JPH07233316A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a polymer synthesized by using a compound metal cyanide complex catalyst and having a structure in which a terminal Si-containing group is bonded to a polyoxyalkylene, an unsaturated monomer-derived polymer and a plasticizer and capable of producing a cured material excellent in adhesion and workability. CONSTITUTION:This curable composition is prepared by blending (A) an organo- polymer synthesized by polymerizing an alkylene oxide (e.g. propylene oxide) in the presence of a catalyst composed of a compound metal cyanide complex (e.g. hexacyanocobaltate glyme complex) and an initiator composed of, e.g. a diethylene glycol-propylene oxide addition polymer having 1000 average molecular weight and having a structure in which a terminal Si-containing group represented by the formula [R<1> is a 1 to 20C univalent hydrocarbon; X is a hydrolyzable group; (a) is 1, 2 or 3] is bonded to a polyalkylene oxide having >=5000 average molecular weight in an amount of >=1 based on one molecule on the average, (B) a polymerizable unsaturated group-containing monomer (e.g. methyl methacrylate) and (C) a polymer plasticizer (e.g. dioctyl phthalate).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified curable composition, and more particularly to a curable composition having remarkably excellent mechanical properties and excellent workability.

[0002]

2. Description of the Related Art Polyether compounds having at least one reactive silicon group in the molecule have been used for coating compositions, sealing compositions and the like by taking advantage of the characteristic that a cured product has rubber elasticity. In particular, the strength of the cured product is insufficient for applications such as adhesives and waterproofing agents, which poses a practical problem. For example, if you use it as an adhesive,
There is a problem that the shear adhesive strength is insufficient, and when this is used as a waterproofing agent, there is a problem that the strength of the film is insufficient.

In order to solve these problems, in JP-A-5-194677, JP-A-5-194678, and JP-A-5-194679, there is at least one reactive silyl group in the molecule. A curable composition composed of a polymer of a polyether compound and a polymerizable unsaturated group-containing monomer has been proposed.

Further, in Japanese Patent Application No. 5-232518, a main chain is a polyoxyalkylene polymer having a narrow molecular weight distribution, a high molecular weight and a low viscosity, and a polyether compound having at least one reactive silyl group in the molecule. A curable composition having a low viscosity, a high strength, and a high elongation, which comprises a polymer of a polymerizable unsaturated group-containing monomer, has been proposed.

By adding a plasticizer to such a curable composition, it is possible to further reduce the viscosity of the composition and improve the elongation of the cured product. However, the weight of the polymerizable unsaturated group-containing monomer is increased. Depending on the type of coalescence, the polymer may gel during storage and the composition may become unusable as an adhesive or the like. In addition, the plasticizer bleeds out after curing, resulting in a decrease in adhesiveness.

[0006]

The present invention is intended to solve such a drawback, that is, a number obtained by polymerizing alkylene oxide with an initiator using the complex metal cyanide complex (D) as a catalyst. An organic polymer (A) having a polyoxyalkylene polymer (E) having an average molecular weight of 5000 or more as a main chain and having at least one silicon-containing group represented by the formula (1) per molecule on average in all molecules, A curable composition comprising a polymer (B) of a saturated group-containing monomer and a polymer plasticizer (C).

--SiX _a R ¹ _3-a (1) In the formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and X is hydrolyzed. The sexual group, a, is 1, 2 or 3.

The polyoxyalkylene polymer (E) used as the main chain of the organic polymer (A) in the present invention is an initiator such as a hydroxy compound having at least one hydroxyl group in the presence of the complex metal cyanide complex (D). A hydroxyl group-terminated one produced by reacting with alkylene oxide is preferable.

The use of the complex metal cyanide complex (D) has a narrower M _w / M _n , a higher molecular weight and a lower viscosity than the polyoxyalkylene polymer produced by using the conventional alkali metal catalyst. An oxyalkylene polymer (E) can be obtained.

The complex metal cyanide complex (D) is preferably a complex containing zinc hexacyanocobaltate as a main component, and its ether and / or alcohol complex is preferable. As the composition, those essentially described in JP-B-46-27250 can be used. As the ether, glymes such as glyme and diglyme are preferable,
Glyme is particularly preferable in terms of handling during the production of the complex. As the alcohol, t-butanol described in JP-A-4-145123 is preferable.

