JP2001031870A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting composition stable at a room temperature for a long period of time and giving a sufficient curing rate on heating by including a specific silyl group-containing organic polymer and a monoalkyl tin compound as a curing catalyst. SOLUTION: This composition is obtained by including (A) 100 pts.wt. silyl group-containing organic polymer having one or more groups having a silicon atom bonding to a hydrolyzable group based on a molecule at the terminal end or the side chain of the molecule, and (B) 0.1-10 pts.wt. monoalkyl tin compound as a curing catalyst. Preferably the component B is one or more compounds selected from (i) a compound of the formula R1SnX3 [R1 is a 1-12C alkyl; X is a 1-18C fatty carboxylic acid residual group, mono maleate residual group or a group of formula I (R2 and R3 are each a 1-4C alkyl; n is 0, 1 or 3), (ii) a compound of the formula (R1SnX2)2O or (iii) a compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to thermosetting compositions having a long useful life, comprising a catalyst which is inert at room temperature and becomes active at elevated temperatures.

[0002]

2. Description of the Related Art Conventionally, curable compositions have been known as two-pack type in which a main agent and a curing agent are mixed at a predetermined ratio at the time of use, and in one-pack type which does not require these mixing operations. The one-pack type is excellent in workability. In particular, the modified silicone resin one-pack type composition is superior to the silicone resin one-pack type composition and the urethane resin-based one-pack resin in adhesiveness, storage stability, mold resistance and the like. It is characterized in that it has no stone contamination like a liquid type composition and no surface tack remains like a urethane resin-based one-part type composition. However, particularly in the case of a modified silicone resin-based one-pack composition having an alkoxy-terminated end, the curing is slow and, in many cases, a curing catalyst such as a metal salt is usually used.

[0003]

The curable composition containing such a curing catalyst has the property of rapidly curing even at room temperature in the presence of moisture and converting to a rubbery substance. When stored, the quality gradually deteriorates. In general, a one-part composition is used in an industrial line, and a method is used in which a low-activity curing catalyst is blended in order to obtain long-term storage stability, and a sufficient curing rate is obtained by heating. However, the use life of such a low activity catalyst is not sufficient. In addition, Japanese Patent Publication No. 5-7426,
Japanese Patent Publication No. 7-76228 proposes a latent organotin catalyst which is inactive at room temperature and changes into an active compound by raising the temperature. However, these compounds are difficult to produce, and these compounds are difficult to produce. Not as stable and impractical as described in the publication.

The present invention has been made in view of the above-mentioned problems of the prior art,
An object of the present invention is to provide a modified silicone resin-based one-pack type curable composition which is stable at room temperature for a long period of time and can obtain a sufficient curing rate when heated.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a monoalkyltin compound as a catalyst, it is possible to obtain a cured product which is stable for a long time at room temperature and shows sufficient curing characteristics when heated. The present inventors have found that a hydrophilic composition can be obtained, and have completed the present invention.

That is, the present invention provides a silyl group-containing organic polymer (A) having at least one group having a silicon atom bonded to a hydrolyzable group at a molecular terminal or a side chain per molecule, and a curing catalyst. Monoalkyltin compound (B)
A monoalkyltin compound (B)
Is 0.1 to 10 parts by weight with respect to 100 parts by weight of the silyl group-containing organic polymer (A).

Further, the present invention provides a method for producing a monoalkyltin compound (B) having the general formula (1), (2) or (3): R ¹ SnX ₃ (1) (R ¹ SnX ₂ ) ₂ O (2)

[0008]

Embedded image

Wherein R ¹ is selected from an alkyl group having 1 to 12 carbon atoms, and X is an aliphatic carboxylic acid residue having 1 to 18 carbon atoms, a monoester maleic acid residue, Equation (4):

[0010]

Embedded image

Wherein R ² and R ³ each represent an alkyl group having 1 to 4 carbon atoms, and n represents 0, 1 or 3.
And at least one monoalkyltin compound represented by the formula (1):

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Organic polymer (A) used in the present invention
Is a group having a silicon atom bonded to a hydrolyzable group (hereinafter sometimes referred to as a silicon group bonded to a hydrolyzable group)
At the end or side chain of the molecule, at least 1
This is a silyl group-containing organic polymer having a main chain, and examples of the main chain of the polymer include an alkylene oxide polymer, a polyether, and an ether / ester block copolymer. Further, a polymer of an ethylenically unsaturated compound or a diene compound may be used.

The alkylene oxide polymer or polyether includes (CH ₂ CH ₂ O) m (CHCH ₃ CH ₂ O) m (CHC ₂ H ₅ CH ₂ O) m (CH ₂ CH ₂ CH ₂ CH ₂ O) And m) having a repeating unit such as m. Where m
Is an integer of 2 or more.

The polymers of the ethylenically unsaturated compound and the diene compound include ethylene, propylene, acrylate, methacrylate, vinyl acetate,
Examples thereof include homopolymers of acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene and the like, and copolymers of two or more of these. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer Polymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylate, polymethacrylate, etc. Is mentioned.

