysilane, phenyldia Acyloxysilanes such as toxisilane, triacetoxysilane, trimethylsiloxymethylacetoxysilane, trimethylsiloxydiacetoxysilane; bis (dimethylketoxymate) methylsilane, bis (cyclohexylketoximate) methylsilane, bis (diethylketoximate) trimethyl Ketoximate silanes such as siloxysilane, bis (methylethylketoximate) methylsilane, tris (acetoxymate) silane; alkenyloxysilanes such as methylisopropenyloxysilane; and the like.

In the hydrosilylation reaction, a group VIII transition metal catalyst is preferably used. For example, a metal complex catalyst selected from group VIII transition metal elements such as platinum, rhodium, cobalt, palladium, nickel, etc. is used effectively. be able to.
Specifically, H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, platinum-olefin complex, Pt metal, RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _{4 and} the like can be used. From the viewpoint of hydrosilylation reactivity, any of platinum-vinylsiloxane complex and platinum-olefin complex can be used. It is particularly preferable.

When the polymer (b) has an alkenyl group, the number of the alkenyl group is at least one per molecule. Further, the bonding position of the alkenyl group may be any of the main chain terminal, the main chain, and the side chain (including the graft body), but is preferably the main chain terminal, and only the main chain terminal. More preferably.
Here, examples of the polymer (b) having an alkenyl group include a polymer having an alkenyl group obtained by polymerizing a monomer mainly composed of isobutylene or ethylene / α-olefin / non-conjugated polyene.

  The molecular weight of such a polymer (b) is not particularly limited, but those having a number average molecular weight in terms of polystyrene in GPC of 500 to 100,000 are difficult in polymerization, compatible, and handling viscosity. Is preferable.

  A polymer (b) is used individually or in mixture of 2 or more types.

  A well-known thing can be used as a polymer (b). Specifically, examples of the PIB skeleton include EPION (both end reactive polyisobutylene oligomer) EP100S, EP303S, EP505S, EP200A, EP400A, EP600A, etc. manufactured by Kaneka Chemical Industry Co., Ltd. An example is Mitsui-EPT manufactured by Mitsui Chemicals.

The polymer fine particles (B) are formed by the above-mentioned polymer (b) and / or can be three-dimensionally crosslinked. The mode of three-dimensional crosslinking is not particularly limited.
For example, when the polymer (b) has a hydrolyzable silicon-containing group as a crosslinkable functional group, a mode in which the polymer (b) is three-dimensionally crosslinked by addition of water or the like can be mentioned. In the hydrolysis, a conventionally known catalyst such as a tin catalyst or an amine catalyst (for example, the curing catalyst (C) exemplified as the curing catalyst for the polymer (A) described above) can be used.
In addition, when the polymer (b) has an alkenyl group as a crosslinkable functional group, the hydrosilane having a hydrolyzable silicon-containing group exemplified above or a compound having another hydrosilyl group (for example, 1 , 3,5,7-tetramethylcyclotetrasiloxane, α, ω-polyorganohydropolysiloxane), and three-dimensional crosslinking may be mentioned. Platinum, rhodium, cobalt, palladium, nickel, etc. A metal complex catalyst selected from the group VIII transition metal elements can be used.

The polymer fine particles (B) are dispersed in the polymer (A) described above.
The method for dispersing is not particularly limited, and examples thereof include a method in which polymer fine particles (B), preferably gel fine polymer particles (B) are added to the polymer (A), and the mixture is dispersed by high-speed stirring.
In particular, when the polymer (b) has an alkenyl group as a crosslinkable functional group, the polymer (b) and the compound having the hydrosilyl group described above are added to the polymer (A), By stirring at high speed, the polymer fine particles (B) may be dispersed while the three-dimensional crosslinking of the polymer (b) proceeds.
In order to stir at high speed, for example, a stirrer having a vibro mixer, a gyro mixer, a high speed disper, etc. can be used, and the external shear force between the fluid containing the polymer (A) and the vessel wall surface or the stirring blade is used. However, what used the internal shear force (Reynolds stress) of the fluid itself may be sufficient.

In the present invention, it is one of preferred embodiments that the polymer fine particles (B) have a hydrolyzable silicon-containing group. When the polymer fine particle (B) has a hydrolyzable silicon-containing group, the hydrolyzable silicon-containing group of the polymer fine particle (B) is cured when the hydrolyzable silicon-containing group of the polymer (A) is hydrolyzed and cured. Are also hydrolyzed and reacted at the same time, a bond between the polymer (A) and the polymer fine particles (B) is formed, and the physical properties after curing become more excellent.
The method for allowing the polymer fine particles (B) to have a hydrolyzable silicon-containing group is not particularly limited, but it is preferable that all or part of the polymer fine particles (B) be introduced by reaction with a silane coupling agent. For example, when the polymer (b) has a functional group, a method of directly reacting a silane coupling agent having a functional group capable of reacting with the functional group and a hydrolyzable silicon-containing group can be mentioned.