The number of functional groups of the polyoxyalkylene polymer (E) is preferably 2 or more, and particularly preferably 2 to 4. Specific examples include a polymer obtained by polymerizing an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, and hexylene oxide, and a polyoxytetramethylene polymer.

Particularly preferred polyoxyalkylene polymers (E) are polyoxypropylene diols, polyoxypropylene triols and polyoxypropylene tetraols. When used in the following methods (a) and (d), an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monool can also be used.

R ¹ in the formula (1) is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, propenyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X in the formula (1) is a hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, an acid amide group or a hydride group. Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. Preferred hydrolyzable groups are lower alkoxy groups having 4 or less carbon atoms, particularly methoxy group, ethoxy group, propoxy group, propenyloxy group and the like.

A in the formula (1) is 1, 2 or 3, and 2 or 3 is particularly preferable.

Next, the method for producing the organic polymer (A) will be described. The organic polymer (A) in the present invention is preferably one produced by introducing a silicon-containing group at the terminal of a polyoxyalkylene polymer having a functional group as described below. Such compounds are liquid at room temperature, and
The cured product retains flexibility even at a relatively low temperature and has favorable properties when used as a sealing material, an adhesive or the like.

(A) A method of reacting a polyoxyalkylene compound having a functional group with an olefin group introduced at the terminal and a hydrosilyl compound represented by the formula (4).

HSiX _a R ¹ _3-a (4) However, in the formula (4), R ¹ , X and a are the same as described above.

As a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene compound and bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond or the like. Or a method of introducing an olefin group into the side chain by copolymerizing by adding an olefin group-containing epoxy compound such as allyl glycidyl ether when polymerizing the alkylene oxide.

(B) A method of reacting the terminal of a polyoxyalkylene compound having a functional group with a compound represented by the formula (5).

R ¹ _3-a SiX _a -R ⁶ NCO (5) However, in the formula (5), R ¹ , X and a are the same as described above, and R ⁶ is 2 having 1 to 17 carbon atoms. It is a valent hydrocarbon group.

(C) After the end of the polyoxyalkylene compound having a functional group is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, the silicon compound represented by the formula (6) is added to the isocyanate group. A method of reacting the W group.

R ¹ _3-a -SiX _a -R ⁶ W (6) However, in the formula (6), R ¹ , R ⁶ , X and a are the same as described above, and W is a hydroxyl group or a carboxyl group. , An active hydrogen-containing group selected from a mercapto group and an amino group (primary or secondary).

(D) An olefin group is introduced at the terminal of a polyoxyalkylene compound having a functional group, and the olefin group is reacted with the mercapto group of the silicon compound represented by the formula (6) in which W is a mercapto group. Method.

The number of silicon-containing groups is 1 or more per molecule on the average of all molecules.

As the organic polymer (A) in the present invention, an organic polymer having a number average molecular weight of 5,000 to 30,000 can be used. The number average molecular weight of the organic polymer (A) is 500.
When it is lower than 0, the cured product becomes hard and the elongation is low,
When the number average molecular weight exceeds 30,000, the flexibility and elongation of the cured product will not be a problem, but the viscosity of the polymer itself will be remarkably increased and the practicality will be reduced. The number average molecular weight is particularly preferably 8,000 to 30,000.

The polymer (B) of the polymerizable unsaturated group-containing monomer used in the present invention is obtained by polymerizing at least one selected from the group consisting of vinyl monomers represented by the formulas (2) and (3). It is preferably a polymer obtained by

CH ₂ = CR ² R ³ (2) In the formula (2), R ² is a hydrogen atom, a halogen atom, or a substituted or unsubstituted monovalent aliphatic group having 1 to 10 carbon atoms. A hydrocarbon group, R ³ is the same group as R ² , a substituted or unsubstituted monovalent aromatic hydrocarbon group, an alkenyl group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group, a pyridyl group, an amide group, And a monovalent organic group having 1 to 20 carbon atoms selected from a glycidyloxy group.

R ⁴ —SiR ⁵ _b X _3-b (3) However, in the formula (3), X is the same as above, and R ⁴
Is an organic residue having a polymerizable double bond, R ⁵ is a carbon number of 1 to
10 is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, and b is 0, 1 or 2.

