JPH0867707A - Curable composition - Google Patents

Abstract

(57) [Summary] [Structure] Polyether (A) containing a reactive silyl group, and a polymer obtained by polymerizing a hydrophilic group-containing polymerizable unsaturated group-containing monomer with another polymerizable monomer in the polyether. A curable composition comprising the united product (B). [Effect] Remarkably high internal curability can be exhibited.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified curable composition, and more particularly to a curable composition having remarkably excellent internal curability.

[0002]

2. Description of the Related Art Polyether compounds having at least one reactive silyl group in the molecule have been used for coating compositions, sealing compositions, etc. by taking advantage of the fact that cured products have rubber elasticity. Especially for applications such as adhesives and sealing agents, the internal curability of the cured product is insufficient and there is a practical problem. For example, when it is used as an adhesive, there is a problem that the rate of development of adhesive strength is insufficient, and when it is used as a sealing agent, it is easily affected by the movement of joints in the initial stage of curing. The problem arises.

However, if an attempt is made to increase the amount of the curing catalyst, for example, in order to solve these problems, at the same time, a problem occurs in the storage stability of the composition, which is a practical problem. Further, although curability can be improved by adding a hydrophilic component such as polyethylene glycol or a hydrophilic group-containing monomer, there are problems in bleed-out after curing, odor of the composition, physical properties of the composition, and the like.

[0004]

The present invention solves the above-mentioned drawbacks and provides a curable composition having particularly excellent internal curability.

[0005]

That is, the present invention provides a polyether (A) containing at least one reactive silyl group in the molecule, and a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule. Alternatively, it is a curable composition containing, as an active ingredient, a polymer (B) obtained by polymerizing it with another polymerizable unsaturated group-containing monomer.

In the present invention, it is essential that the component (B) used as the hydrophilic component is a polymer of a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule, and for the first time, the hydrophilic component is obtained. It is possible to prevent bleeding out of the resin and to develop appropriate cured physical properties according to the purpose.

The polyether (A) containing at least one reactive silyl group in the molecule used in the present invention is disclosed in JP-B-45-36319 and JP-B-46.
-12154, Japanese Patent Publication No. 49-32673,
JP-B-50-156599, JP-B-51-735
61, Japanese Patent Publication 54-6096, Japanese Patent Publication 55
-13767 publication, Japanese Patent Publication No. 55-13768 publication,
JP-B-55-82123, JP-B-55-1236
20, Japanese Patent Publication No. 55-125121, Japanese Patent Publication No. 55-131021, Japanese Patent Publication No. 55-131022.
JP-B, JP-B-55-135135, JP-B-55
-137129, JP-A-3-47825,
It is proposed in JP-A-3-72527, JP-A-3-43449, JP-A-3-79627 and the like.

The polyether (A) is obtained by, for example, ring-opening polymerization of a monoepoxide having 3 or more carbon atoms in the presence of an initiator, and then converting some or all of the hydroxyl groups at the molecular ends into reactive silyl groups. Obtained by

Examples of the catalyst include alkali catalysts such as KOH catalyst, porphyrin catalysts, and complex metal cyanide complex catalysts such as zinc hexacyanocobaltate catalyst.

As the monoepoxide having 3 or more carbon atoms,
Examples thereof include aliphatic alkylene oxides such as propylene oxide, 1,2-butylene oxide and epichlorohydrin, and aromatic alkylene oxides such as styrene oxide. Aliphatic alkylene oxides, particularly propylene oxide are preferable. It is also possible to use a small amount of ethylene oxide together with this.

The initiator used in the present invention includes polyhydric alcohols, polyhydric phenols, polyhydric carboxylic acids, polyhydric active hydrogen-containing compounds such as polyhydric amines, unsaturated alcohols,
Examples thereof include unsaturated group-containing active hydrogen-containing compounds such as unsaturated phenols and unsaturated carboxylic acids.

The reactive silyl group is condensed by moisture, a curing agent, etc., like a silanol group or a hydrolyzable silyl group,
It can react to accelerate the increase in the molecular weight of the polyether, and is represented by the following formula (2).

[0013]

## STR2 ## ^{_{X 3-n -Si (R 3}} ) n - ··· (2) formula R ³ is a monovalent hydrocarbon group or a halogenated hydrocarbon group, X is a hydroxyl group, a halogen atom, an alkoxy group, A hydrolyzable group such as an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group, and n is 0, 1 or 2.