  Such a silane coupling agent is not particularly limited, but is preferably amino silane, vinyl silane, epoxy silane, (meth) acryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof.

Examples of aminosilane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, and bistriethoxysilylpropylamine. Bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, Examples thereof include N-2- (aminoethyl) -3-aminopropyltriethoxysilane and N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane.
Examples of the vinyl silane include vinyl trimethoxy silane, vinyl triethoxy silane, and tris- (2-methoxy ethoxy) vinyl silane.
Examples of the epoxy silane include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyl. Examples include dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
Examples of methacrylic silane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Examples of the isocyanate silane include isocyanate propyl trimethoxy silane and isocyanate propyl triethoxy silane.
Examples of the ketimine silane include ketiminated propyltrimethoxysilane.
These may be used alone or in combination of two or more.

  It is preferable that the quantity of a silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of polymers (A) mentioned above.

  In these methods, the polymer fine particles (B) can be reacted with the silane coupling agent after the production, and the polymer fine particles (B) can be reacted with the silane coupling agent during the production.

  The polymer fine particles (B) have an average particle diameter of 0.01 to 100 μm from the viewpoint of being uniformly dispersed in the polymer (A), and having excellent adhesion and elongation after curing. Preferably, it is 0.1-50 micrometers.

  The content of the polymer fine particles (B) in the curable composition of the present invention is 1 to 100 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 100 parts by mass of the polymer (A) described above. 40 parts by mass. Within the above range, a curable composition having workability (for example, physical properties such as viscosity and thixotropic properties) and appearance characteristics (for example, color tone, gloss, etc.) equivalent to or higher than those of conventional curable compositions is obtained.

<Curing catalyst (C)>
It is preferable that the curable composition of this invention contains the curing catalyst (C) of a polymer (A) other than the said polymer (A) and polymer fine particle (B). By containing a curing catalyst, the curable composition of the present invention can accelerate the progress of the curing reaction and shorten the work time to reach the curing, thereby reducing the tack-free time and practically. Excellent.

  The curing catalyst (C) is not particularly limited, and examples thereof include zinc octoate, iron octoate, manganese octoate, tin octoate, zinc naphthenate, iron naphthenate, tin butanoate, tin caprylate, and tin oleate. Carboxylic acid metal salts such as: dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate, dibutyltin oxide, reaction product of dibutyltin oxide and phthalate, dibutyltin dimethoxide , Organotin compounds such as dibutyltin (triethoxysiloxy), dibutyltin diacetylacetonate, dibutyltin silicate; tin chelate compounds such as dibutyltin diacetylacetonate; tetraethoxytitanium Titanic acid esters such as tetrapropoxy titanium, tetrabutoxy titanium, tetra-2-ethylhexyloxy titanium, tetraisopropenyloxy titanium; diisopropoxy titanium bis (acetylacetonate), diisopropoxy titanium bis (ethyl acetoacetate), 1, Titanium chelate compounds such as 3-propanedioxytitanium bis (acetylacetonate), 1,3-propanedioxytitanium bis (ethylacetoacetate), titanium tris (acetylacetonate); tetraisopropoxyzirconium, tetrabutoxyzirconium, tri Zirconium alkoxides such as butoxyzirconium stearate; Zirconium chelate compounds such as zirconium tetra (acetylacetonate); Triethoxyal Aluminum alkoxides such as aluminum, tripropoxyaluminum and tributoxyaluminum; aluminum chelate compounds such as diisopropoxyaluminum (ethyl acetoacetate), aluminum tris (acetylacetonate) and aluminum tris (ethylacetoacetate); butylamine and hexyl Primary amines such as amine, octylamine, dodecylamine, oleylamine, cyclohexylamine, benzylamine; secondary amines such as dibutylamine; such as diethylenetriamine, triethylenetetramine, guanidine, diphenylguanidine, xylylenediamine Polyamine; triethylenediamine, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-di Cyclic amines such as azabicyclo [5.4.0] -7-undecene; aminoalcohol compounds such as monoethanolamine, diethanolamine and triethanolamine; such as 2,4,6-tris (dimethylaminomethyl) phenol Amine compounds such as aminophenol compounds and their carboxylates; quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds The reaction product etc. are mentioned. These curing catalysts (C) may be used independently and may use 2 or more types together.