Examples of the polymerizable unsaturated group-containing monomer represented by the formula (2) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, Ester of acrylic acid or methacrylic acid such as 2-ethylhexyl methacrylate, benzyl acrylate, and benzyl methacrylate; carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and acid anhydrides such as maleic anhydride; glycidyl Acrylate, epoxy compounds such as glycidyl methacrylate; amino compounds such as diethylaminoethyl acrylate and diethylaminoethyl methacrylate; acrylamide, methacrylamide, itaconic acid diamide, α-ethylacrylamide, croto Amide compounds such as acid amide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl acrylamide and N-butoxymethyl methacrylamide; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate,
Vinyl compounds containing hydroxyl groups such as 2-hydroxy vinyl ether, N-methylol acrylamide, Aronix 5700 (manufactured by Toagosei Kagaku Kogyo Co., Ltd.); acrylonitrile, iminol methacrylate, styrene, α-methylstyrene, chlorostyrene, vinyl chloride, vinylidene chloride. , Vinyl acetate, vinyl propionate, vinyl pyridine, butadiene, chloroprene, isobutylene, propylene, ethylene, aminoethyl vinyl ether and the like.

The silicon-containing monomer represented by the formula (3) includes vinylsilane such as vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane and vinyltrichlorosilane; Acryloxysilanes such as 3-acryloxypropylmethyldimethoxysilane and 3-acryloxypropyltrimethoxysilane; Methacryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane; Allylmethyldimethoxysilyl Examples thereof include allyl esters of phthalic acid containing a reactive silicon-containing group such as propyl phthalate and allyltrimethoxysilylpropyl phthalate, and particularly 3-methacryloxypropyl Trimethoxysilane is preferred. In addition to these, for example, a polysiloxane compound having 2 to 30 silicon atoms can be used, that is, C =
Any compound having a C bond and a silicon atom having a hydrolyzable group bonded thereto may be used.

These polymerizable unsaturated group-containing monomers are
It may be selected according to the desired improvement quality, for example, ethyl acrylate for the purpose of improving weather resistance,
So-called acrylic monomers such as isobutyl acrylate, methyl methacrylate and 3-methacryloxypropyltrimethoxysilane are preferred, and for the purpose of improving the adhesiveness, acrylamide, epoxy group-containing monomer, 2-ethylhexyl acrylate and 3-methacryloxypropyltrimethoxysilane and the like are preferable. The vinyl monomers may be used alone or in combination of two or more. Further, like the organic polymer (A), a vinyl monomer may be previously polymerized so that the olefin group may remain in the side chain or terminal, and subsequently the reactive silicon-containing group may be introduced.

Polymerization of the polymerizable unsaturated group-containing monomer can be carried out by a usual method. As the polymerization initiator, various compounds such as a radical generator can be used, and in some cases, the polymerization can be performed by radiation or heat without using the polymerization initiator.

Examples of the polymerization initiator include peroxide type, azo type, or redox type polymerization initiators and metal compound catalysts. Examples of the polymerization initiator often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide, diisopropyl peroxycarbonate and the like. Further, a solvent can be used if necessary, and can be appropriately selected depending on the type of unsaturated group-containing monomer used for the polymerization.

The curable composition of the present invention can be obtained by mixing the polymer (B) of the above-mentioned polymerizable unsaturated group-containing monomer and the organic polymer (A). Can also be taken.

A method of polymerizing a polymerizable unsaturated group-containing monomer in the presence of an organic polymer (A), a polymerizable unsaturated group in the presence of a polymer (F) having a functional group capable of introducing a silicon-containing group. Examples thereof include a method of polymerizing the contained monomer and a method of polymerizing the polymerizable unsaturated group-containing monomer in a solvent. The polymer (F) having a functional group capable of introducing a silicon-containing group is a polymer before the introduction of the silicon-containing group in the above-mentioned method for producing the organic polymer (A), which has a hydroxyl group at the terminal or It is a polyoxyalkylene compound having an unsaturated group.