The method of introducing the reactive silyl group can be specifically exemplified by the following methods, but is not limited to these methods.

(A) A specific organosilicon compound having at least one, preferably only one isocyanate group and at least one reactive silyl group in the molecule as shown by the formula (3) is substituted with a hydroxyl group. It reacts with the terminal hydroxyl group of the polyether compound.

[0016]

X _3-n -Si (R ³ ) _n -R ⁴ -NCO (3) In the formula, R ₃ , X and n are the same as above, and R ₄ is a divalent hydrocarbon group or halogen. Hydrocarbon groups.

The following compounds can be shown as specific organic silicon compounds.

[0018]

Embedded image (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO, (CH ₃ O) ₃ Si (CH ₂ ) ₃ NCO, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) _{3 NCO, (CH 3 O) 3} SiNCO, (CH 3 O) 2 Si (NCO) 2.

(B) a terminal unsaturated group obtained by reacting a terminal unsaturated group-containing isocyanate compound or a terminal unsaturated group-containing halogen compound with a terminal hydroxyl group of the polyoxyalkylene compound, or a polyoxyalkylene compound derived from an initiator. The terminal unsaturated group and the hydrosilicon compound represented by the formula (4) are reacted in the presence of a Group 8 metal such as platinum or a catalyst composed of the compound.

[0020]

[Image Omitted] X _3-n -Si (R ³ ) _n H (4) In the formula, R ³ , X and n are the same as described above.

Specific examples include allyl isocyanate as the terminal unsaturated group-containing isocyanate compound and allyl chloride as the terminal unsaturated group-containing halogen compound.
In addition to the above methods, the methods described in JP-A-5-194678 and the like can be mentioned.

The molecular weight of the thus obtained polyether (A) used in the present invention is preferably from 1,000 to 50,000, particularly preferably from 4,000 to 30,000.

The polymer as the component (B) used in the present invention is obtained by polymerizing a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or another polymerizable unsaturated group-containing monomer. .

As the polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule, a polymerizable unsaturated group-containing polymerizable unsaturated group having an ethylene oxide chain, an acid amide group, a hydroxyl group, a carboxylxyl group or a carboxylate group can be used. Group-containing monomers are mentioned.

The polymerizable unsaturated group-containing monomer having an ethylene oxide chain is preferably a monomer having at least one ethylene oxide ring-opening unit, preferably 1 to 50 units, and particularly 1 to 30 units. Specifically, for example, there are monomers represented by the following formulas (1) and (5).

[0026]

CH ₂ ═C (R ¹ ) COO— (CH ₂ CH ₂ O) _m R ² (1) In the formula, R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and m is An integer of 1 or more.

[0027]

Embedded image CH ₂ ═C (R ⁵ ) COO— (CH ₂ CH ₂ O) _p COC (R ⁶ ) ═CH ₂ (5) In the formula, R ⁵ and R ⁶ are hydrogen atoms or monovalent. Hydrocarbon group, p is an integer of 1 or more.

It is preferable that m in the formula (1) and p in the formula (5) are 1 to 50, especially 1 to 30, respectively.

Examples of the other polymerizable unsaturated group-containing monomer having a hydrophilic group include acrylamide, vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid salt, and methacrylic acid salt.

The other polymerizable unsaturated group-containing monomer to be copolymerized with the polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule is the polymerizable unsaturated group-containing monomer represented by the formula (6) alone. Alternatively, it is a mixture of two or more kinds.

[0031]

CH ₂ ═CR ⁷ R ⁸ (6) In the formula, R ⁷ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, and R ⁸ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group. , An alkoxycarbonyl group, a glycidyloxycarbonyl group, a glycidyloxy group, a nitrile group, an alkenyl group, an acyloxy group, or a pyridyl group.

Examples of the polymerizable unsaturated group-containing monomer represented by the formula (6) include the following.

Allyl glycidyl ether; styrene, α
A styrene-based monomer such as methylstyrene or chlorostyrene; methyl (meth) acrylate (indicates methyl acrylate and methyl methacrylate, the same applies hereinafter), ethyl (meth) acrylate, butyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, etc. Acrylic monomers; Acrylonitrile, 2,4-dicyanobutene-1 and other cyano group-containing monomers; Vinyl acetate,
Vinyl ester-based monomers such as vinyl propionate; butadiene, isoprene, chloroprene and other diene-based monomers; and olefins other than these, unsaturated esters, halogenated olefins, vinyl ethers.