  Among these, metal compounds are preferable because they are less likely to volatilize during storage and handling. Among them, amine compounds and carboxylic acid metal salts, organotin compounds, tin chelates are obtained because excellent catalytic ability can be obtained with a small amount of compounding. Compounds and titanates are preferred.

  Moreover, 0.1-20 mass parts is preferable with respect to 100 mass parts of polymers (A), and, as for the content of a curing catalyst (C), it is more preferable that it is 0.1-10 mass parts. When the content of the curing catalyst (C) is within this range, the effect of the curing catalyst can be sufficiently exerted, there is no problem with compatibility with other components, and local heat generation and foaming may occur during curing. Absent.

<Compatibilizer (D)>
The curable composition of the present invention preferably contains a compatibilizer (D) in addition to the polymer (A) and the polymer fine particles (B). The compatibilizing agent is contained for various purposes. Examples of the purpose include generation of polymer fine particles, dispersion of polymer fine particles, and adjustment of physical properties after curing.
In general, for example, when the polymer A and the polymer B are in an incompatible mixed system, the copolymer of the polymer A monomer and the polymer B monomer is a surfactant. It plays such a role, and at the interface between the polymer A and the polymer B, functions such as lowering the interfacial tension, controlling the interface layer, and repelling action of the dispersion layer are exhibited. That is, the compatibilizing agent bears important functions such as fine dispersion and improved adhesion between the two at the interface.

  Examples of such a compatibilizing agent (D) include those that are the same as the blend component; some of the other components that are compatible with the blend component; a copolymer that includes a monomer other than the polymer A and the polymer B Each having the same or similar solubility parameter value; a copolymer of another monomer that reacts with polymer A or polymer B and is compatible with the other polymer; polymer A and polymer B In the blending process, a graft and / or block copolymer is partially formed to act as a compatibilizing agent.

Further, the compatibilizing agent (D) in the present invention has two or more substances having different chemical characteristics in the same molecule, and the surfactant, admixture, emulsifier, solubilization depending on its function. It is called an agent or a dispersant.
Examples of the compatibilizer (D) used in the present invention include polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, lecithin, saponin, amine ethoxylate, and alcohol ethoxylate. Nonionic surfactants are preferred.
The compatibilizer (D) is preferably added at the time of dispersion when the method of dispersing the polymer fine particles (B) is a method of adding the polymer fine particles (B) to the polymer (A) and stirring. When the polymer fine particles (B) are dispersed while the three-dimensional crosslinking of the polymer (b) proceeds in the polymer (A), the polymer fine particles (B) may be added after the formation of the polymer fine particles (B). It may be added during the generation of B) or at the initial stage of the generation of polymer fine particles (B), and it is preferable to select a method as appropriate according to various conditions.

  The compatibilizing agent (D) can be used alone or in combination of two or more. The ratio in the case of using 2 or more types in combination can be appropriately determined according to the use in which the curable composition of the present invention is used, the physical properties required for the curable composition of the present invention, and the like.

  Content of a compatibilizing agent (D) is 0.1-10 mass parts with respect to 100 mass parts of polymers mentioned above, Preferably it is 0.2-5 mass parts.

In one preferred embodiment, the curable composition of the present invention contains calcium carbonate.
The calcium carbonate used in the present invention is not particularly limited, and examples thereof include heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate), and colloidal calcium carbonate.
Moreover, the surface treatment calcium carbonate surface-treated with a fatty acid, a resin acid, a fatty acid ester, a higher alcohol addition isocyanate compound, etc. can also be used. Specifically, as calcium carbonate surface-treated with a fatty acid, Calfine 200 (manufactured by Maruo Calcium Co., Ltd.), Ryton 26-A (heavy calcium carbonate, manufactured by Bihoku Flour Industries Co., Ltd.), Shiraka Hana CCR (manufactured by Shiraishi Kogyo Co., Ltd.) ), Calcium carbonate surface-treated with modified fatty acid, Ryton A-4 (heavy calcium carbonate, manufactured by Bihoku Flour Chemical Co., Ltd.), calcium carbonate surface-treated with fatty acid ester, Sealet 200 (manufactured by Maruo Calcium Co., Ltd.) Snowlight SS (heavy calcium carbonate, manufactured by Maruo Calcium Co., Ltd.) is preferably used. Of these, those that have been surface-treated with fatty acids, modified fatty acids, fatty acid esters, higher alcohol-added isocyanate compounds, and the like are particularly preferred. The surface-treated calcium carbonate contributes to shape retention and workability because the viscosity is increased, and contributes to storage stability because the surface is hydrophobic.
These may be used alone or in combination of two or more.

  The content of calcium carbonate is preferably 50 to 400 parts by mass with respect to 100 parts by mass of the polymer (A) described above.