When the polymerization of the polymerizable unsaturated group-containing monomer is carried out in the presence of the organic polymer (A), after the polymerization of the monomer, the objective is not mixed with the organic polymer (A). A composition of When the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polymer (F), the desired composition can also be obtained by introducing a silicon-containing group into the polymer (F) after the polymerization. . When the polymerizable unsaturated group-containing monomer is polymerized in a solvent, the desired composition is obtained by distilling off part or all of the solvent after mixing with the organic polymer (A).

The polymer (B) of the polymerizable unsaturated group-containing monomer in the composition of the present invention is finely dispersed in the organic polymer (A) even if it is uniformly dispersed. However, in consideration of workability such as viscosity of the composition, it is preferable that the composition is uniformly dispersed.

The amount of the polymer (B) containing the polymerizable unsaturated group-containing monomer is 0.1 to 1000 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of the organic polymer (A). Good.

The polymer plasticizer (C) used in the present invention has a molecular weight of about 500 to 15,000, particularly 1000 to 100.
It is preferably about 00. Examples of the polymer plasticizer (C) include polyethers such as polyoxypropylene glycol and its derivatives; polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol; poly-α.
-Polystyrenes such as methylstyrene, polystyrene;
Polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene,
Examples thereof include hydrogenated polybutene and chlorinated paraffins, but are not limited thereto. Among these, polyester plasticizers, polyethers, polystyrenes, polybutadiene, polybutene and the like are preferable from the viewpoint of compatibility and viscosity.

In the case of polyethers, those obtained by polymerizing an alkylene oxide with an initiator using the double metal cyanide complex (D) as a catalyst are preferable from the viewpoint of low viscosity. The polymer plasticizer (C) may be used alone or in combination of two or more kinds. In addition, you may mix | blend these polymeric plasticizers as a solvent at the time of manufacture of the polyoxyalkylene type polymer used as (A) component.

The polymer plasticizer (C) is used in an amount of 1 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the organic polymer (A). If it is less than 1 part by weight, the effect as a plasticizer cannot be exhibited, and if it exceeds 200 parts by weight, the mechanical strength of the cured product becomes insufficient.

The composition of the present invention may further contain fillers, plasticizers other than polymer plasticizers, solvents, additives, curing catalysts and the like.

Examples of the filler include calcium carbonate, kaolin, talc, clay, silica, magnesium carbonate, aluminum silicate and the like; inorganic pigments such as titanium oxide, zinc oxide and iron oxide; asbestos, glass powder, carbon black and the like. Examples include reinforcing agents.

Plasticizers other than polymer plasticizers may be added within the range in which the object of the present invention is achieved. Specific examples of such a plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate; dioctyl adipate, isodecyl succinate,
Aliphatic carboxylic acid esters such as dibutyl sebacate and butyl oleate; glycol esters such as pentaerythritol ester; phosphoric acid esters such as trioctyl phosphate and tricresyl phosphate; epoxidized soybean oil,
Epoxy plasticizers such as benzyl epoxy stearate; chlorinated paraffins and the like can be used alone or as a mixture of two or more kinds.

Examples of the solvent include aromatic hydrocarbon solvents such as xylene and toluene, and lower alcohols such as methanol and ethanol.

Examples of the additives include adhesion-imparting resins such as epoxy resins and phenol resins; γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxy. Various silane coupling agents having functional groups such as silane, adhesion promoters such as alkyl titanates, aromatic polyisocyanates, etc .; hydrogenated castor oil, anti-sagging agents such as calcium stearate, zinc stearate; UV absorbers. , Antiaging agents and the like.

As the curing catalyst, compounds known as catalysts for hydrolysis and condensation reactions of hydrolyzable silicon groups can be used. That is, metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, tin octylate and dibutyltin dilaurate; dibutylamine-2.
Amine salts such as ethylhexoate and the like; as well as other acidic and basic catalysts may be used. The curing catalyst is used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the organic polymer (A).

[0049]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Reference Examples 1 and 2 show production examples of the organic polymer (A) and the polymer (F) having a functional group capable of introducing a silicon-containing group. Production Examples 1 to 4 show production examples of compositions comprising the organic polymer (A) having a silicon-containing group and the polymer (B) of a polymerizable unsaturated group-containing monomer.