If necessary, the silicon compound represented by the formula (7) can also be used as the polymerizable unsaturated group-containing monomer in the present invention.

[0035]

Embedded image ^{_{Y 3-q -SiR 9 q R}} 10 ··· (7) wherein R ⁹ is a monovalent hydrocarbon radical or halogenated hydrocarbon radical, Y is a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group , An amide group, an amino group, an aminoxy group or a ketoximate group, a hydrolyzable group, R ¹⁰ is an organic residue having a polymerizable unsaturated group, and q is 0, 1 or 2.

Specific examples of the silicon compound represented by the formula (7) include the following.

Reactive silyl group-containing (meth) acryloyloxyalkyl compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropylmethyldimethoxysilane; vinylmethyldimethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane, isopropenylmethyldimethoxysilane, isopropenyltrimethoxysilane, isopropenyltriethoxysilane.

The polymerizable unsaturated group-containing monomer to be copolymerized can be appropriately selected as needed. It is preferable to use a cyano group-containing monomer such as acrylonitrile or a styrene-based monomer such as styrene, since particularly excellent adhesiveness and mechanical strength can be exhibited.

The amount of the polymer of the polymerizable unsaturated group-containing monomer is not particularly limited and may be 0.1 to 1000 parts by weight, particularly 0.1 to 100 parts by weight, based on 100 parts by weight of the polyether (A). It is preferable to use within the range from the viewpoint of workability and the like.

When the polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule is copolymerized with another polymerizable unsaturated group-containing monomer, a polymerizable unsaturated group having a hydrophilic group in the molecule is used. The group-containing monomer is preferably 10% by weight or more, and particularly preferably 30% by weight or more of the total amount of the polymerizable unsaturated group-containing monomer.

The polymerizable unsaturated group-containing monomer is polymerized by a method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the polyether (A), a method of polymerizing the polymerizable unsaturated group-containing monomer in a solvent, Examples thereof include a method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the polyether (D).

The polyether (D) is a polyether compound before introducing the reactive silyl group in the above-mentioned method for producing the polyether (A), and is a polyether having a hydroxyl group or an unsaturated group at the terminal. is there.

The polyether (D) may be a polyether (C) having a polymerizable unsaturated group in the molecule. In this case, in particular, the polymer (B) of the polymerizable unsaturated group-containing monomer
When coexisting with the polyether (A), excellent storage stability can be secured. Even when the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polyether (A) or in a solvent, the above-mentioned polymerizable unsaturated group-containing polyether (C)
The same effect can be obtained by coexisting.

The polyether (C) having a polymerizable unsaturated group is a polymer having one or more polymerizable unsaturated groups in one molecule and the main chain consisting essentially of a polyether chain. Examples of the polymerizable unsaturated group in this case include the groups shown below. These polymerizable unsaturated groups may be present at the ends or side chains of the polyether. In addition,
In the following, φ represents a phenylene group.

[0045]

Embedded image _{-OCH 2 CH = CH 2, -OC} (CH 3) = CH 2, -OCH 2 CH 2 CH = CH 2, -OCOCH 2 CH = CH 2, -OCOCH = CH 2, -OCOC (CH _{3) = CH 2, -OCH 2} -φ-CH = CH 2.

As the method for producing the polyether (C) having a polymerizable unsaturated group, a method of converting a terminal hydroxyl group of a hydroxyl group-terminated polyether obtained by ring-opening addition polymerization of monoepoxide into a polymerizable unsaturated group, A method of ring-opening addition-polymerizing a monoepoxide with an active hydrogen-containing compound containing a polymerizable unsaturated group, or a method of copolymerizing a mono-epoxide containing a polymerizable unsaturated group such as allyl glycidyl ether during the ring-opening addition polymerization of a monoepoxide. By polymerizing,
Examples thereof include a method of introducing a polymerizable unsaturated group into a side chain or a terminal. As a specific method, the method previously proposed by the inventor (see Japanese Patent Application Laid-Open No. 3-72527) and the like can be mentioned.

The polyether (C) having a polymerizable unsaturated group may be a polyether having a reactive silyl group together with a polymerizable unsaturated group in the molecule. In this case, a cured product having excellent mechanical properties can be obtained. The reactive silyl group, like a silanol group and a hydrolyzable silyl group,
It causes condensation and reaction with moisture, curing agent, etc.
It is shown by equation (8).