In one preferred embodiment, the curable composition of the present invention contains a hydrolyzable compound having a molecular weight of 1000 or less. The hydrolyzable compound is effectively used to absorb moisture contained in the polymer, calcium carbonate, etc. and improve storage stability.
Examples of such hydrolyzable compounds include relatively low molecular weight silane coupling agents such as vinyl silane, oxime silane, amino silane, epoxy silane, and mercapto silane; methyl orthoformate, ethyl orthoformate, 2-phenyl-3- Examples include hydrolyzable compounds such as oxazolidineethanol and polyoxyalkylene-methylstearoxypolysiloxane copolymers.
These may be used alone or in combination of two or more.

  The content of the hydrolyzable compound having a molecular weight of 1000 or less is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymer (A) described above.

The curable composition of the present invention can further contain the above-mentioned silane coupling agent separately from the one for introducing a hydrolyzable silicon-containing group into the polymer fine particles (B).
The content of the silane coupling agent is the sum of the content of the polymer fine particles (B) for introducing the hydrolyzable silicon-containing group and the content of the silane coupling agent, and is preferably within the above range.

  The curable composition of the present invention can contain various additives as necessary in addition to the above-mentioned various components within a range not impairing the object of the present invention. Examples of additives include fillers other than calcium carbonate, plasticizers, softeners, thixotropy imparting agents, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants, adhesion imparting agents, and dispersions. Agents and solvents.

  As fillers other than calcium carbonate, those having various shapes can be used. For example, fumed silica, calcined silica, precipitated silica, ground silica, fused silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide, barium oxide, magnesium oxide; magnesium carbonate, zinc carbonate; Fired clay; organic or inorganic fillers such as carbon black; these fatty acids, resin acids, fatty acid ester treated products, fatty acid ester urethane compound treated products; resin balloons.

  Examples of the plasticizer or softener include, for example, plasticizers such as diisononyl phthalate (DINP), phthalates such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; dioctyl adipate, succinate Aliphatic dibasic acid esters such as isodecyl acid and dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol ester; aliphatic esters such as butyl oleate and methyl acetylricinoleate; tricresyl phosphate and phosphoric acid Phosphate esters such as trioctyl, octyl diphenyl phosphate; propylene glycol adipate polyester, butylene glycol polyester adipate; epoxidized soybean oil, epoxidized linseed oil, epoxy stearate Epoxy plasticizers such as Gil; Polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols; Polyethers such as polypropylene glycol and its derivatives; Polystyrenes such as poly-α-methylstyrene and polystyrene; Examples thereof include polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene; petroleum softeners such as paraffinic oil, naphthenic oil, and aromatic oil.

Examples of the thixotropic agent (thixotropic agent) include dry silica, white carbon, hydrogenated castor oil, calcium carbonate, Teflon (registered trademark), organic amide wax, calcium stearate, organic bentonite, and Japanese Patent Application Laid-Open No. 2003-171121. And calcium carbonate described in the above.
Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine, bengara, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; organic pigments such as azo pigments and copper phthalocyanine pigments. It is done.

Examples of the antiaging agent include hindered phenol compounds, hindered amine compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, and nickel complex salts.
Examples of the antioxidant include butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), phenolic compounds, amine compounds, sulfur compounds, and phosphorus compounds.
Examples of the antistatic agent include quaternary ammonium salts; hydrophilic compounds such as polyglycols and ethylene oxide derivatives.

Examples of the flame retardant include chloroalkyl phosphate, dimethyl / methylphosphonate, bromine / phosphorus compound, ammonium polyphosphate, neopentyl bromide-polyether, and brominated polyether.
Examples of the adhesion imparting agent include terpene resins, phenol resins, terpene-phenol resins, rosin resins, xylene resins, and epoxy resins.
The above additives can be used in combination as appropriate.

  The method for producing the curable composition of the present invention from each component as described above is not particularly limited. As described above, after dispersing or forming the polymer fine particles (B) in the polymer (A), Examples include a method in which other components are sufficiently kneaded and uniformly dispersed under a reduced pressure or an inert gas atmosphere such as nitrogen using a stirring apparatus such as a mixing mixer.

The curable composition of the present invention is moisture curable and can be used as a one-component composition. In addition, if necessary, the main component is a component other than the curing agent (the curing catalyst (C) described above), and before use, the main component (liquid A) and the curing agent (liquid B) are mixed and used according to a conventional method. It can also be used as a composition in the form.
When the curable composition of the present invention is exposed to moisture, the curing reaction proceeds by hydrolysis of the hydrolyzable silicon-containing group. In addition, the curing reaction can be advanced by appropriately supplying water.

  When using the curable composition of this invention as a sealing material etc., you may use it, after apply | coating a primer to a to-be-adhered body. A conventionally well-known thing can be used as a primer.