Reference Example 1 Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a diethylene glycol-propylene oxide adduct having a molecular weight of 1000 as an initiator according to the method described in Japanese Patent Application Laid-Open No. 3-72527. Polyoxypropylene diol having an average molecular weight of 19000 was obtained, the terminal hydroxyl group was converted to an allyl ether group, and an allyl group-containing organic polymer (A1) was obtained.

Reference Example 2 Methyldimethoxysilane was added to the allyl group-containing organic polymer (A1) obtained in Reference Example 1 using chloroplatinic acid as a catalyst to give an average of 1.
Organic polymer having 6 hydrolyzable silicon groups (P1)
Got

[Production Example 1] 100 g of the organic polymer (P1) obtained in Reference Example 2 was placed in a 4-necked flask, and 10 g of methyl methacrylate, 20 g of n-butyl methacrylate and 0 of azobisisobutyronitrile were kept at 110 ° C. ．
6 g of the mixture was added dropwise over 2 hours with stirring under N ₂ atmosphere, and then stirring was continued for 0.5 hour at the same temperature. After completion of the reaction, unreacted monomers are removed by heating and degassing under reduced pressure for 2 hours at 110 ° C. and 0.1 mmHg, and a composition comprising an organic polymer having a silicon-containing group and a polymer of a polymerizable unsaturated group-containing monomer ( C1) was obtained.

[Production Example 2] 100 g of the organic polymer (P1) obtained in Reference Example 2 was placed in a 4-necked flask and 21 g of glycidyl methacrylate, 9 g of acrylonitrile and 0.6 g of azobisisobutyronitrile were kept at 110 ° C. The mixture was added dropwise with stirring under N ₂ atmosphere over 2 hours, and then stirring was continued at the same temperature for 0.5 hour. After completion of the reaction, unreacted monomers are removed by heating and degassing under reduced pressure for 2 hours at 110 ° C. and 0.1 mmHg, and a composition comprising an organic polymer having a silicon-containing group and a polymer of a polymerizable unsaturated group-containing monomer ( C2) was obtained.

[Production Example 3] 100 g of the allyl group-containing organic polymer (A1) obtained in Reference Example 1 was placed in a four-necked flask,
Glycidyl methacrylate 21 while maintaining at 110 ° C
g, 9 g of acrylonitrile, and 0.6 g of azobisisobutyronitrile were added dropwise over 2 hours with stirring under an N ₂ atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction is completed, unreacted monomer is heated to 110 ° C and 0.1 m
After removing by deaeration under reduced pressure by heating at mHg for 2 hours, methyldimethoxysilane was added to this to perform a silylation reaction to convert the allyl group at the polyoxypropylene terminal into a methyldimethoxysilyl group, and to add an organic polymer having a silicon-containing group. A composition (C3) comprising the polymer and a polymer of the polymerizable unsaturated group-containing monomer was obtained.

[Production Example 4] Reference Example 1 in 100 g of toluene
50 g of the allyl group-containing organic polymer (A1) obtained in (3) was dissolved, placed in a four-necked flask, and maintained at 100 ° C., 70 g of glycidyl methacrylate and 30 acrylonitrile.
g, 3-methacryloxypropyltrimethoxysilane 5
g, and a mixture of 0.6 g of azobisisobutyronitrile with N
_The mixture was added dropwise over 2 hours with stirring under ₂ atmospheres. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, 250 g of the organic polymer (P1) obtained in Reference Example 2 was added and mixed with stirring, and then toluene and unreacted monomer were mixed with 1 under stirring.
The mixture was heated at 10 ° C. and 0.1 mmHg for 2 hours under reduced pressure under reduced pressure to be distilled off to obtain a composition (C4) composed of an organic polymer having a silicon-containing group and a polymer of a polymerizable unsaturated group-containing monomer.

[Examples and Comparative Examples] 100 parts by weight of the composition (any one of C1 to C4) obtained in Production Examples 1 to 4, Table 1
50 parts by weight of the polymeric plasticizer shown in, calcium carbonate 120
Parts by weight, 6 parts by weight of hydrogenated castor oil, 1 part by weight of phenolic antioxidant, 2 parts by weight of aminosilane were added and kneaded using a 3 paint roll, and then 1 part by weight of dibutyltin dilaurate was added so that moisture was not added. A curable composition was obtained by adding below (Examples 1 to 4).