[0048]

[Image Omitted] Z _3-r —Si (R ¹¹ ) _r − (8) In the formula, R ¹¹ is a monovalent hydrocarbon group or a halogenated hydrocarbon group, Z is a hydroxyl group, a halogen atom, an alkoxy group, Hydrolyzable group such as acyloxy group, amide group, amino group, aminoxy group or ketoximate group, r is 0, 1 or 2.

Polyethers having a reactive silyl group together with a polymerizable unsaturated group in such a molecule include, for example, a part of the terminal allyl group of the allyl group-terminated polyether and the formula (9).
It can be produced by reacting the hydrosilicon compound represented by the formula (1) in the presence of a Group 8 metal such as platinum or a catalyst comprising the compound, but is not particularly limited thereto.

[0050]

Embedded image Z _3-r —Si (R ¹¹ ) _r H (9) In the formula, R ¹¹ , Z and r are the same as defined above.

The solvent can be appropriately selected according to the kind of the polymerizable unsaturated group-containing monomer used for the polymerization. The polymerization initiator used for the polymerization is not limited to the radical generator, various compounds capable of polymerizing the polymerizable unsaturated group-containing monomer can be used,
In some cases, the polymerization can be carried out by radiation or heat without using a polymerization initiator. Examples of the polymerization initiator include peroxide-based, azo-based, or redox-based polymerization initiators and metal compound catalysts. Specific examples of polymerization initiators often used include azobisisobutyronitrile,
Examples thereof include benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, diisopropyl peroxy carbonate and the like.

The composition of the present invention comprises a polymer (B) of a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule and a polyether (A) containing at least one reactive silyl group in the molecule. ) Is obtained by mixing the polymerizable unsaturated group-containing monomer with a polyether (A) containing at least one reactive silyl group in the molecule.
When the reaction is carried out in the presence of, the desired composition can be obtained after the polymerization of the monomer without mixing with the polyether (A) newly containing at least one reactive silyl group in the molecule.

When the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polyether (D), after polymerization,
The desired composition can also be obtained by subsequently introducing a reactive silyl group into the polyether (D). When the polymerizable unsaturated group-containing monomer is polymerized in a solvent, it is mixed with a polyether (A) containing at least one reactive silyl group in the molecule, and then a part or all of the solvent is distilled off. You may.

The polymer (B) of the polymerizable unsaturated group-containing monomer in the composition is uniformly dispersed in fine particles in the polyether (A) containing at least one reactive silyl group in the molecule. However, it is preferable that they are uniformly dispersed in consideration of workability such as viscosity of the composition.

In the curable composition of the present invention, a curing accelerating catalyst that accelerates the curing reaction of the reactive silyl group may be used in order to accelerate the curing with moisture. Examples of the curing accelerator catalyst include metal titanates, organosilicon titanates, bismuth tris-2-ethylhexoate, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate; dibutylamine-2-ethylhexylate. Amine salts such as xoates and the like; as well as other acidic catalysts and basic catalysts such as laurylamine may be used.

Further, a dehydrating agent may be added to the curable composition of the present invention to improve storage stability. As the dehydrating agent, alkyl orthoformates; hydrolyzable organic silicon compounds such as vinyltrimethoxysilane and tetraethylsilicate; hydrolyzable organic titanium compounds and the like can be used.

The curable composition of the present invention may further contain a filler, a plasticizer, etc., if necessary. Known fillers can be used as the filler, and specifically, fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined Clay, clay, talc,
Fillers such as titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and glass balloons, and fibrous fillers such as asbestos, glass fibers and filaments can be used.

As the plasticizer, known plasticizers can be used, and specifically, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate;
Aliphatic carboxylic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, butyl oleate; glycol esters such as pentaerythritol ester; phosphoric acid esters such as trioctyl phosphate, 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. Further, polyoxypropylene monool, polyoxypropylene diol, and terminal modified products thereof can also be used. Examples of the terminal-modified product include a compound in which a terminal hydroxyl group is modified into an alkoxy group or an alkenyloxy group, a compound blocked with a hydrocarbon group through a urethane bond, an ester bond, a urea bond or a carbonate bond, and the like.

The curable composition of the present invention may further contain various known additives. As the additives, adhesion promoters such as aminosilane, epoxysilane, phenol resin, epoxy resin, pigments, various antiaging agents, ultraviolet absorbers and the like can be used.

The curable composition of the present invention cures at room temperature in the presence of moisture and can be used especially for elastic sealants and adhesives.