  The curable composition of the present invention is a sealing material, a sealing agent, a potting agent, an elastic adhesive, a coating material, a lining material, and an adhesive for civil engineering, concrete, wood, metal, glass, and plastic. It is suitably used for such applications.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Preparation of dispersion mixture>
Dispersion mixtures 1 to 8 in which the polymer fine particles (B) were dispersed in the polymer (A) were prepared by the following method.

(Preparation of dispersion mixture 1)
15 parts by mass of polymer b1 (EPION EP200A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 1,3,5,7-tetramethylcyclotetrasiloxane (hereinafter, "TMCTS" is abbreviated.) 0.9 parts by mass and 1.125 parts by mass of dimethylmaleic acid (diluted 1/100, manufactured by Kanto Chemical Co., Ltd.) as a reaction retarder were added, followed by stirring for 10 minutes.
After adding 70 parts by mass of polymer A1 (MS polymer S810, Kaneka Chemical Co., Ltd.) to the mixture after stirring and stirring for 10 minutes, platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals, (Japan Co., Ltd.) 1.68 parts by mass was added and stirred for 3 minutes to prepare dispersion mixture 1 in which polymer fine particles B1 derived from polymer b1 were dispersed in polymer A1.

(Preparation of dispersion mixture 2)
15 parts by mass of polymer b2 (EPION EP400A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 0.9 part by mass of TMCTS, and dimethylmaleic acid (1/100 dilution) , Manufactured by Kanto Chemical Co., Ltd.) and stirred for 10 minutes.
After adding 70 parts by mass of polymer A1 (MS polymer S810, Kaneka Chemical Co., Ltd.) to the mixture after stirring and stirring for 10 minutes, platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals, (Distributed by Japan) 0.84 parts by mass was added and stirred for 3 minutes to prepare dispersion mixture 2 in which polymer particles B2 derived from polymer b2 were dispersed in polymer A1.

(Preparation of dispersion mixture 3)
15 parts by mass of polymer b3 (EPION EP600A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 0.6 parts by mass of TMCTS, and dimethylmaleic acid (1/100 dilution) , Manufactured by Kanto Chemical Co., Ltd.) and stirred for 10 minutes.
After adding 70 parts by mass of polymer A1 (MS polymer S810, Kaneka Chemical Co., Ltd.) to the mixture after stirring and stirring for 10 minutes, platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals, (Distributed by Japan) 0.495 parts by mass was added and stirred for 3 minutes to prepare dispersion mixture 3 in which polymer particles B3 derived from polymer b3 were dispersed in polymer A1.

(Preparation of dispersion mixture 4)
15 parts by mass of polymer b3 (EPION EP600A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 0.3 part by mass of TMCTS, and dimethylmaleic acid (1/100 dilution) , Kanto Chemical Co., Ltd.) 0.33 parts by mass and γ-glycidoxypropyltrimethoxysilane (A-187, Nihon Unicar Co., Ltd.) 0.354 parts by mass were stirred for 10 minutes.
After adding 70 parts by mass of polymer A1 (MS polymer S810, Kaneka Chemical Co., Ltd.) to the mixture after stirring and stirring for 10 minutes, platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals, (Distributed by Japan) 0.495 parts by mass was added and stirred for 3 minutes to prepare dispersion mixture 4 in which polymer fine particles B4 having hydrolyzable silicon-containing groups were dispersed in polymer A1.

(Preparation of dispersion mixture 5)
15 parts by mass of polymer b3 (EPION EP600A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 0.3 part by mass of TMCTS, and dimethylmaleic acid (1/100 dilution) , Manufactured by Kanto Chemical Co., Ltd.) and stirred for 10 minutes.
To the mixture after stirring, 70 parts by mass of polymer A1 (MS polymer S810, manufactured by Kaneka Chemical Co., Ltd.) was added and stirred for 10 minutes, and further platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals Japan). 0.495 parts by mass) was added and stirred for 3 minutes, and 0.345 parts by mass of γ-glycidoxypropyltrimethoxysilane (A-187, Nihon Unicar) was added and stirred for 15 minutes. Thus, a dispersion mixture 5 was prepared in which polymer fine particles B5 having hydrolyzable silicon-containing groups on the surface thereof were dispersed in the polymer A1.