Next, a curable composition was obtained in the same manner as in Example (Comparative Example 1) except that the composition (C4) was used and the polymer plasticizer was replaced with dioctyl phthalate (DOP). A curable composition was obtained in the same manner as in Example except that the composition (C4) was used and no polymer plasticizer was used (Comparative Example 2).

Regarding these, aluminum (JIS H
4000 A1050P) and initial and 10
Tensile shear strength after heating at 0 ° C for 7 days (unit: kgf /
cm ² ) was measured. The result is 20 ° C of the curable composition.
It is shown in Table 1 together with the viscosity (unit: P) in.

The polymeric plasticizers used are as follows: A: polyoxypropylene triol having a molecular weight of 3000, B: a molecular weight of 1000 produced using a complex metal cyanide complex with n-butanol as an initiator. Polyoxypropylene monool, C: an oxypropylene polymer obtained by allyl etherifying the terminal monol of the polymer plasticizer B.

[0061]

[Table 1]

[0062]

The composition of the present invention comprising an organic polymer having a hydrolyzable silicon group produced using a double metal cyanide complex, a polymer of a polymerizable unsaturated group-containing monomer, and a polymer plasticizer is It has the effect of excellent adhesiveness and workability of the cured product as compared with the conventionally known ones.

Claims (7)

[Claims] 1. A polyoxyalkylene polymer (E) having a number average molecular weight of 5000 or more obtained by polymerizing an alkylene oxide with an initiator using a complex metal cyanide complex (D) as a catalyst, and having a main chain of the formula (1). An organic polymer (A) having a silicon-containing group represented by 1 or more per molecule on average in all molecules, a polymer of a polymerizable unsaturated group-containing monomer (B),
And a curable composition comprising a polymer plasticizer (C). —SiX _a R ¹ _3-a (1) In the formula (1), R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydrolyzable group, a is 1, 2 or 3. 2. The curable composition according to claim 1, wherein the complex metal cyanide complex (D) is a complex containing zinc hexacyanocobaltate as a main component. 3. The alkylene oxide is ethylene oxide,
The curable composition according to claim 1, which is at least one selected from propylene oxide and butylene oxide. 4. An organic polymer (A) and a polymer (B) of a polymerizable unsaturated group-containing monomer are obtained by polymerizing a polymerizable unsaturated group-containing monomer in the organic polymer (A). The curable composition according to claim 1. 5. The organic polymer (A) and the polymer (B) of a polymerizable unsaturated group-containing monomer have the polyoxyalkylene polymer (E) as a main chain and are represented by the formula (1). The polymer (F) having a functional group capable of introducing a silicon group, obtained by polymerizing a polymerizable unsaturated group-containing monomer and subsequently introducing a silicon-containing group. Curable composition. 6. The organic polymer (A) and the polymer (B) of the polymerizable unsaturated group-containing monomer are mixed with the organic polymer (A) after polymerizing the polymerizable unsaturated group-containing monomer in a solvent. Then, the curable composition according to any one of claims 1 to 3, which is obtained by distilling off a part or all of the solvent. 7. A polymer (B) of a polymerizable unsaturated group-containing monomer is obtained by polymerizing at least one selected from the group consisting of vinyl monomers represented by the formulas (2) and (3). Curable composition in any one of Claims 1-6 which is a polymer. ^{_{CH 2 = CR 2 R 3 ···}} (2) In Expression (2), R ² is a hydrogen atom, a monovalent aliphatic hydrocarbon group in the substituted or unsubstituted halogen atom or having 1 to 10 carbon atoms , R ³ is the same group as R ² , a substituted or unsubstituted monovalent aromatic hydrocarbon group, an alkenyl group, a carboxyl group, an acyloxy group, an alkoxycarbonyl group, a nitrile group, a pyridyl group, an amide group, and a glycidyloxy group. It is a monovalent organic group having 1 to 20 carbon atoms selected from the group. R ⁴ —SiR ⁵ _b X _3-b (3) In the formula (3), X is a hydrolyzable group, R ⁴ is an organic residue having a polymerizable double bond, and R ⁵ is a carbon number. 1-1
0 is a monovalent hydrocarbon group selected from an alkyl group, an aryl group and an aralkyl group, and b is 0, 1 or 2.