[0061]

【Example】

[Production Example 1] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol.
Isocyanatopropylmethyldimethoxysilane was added to this to undergo a urethane reaction to convert the hydroxyl groups at both ends into methyldimethoxysilylpropyl groups, and to give an average molecular weight of 10
000 polyethers P1 were obtained.

[Production Example 2] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using glycerin as an initiator to obtain polyoxypropylene triol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into a methyldimethoxysilyl group, and to give an average molecular weight of 170
00 polyether P2 was obtained.

Production Example 3 Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Average molecular weight 1
7000 polyether P3 was obtained.

[Production Example 4] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 50% of allyl groups into methyldimethoxysilyl groups,
Polyether P4 having an average molecular weight of 17,000 was obtained.

[Production Example 5] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 100% of the allyl group into a methyldimethoxysilyl group to obtain a polyether P5 having an average molecular weight of 17,000. .

[Production Example 6] A polyoxypropylene diol having an average molecular weight of 3,000 was converted to a terminal sodium metal alkoxide with sodium metal, and then reacted with dibromomethane to increase the molecular weight to obtain a high molecular weight polyol having an average molecular weight of 8000. . The terminal hydroxyl group of the obtained high molecular weight polyol was converted into a methyldimethoxysilyl group in the same manner as in Production Example 2 to obtain polyether P6.

[Production Example 7] Propylene oxide was polymerized with KOH catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. The terminal hydroxyl group of the obtained high molecular weight polyol was converted into a methyldimethoxysilyl group in the same manner as in Production Example 2 to give an average molecular weight of 80.
00 polyether P7 was obtained.

[Production Examples 8 to 16] Production Examples 1 and 2,
50 g of the polyether obtained in Production Example 5, Production Example 6 or Production Example 7 was placed in a 4-necked flask of 300 cm ³ , and 1
While maintaining the temperature at 10 ° C, 50 g of polyether, 30 g of the monomers shown in Table 1 and 0.6 of azobisisobutyronitrile
The mixture of g was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, unreacted monomers were removed by degassing under reduced pressure by heating at 110 ° C. and 0.1 mmHg for 2 hours to obtain a mixture of polyether (A) and polymer (B). Table 1 shows the types of polyether and the types of monomers used. The monomers used in Table 1 and the like are shown by the abbreviations in Table 2.

[Production Example 17] Propylene oxide was polymerized with diethylene glycol as an initiator using a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol having an average molecular weight of 17,000. 50 g of this polyol was put into a 300 cm ³ four-necked flask and
Keeping at ℃, polyether 50g, M-20G 25
g, and a mixture of 0.6 g of azobisisobutyronitrile were added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, unreacted monomers were removed by degassing under reduced pressure by heating at 110 ° C. and 0.1 mmHg for 2 hours. Subsequently, isocyanatopropylmethyldimethoxysilane was added thereto to carry out a urethane-forming reaction to convert the hydroxyl groups at both terminals into methyldimethoxysilylpropyl groups to obtain a mixture of polyether (A) and polymer (B).

Production Example 18 15 g of the polyether P3 obtained in Production Example 3 was dissolved in 100 g of the polyether P5 obtained in Production Example 5 and placed in a 4-necked flask for 10
While maintaining at 0 ° C., a mixture of 21 g of M-20G, 9 g of acrylonitrile, and 0.2 g of azobisisobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction was completed, the unreacted monomer was heated and degassed under reduced pressure for 2 hours at 110 ° C. and 0.1 mmHg to distill off to obtain a mixture of polyether (A) and polymer (B).

Production Example 19 15 g of the polyether P4 obtained in Production Example 4 was dissolved in 100 g of the polyether P5 obtained in Production Example 5 and placed in a 4-necked flask.
While maintaining at 0 ° C., a mixture of 21 g of M-20G, 9 g of acrylonitrile, and 0.2 g of azobisisobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction was completed, the unreacted monomer was heated and degassed under reduced pressure for 2 hours at 110 ° C. and 0.1 mmHg to distill off to obtain a mixture of the polyether (A) and the polymer (B).

[Preparation Example 20] 50 g of the polyether P3 obtained in Preparation Example 3 was dissolved in 100 g of toluene, placed in a four-necked flask, and kept at 100 ° C. to give M-20G.
70 g, acrylonitrile 30 g, and azobisisobutyronitrile 0.6 g were added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, 250 g of the polyether P5 obtained in Production Example 5 was added and mixed with stirring, and then, with stirring.
Toluene and unreacted monomer at 110 ° C, 0.1 mmH
The mixture was heated and degassed under reduced pressure for 2 hours and then distilled off to obtain a mixture of the polyether (A) and the polymer (B).