(Preparation of dispersion mixture 6)
15 parts by mass of polymer b3 (EPION EP600A, Kaneka Chemical Co., Ltd.), 15 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.), 0.3 part by mass of TMCTS, and dimethylmaleic acid (1/100 dilution) , Manufactured by Kanto Chemical Co., Ltd.) and stirred for 10 minutes.
To the mixture after stirring, 70 parts by mass of polymer A1 (MS polymer S810, manufactured by Kaneka Chemical Co., Ltd.) was added and stirred for 10 minutes, and further platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals Japan). 0.495 parts by mass) was added and stirred for 3 minutes. Further, 0.308 parts by mass of isocyanate silane (trade name: Y-5187, manufactured by Nihon Unicar) was added and stirred for 15 minutes. A dispersion mixture 6 was prepared in which polymer fine particles B6 having hydrolyzable silicon-containing groups were dispersed in the coalescence A1.

(Preparation of dispersion mixture 7)
After adding 24 parts by mass of process oil (PS32, Idemitsu Kosan Co., Ltd.) and TMCTS 0.36 parts by mass to 6 parts by mass of polymer b4 (EPT V-3011, manufactured by Mitsui Chemicals), the mixture was stirred for 3 minutes.
To the mixture after stirring, 70 parts by mass of polymer A1 (MS polymer S810, manufactured by Kaneka Chemical Co., Ltd.) was added and stirred for 10 minutes, and further platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals Japan). A dispersion mixture 7 in which polymer fine particles B7 derived from the polymer b4 were dispersed in the polymer A1 was prepared by adding 0.036 parts by mass and stirring for 30 minutes.

(Preparation of dispersion mixture 8)
After adding 24 parts by mass of process oil (PS32, manufactured by Idemitsu Kosan Co., Ltd.) and 0.72 parts by mass of TMCTS to 6 parts by mass of polymer b4 (EPT V-3011, manufactured by Mitsui Chemicals), the mixture was stirred for 3 minutes.
To the mixture after stirring, 70 parts by mass of polymer A1 (MS polymer S810, manufactured by Kaneka Chemical Co., Ltd.) was added and stirred for 10 minutes, and further platinum catalyst (PT-VTSC-3.0X, OMG Precious Metals Japan). 0.036 parts by mass) was added and stirred for 30 minutes to prepare dispersion mixture 7 in which polymer fine particles B8 derived from polymer b4 were dispersed on the surface of polymer A1.

(Examples 1-8 and Comparative Example 1)
The obtained dispersion mixtures 1 to 8 and the components shown in Table 1 below are mixed using a stirrer with the composition (parts by mass) shown in Table 1, and the two-component form shown in Table 1 is used. A curable composition (liquid A, liquid B) was obtained.

The components shown in Table 1 are as follows.
Polymer A1: MS polymer S810, manufactured by Kaneka Chemical Co., Ltd. Epoxy resin: YD128, manufactured by Tohto Kasei Co., Ltd. Plasticizer: Diisononyl phthalate (DINP, manufactured by Shin Nippon Chemical Co., Ltd.)
-Epoxidized soybean oil: Epoxy hexahydrophthalic acid diester plasticizer, Sansosizer E-PS, manufactured by Shin Nippon Rika Co., Ltd.-Anti-aging agent 1: Kimasorb 944LD, manufactured by Ciba Specialty Chemicals-Anti-aging agent 2: Tinuvin P, manufactured by Ciba Specialty Chemicals Co., Ltd. ・ Calcium carbonate 1: Calfine 200, manufactured by Maruo Calcium Co., Ltd. ・ Calcium carbonate 2: Lighton A-4, manufactured by Bihoku Flour Industries Co., Ltd. ・ Resin balloon: MFL-100SSL, Matsumoto Yushi Seiyaku・ Thixotropic agent: Disparon # 305, manufactured by Enomoto Kasei Co., Ltd. ・ Curing catalyst: Curing agent for Super II, manufactured by Yokohama Rubber ・ Color master: Color master for Super II, manufactured by Yokohama Rubber

  About each obtained curable composition, the physical property after hardening, workability | operativity (thixotropy property, stringing property), initial tack, and weather resistance were evaluated as follows.

<Physical property test after curing>
As shown below, tensile physical properties as cured product properties of each curable composition thus obtained were subjected to heat aging (standard curing + 80 ° C. for 7 days) after standard curing (curing for 23 ° C. and 50% RH for 7 days, 50 ° C. for 7 days). Each was evaluated after (curing) and after water aging (standard curing + immersion in water at 23 ° C. for 7 days).
The results are shown in Table 2.

Using the obtained curable composition, a test piece was prepared according to JIS A5758: 1997. After the above-described standard curing, after heat aging and after water aging, autographs according to JIS A1439: 1997 ( Model No .: AGS-10Kng (manufactured by Shimadzu Corporation), and a tensile test was conducted at a tensile speed of 50 mm / min. Tensile stress (M ₅₀ ) [N / cm ² ] when elongation was 50% and elongation was 150% Tensile stress (M ₁₅₀ ) [N / cm ² ], tensile stress at break (T _B ) [N / cm ² ], and elongation at break (E _B ) [%].
In addition, the breaking state at the time of breaking was observed, and the breaking state was indicated by CF (cohesive failure), TCF (thin layer cohesive failure), and AF (interface separation).

<Workability>
As evaluation of workability, thixotropy and stringiness of each obtained curable composition were examined.
The results are shown in Table 3.
(Thixotropic)
The thixotropy was evaluated by measuring a thixo index (hereinafter simply referred to as “TI”) immediately after preparation of the obtained curable composition at 23 ° C. Here, the TI value is obtained from the ratio of viscosity (Pa · s) measured at a rotation speed of 1 rpm and 10 rpm using a BS viscometer (No. 7 rotor) at 20 ° C. [TI value = (1 rpm Viscosity at 10 rpm) / (viscosity at 10 rpm)].
(Threading property)
The stringiness when the curable composition immediately after preparation of the obtained curable composition was scrubbed with a spatula was evaluated. In Table 1, the case where the yarn was not pulled was evaluated as ◯, and the case where the yarn was pulled was evaluated as ×.

<Initial tack>
Each of the obtained curable compositions was cured under conditions of 23 ° C. and 50% RH, and allowed to cure for 24 hours. After curing, it was examined whether or not there was tack on the surface, and the case where tack was completely absent was evaluated as ◯, the case where tack was felt was evaluated as Δ, and the case where tack was felt strongly was evaluated as ×.
The results are shown in Table 3.

<Weather resistance>
Each obtained curable composition was smoothly placed on the surface of a wooden siding board (50 × 50 × 12 mm) for a detached house so that the thickness was 0.2 mm and 2 mm, and 23 ° C., 50%. It was cured at RH for 1 week and further at 30 ° C. for 1 week.
Then, irradiation was performed for a predetermined time (600 hours, 1200 hours) using a metal halide weather meter (conditions: 63 ° C., 50% RH, light energy 75 mW / cm ² , shower 120 seconds / 2 hours later), Compared.
The results are shown in Table 3. In Table 3 below, the thinly coated portion refers to a 0.2 mm thick coated portion, and the thick coated portion refers to a 2 mm thick coated portion.

<Preparation of dispersion mixture 9>
In 70 g of polymer A2 (MS polymer S943, Kaneka Chemical Co., Ltd.), ethylene-propylene- [5-vinyl-2-norbornene] copolymer (Mitsui Chemicals, Mooney viscosity ML _{1 + 4} (100 ° C.) 9) Polymer b5 (26 g) prepared by reacting ethylene content 63 mol%, iodine value 15) with trichlorosilane in the presence of chloroplatinic acid at 120 ° C. for 2 hours, and a liquid compatibilizer (Rheidol SP-L10, After adding 2.0 g of Kao) and 2.0 g of a solid compatibilizer (Excel T-95 powder, Kao), stirring for 10 minutes using a conditioning mixer (AR-250, manufactured by Sinky) Then, a dispersion mixture 9 was prepared in which polymer fine particles B9 having a particle diameter of 0.5 to 3 μm derived from the polymer b5 were dispersed in the polymer A2.

(Example 9 and Comparative Example 2)
The obtained dispersion mixture 9 and each component shown in Table 4 below were dispersed by vigorously mixing using a stirrer with the composition (parts by mass) shown in Table 4 and shown in Table 4 A one-component curable composition was obtained.
In the preparation of the composition, first, the dispersion mixture 9 and calcium carbonates 1 and 2 were dispersed by stirring for 5 minutes using a conditioning mixer (AR-250, manufactured by Sinky Corporation), and then the mixture after stirring. All the remaining ingredients are added to the mixture, and the mixture is stirred for 2 minutes using a conditioning mixer (AR-250, manufactured by Sinky). Further, using a vacuum conditioning mixer (ARV-200, vacuum degree 100 mmHg, manufactured by Sinky) It was done by stirring for 1 minute.
In Comparative Example 2, a curable composition was obtained by using the polymer A2 in place of the dispersion mixture 9 and carrying out similar stirring.

The components shown in Table 4 are as follows.
-Polymer A2: MS polymer S943, manufactured by Kaneka Chemical Co., Ltd.-Calcium carbonate 1: Calfine 200, manufactured by Maruo Calcium Co., Ltd.-Calcium carbonate 2: Ryton A-4, manufactured by Bihoku Powdered Industries, Ltd.-Filler: Titanium oxide , R-820, manufactured by Ishihara Sangyo Co., Ltd. Plasticizer 1: Bifunctional PPG (Exenol 3020, manufactured by Asahi Glass Co., Ltd., molecular weight 3000)
Plasticizer 2: DOS, manufactured by Toyokuni Oil Co., Ltd. Silane coupling agent 1: Vinyltrimethoxysilane, A-171, manufactured by Nihon Unicar Co., Ltd. Silane coupling agent 2: 3-aminopropyltrimethoxysilane, A-1110, Made by Nippon Unicar Co., Ltd. ・ Curing catalyst: No. 918, made by Sansha Co., Ltd.