[Production Example 21] 50 g of the polyether P4 obtained in Production Example 4 was dissolved in 100 g of toluene, placed in a four-necked flask, and kept at 100 ° C. to give M-20G.
70 g, acrylonitrile 30 g, and azobisisobutyronitrile 0.6 g were added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, 250 g of the polyether P5 obtained in Production Example 5 was added and mixed with stirring, and then, with stirring.
Toluene and unreacted monomer at 110 ° C, 0.1 mmH
The mixture was heated and degassed under reduced pressure for 2 hours and then distilled off to obtain a mixture of the polyether (A) and the polymer (B).

Examples 1 to 13 and Comparative Examples 1 to 2 150 parts by weight of calcium carbonate based on 100 parts by weight of the mixture of polyether (A) and polymer (B) obtained in the above Production Examples 8 to 21. Parts, 50 parts by weight of dioctyl phthalate, 20 parts by weight of titanium oxide, 3 parts by weight of thixotropic agent, 1 part by weight of hindered phenol antioxidant, 1 part by weight of benzotriazole ultraviolet absorber, 2 parts by weight of aminosilane, dibutyl. 1 part by weight of tin dilaurate and 0.5 part by weight of laurylamine were kneaded under conditions where moisture was not included to obtain curable compositions (Examples 1 to 13 and Comparative Example 1).

Further, the polyether (A) and the polymer (B)
A curable composition having the same composition as the above except that the polyether P2 obtained in Production Example 2 was used instead of the mixture (Comparative Example 2).

Upon exposure to moisture, these compositions immediately started to cure and changed into good rubber elastic bodies.
Each curable composition was placed in an atmosphere of 20 ° C. and 65% for 1 day, and the curing depth was measured to examine the internal curability. Table 3 shows the results.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

As described above, the polyether (A) containing at least one reactive silyl group in the molecule,
Curable composition containing a polymer (B) obtained by copolymerizing a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule, alone or with another polymerizable unsaturated group-containing monomer, as an essential component Has a significantly higher internal curability.

Claims (9)

[Claims] 1. A polyether (A) having at least one reactive silyl group in the molecule, and a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or another polymerizable unsaturated group. A curable composition containing, as an active ingredient, a polymer (B) obtained by polymerizing a contained monomer. 2. The curable composition according to claim 1, wherein the polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule has a structure represented by the following formula (1). CH ₂ ═C (R ¹ ) COO— (CH ₂ CH ₂ O) _m R ² (1) In the formula, R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and m is An integer of 1 or more. 3. The curable composition according to claim 1, wherein the polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule is acrylamide. 4. The curable composition according to claim 1, wherein the polymer (B) is uniformly dispersed in the polyether (A). 5. The polyether (A) and the polymer (B) are
A polymer (A) obtained by polymerizing a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or another polymerizable unsaturated group-containing monomer in the polyether (A). The curable composition according to any one of 1. 6. The polyether (A) and the polymer (B) are
In the polyether (A), in the presence of the polyether (C) having an average of at least one polymerizable unsaturated group in the molecule, a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or The curable composition according to any one of claims 1 to 4, which is obtained by polymerizing it with another polymerizable unsaturated group-containing monomer. 7. The polyether (A) and the polymer (B) are
By polymerizing a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or another polymerizable unsaturated group-containing monomer in a polyether (D) having a functional group capable of introducing a reactive silyl group After obtaining the polymer,
The curable composition according to any one of claims 1 to 4, which is obtained by subsequently introducing a reactive silyl group into the polyether (D). 8. The polyether (A) and the polymer (B) are
After obtaining a polymer (B) by polymerizing a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or another polymerizable unsaturated group-containing monomer in a solvent, a polyether (A) is obtained. The curable composition according to any one of claims 1 to 4, which is obtained by mixing with, and then distilling off the solvent. 9. The polyether (A) and the polymer (B) are
In a solvent, in the presence of a polyether (C) having an average of at least one polymerizable unsaturated group in the molecule, a polymerizable unsaturated group-containing monomer having a hydrophilic group in the molecule or other polymerizable compounds A polymer (B) is obtained by polymerizing an unsaturated group-containing monomer, then mixed with a polyether (A), and then the solvent is distilled off. The curable composition according to any one of 1.