About each obtained curable composition, the physical property after hardening, workability | operativity (thixotropic property, stringing property), initial stage tack, and weather resistance were evaluated by the method mentioned above, and tack free time and deep part hardening were carried out as follows. Sex was evaluated.
The results are shown in Tables 5 and 6.

<Tack free time (TFT)>
Each of the obtained curable compositions was cured under conditions of 23 ° C. and 50% RH, and the tack free time (minutes) was measured according to JIS A5758: 1997.
The results are shown in Table 3.

<Deep part curability>
Each obtained curable composition was filled in an aluminum channel (size: 30 mm × 100 mm × 15 mm) so that air did not enter, and finished with a spatula so that the surface was flat, and the condition was 23 ° C. and 50% RH. I left it alone. The progress of curing from the surface to the inside was measured by measuring the thickness of the fragments cut from the surface by knife cutting. If the progress of curing after 1 week is 5 mm or more, the deep part curability is very excellent.

As shown in Table 2, Table 3, Table 5 and Table 6, the curable compositions of Examples 1 to 9 are excellent in workability because they have good thixotropy and stringiness, and are cured. It turned out that it was excellent also in the weather resistance after that, and since the surface appearance was not glossy, it turned out that it is very useful with a sealing material. Further, when used as a one-component form (Example 9), it is superior to a curable composition having a general alkylene skeleton, and is equivalent to a curable composition comprising an alkylene oxide monomer unit. It was found to have deep part curability.
In contrast, it was found that the curable compositions of Comparative Examples 1 and 2 having no polymer fine particles were inferior in workability and weather resistance.

Claims (15)

Containing a polymer and fine polymer particles dispersed in the polymer,
The polymer is a polymer (A) having an alkylene oxide monomer unit in the main chain and having at least one hydrolyzable silicon-containing group per molecule;
The curable composition, wherein the polymer fine particles are polymer fine particles (B) in which the polymer (b) having an alkylene skeleton in the main chain can and / or three-dimensionally crosslink.   The polymer fine particle (B) is a polymer fine particle (B) capable of and / or three-dimensionally crosslinked by the reaction of the functional group of the polymer (b) having a crosslinkable functional group. The curable composition according to 1.   Furthermore, the curable composition of Claim 1 or 2 containing the curing catalyst (C) of the said polymer (A).   Furthermore, the curable composition in any one of Claims 1-3 containing a compatibilizing agent (D).   The curable composition according to any one of claims 1 to 4, wherein the alkylene skeleton of the polymer (b) is composed of an isobutylene monomer unit.   The curable composition according to any one of claims 1 to 4, wherein the alkylene skeleton of the polymer (b) is composed of an ethylene / α-olefin / non-conjugated polyene monomer unit.   The polymer (b) has a hydrolyzable silicon-containing group, and the polymer fine particles (B) can and / or are three-dimensionally crosslinked by hydrolysis of the polymer (b). The curable composition according to any one of 6 above.   The polymer (b) has an alkenyl group, and the polymer fine particles (B) can and / or be three-dimensionally crosslinked by a hydrosilylation reaction between the polymer (b) and a compound having a hydrosilyl group. The curable composition in any one of Claims 1-6.   The curable composition according to any one of claims 1 to 8, wherein the polymer fine particle (B) has a hydrolyzable silicon-containing group.   The curing according to claim 9, wherein all or part of the hydrolyzable silicon-containing group of the polymer fine particles (B) is introduced into the polymer fine particles (B) by reaction with a silane coupling agent. Sex composition.   The curable composition according to claim 10, wherein the silane coupling agent is aminosilane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane, or a mixture or reaction product thereof.   The amount of the said silane coupling agent is 0.1-10 mass parts with respect to 100 mass parts of said polymers (A), The curable composition of Claim 10 or 11.   The curable composition according to any one of claims 1 to 12, comprising 1 to 100 parts by mass of the polymer fine particles (B) with respect to 100 parts by mass of the polymer (A).   The curable composition in any one of Claims 3-13 containing 0.1-20 mass parts of said curing catalysts (C) with respect to 100 mass parts of said polymers (A).   The curable composition in any one of Claims 4-14 containing 0.1-10 mass parts compatibilizer (D) with respect to 100 mass parts of said polymers (A).