The silicon group bonded to the hydrolyzable group may be, for example, a catalyst or the like used in the presence of moisture or a crosslinking agent, as in the case of a silicon-containing group having a hydrolyzable group bonded to a silicon atom. Is a group that causes a condensation reaction. Specifically, a halogenated silyl group, an alkoxysilyl group,
Examples include an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group, an aminooxysilyl group, an oximesilyl group, and an amidesilyl group. Here, the number of these hydrolyzable groups bonded to the silicon atom in the silicon group bonded to the hydrolyzable group is selected from the range of 1 to 3. Further, the number of hydrolyzable groups bonded to one silicon atom may be one or more. Further, a hydrolyzable group and a non-hydrolyzable group may be bonded to one silicon atom. As the silicon group bonded to the hydrolyzable group, an alkoxysilyl group (including a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group) is particularly preferable in terms of easy handling. The silicon group bonded to the hydrolyzable group may be present at the terminal of the polymer molecule or at a side chain. The number of silicon groups bonded to a hydrolyzable group may be at least one per molecule of the polymer, but from the viewpoint of curing speed and cured physical properties, it is preferable that the number is at least 1.5 on average per molecule. . A known method can be adopted as a method for bonding the silicon group bonded to the hydrolyzable group to the main chain polymer.

Although the molecular weight of the organic polymer (A) used in the present invention is not particularly limited, those having an excessively high molecular weight have a high viscosity and are difficult to use when a curable composition is used. The number average molecular weight is desirably 30,000 or less. Such an organic polymer can be produced by a known method. For example, a commercially available product such as Kaneka MS polymer manufactured by Kaneka Chemical Industry Co., Ltd. may be used.

The curing catalyst (B) used in the present invention includes:
One or more of the monoalkyltin compounds represented by the general formulas (1), (2) and (3) are preferably used.
In these general formulas, the number of carbon atoms represented by R ¹ is 1 to 1
Examples of the alkyl group 2 include methyl, ethyl, propyl,
Butyl, isobutyl, octyl, 2-ethylhexyl,
A straight-chain or branched-chain alkyl such as lauryl can be mentioned. Among X, examples of the aliphatic carboxylic acid residue having 1 to 18 carbon atoms include acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, octanoic acid, 2-ethylhexanoic acid, and neodecanoic acid (Versatic acid from Shell). Lauric acid, stearic acid, oleic acid and the like. Among X, the monoester maleic acid residue includes alkyl monoester maleic acid having an alkyl group having 1 to 18 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, and stearyl. And the residue of benzyl monoester maleic acid. In X, the group represented by the general formula (4) (alkoxysilicate group or alkoxyalkylsilicate group) includes a trimethoxysilicate group, a triethoxysilicate group, a tripropoxysilicate group, a tributoxysilicate group, and a dimethoxymethylsilicate group. , An alkoxysilicate group having an alkoxy group having 1 to 4 carbon atoms such as a methoxydimethylsilicate group, an alkoxyalkyl silicate group having an alkoxy group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. .

The curing catalyst (B) used in the present invention includes:
In the general formulas (1), (2) and (3), those in which X is a halogen or an alkylmercapto group can also be used. Examples of the halogen represented by X include chlorine, bromine, iodine, and the like. The alkyl mercapto group represented by X has a carbon number of 1 to 1, such as a methyl mercapto group, an ethyl mercapto group, a butyl mercapto group, an isobutyl mercapto group, an octyl mercapto group, a 2-ethylhexyl mercapto group, a stearyl mercapto group, and a lauryl mercapto group. 18 alkylmercapto groups.

Examples of the monoalkyltin compound represented by the general formula (1) include, for example, monomethyltin triacetate, monomethyltin tripivalate, monomethyltin trioctoate, monomethyltin tris (2-ethylhexanoate), and monomethyltin trineo Decanate, monomethyltin trilaurate, monomethyltin tristearate, monobutyltin triacetate, monobutyltin tripivalate, monobutyltin trioctoate, monobutyltin tris (2-ethylhexanoate), monobutyltin trineodecanate, monobutyltin trilaurate, Monobutyltin tristearate, monooctyltin triacetate, monooctyltin tripivalate, monooctyltin trioctoate, monooctyltin tris (2-ethylhexanoate) Monooctyltin tri neodecanate, monooctyltin Toriraureto, monooctyltin tristearate, monoalkyl tin fatty acid salt, such as monolauryl tin triacetate; monooctyltintris (butyl maleate), monobutyltin tris (benzyl maleate)
And the like. Monoalkyltin monoester malate salts such as monobutyltin tris (triethoxysilicate), monobutyltin tris (dimethoxymethyl silicate), and monoalkyltin alkoxysilicates such as monooctyltin tris (triethoxysilicate). Further, monoalkyltin halides such as monomethyltin trichloride, monobutyltin trichloride and monooctyltin trichloride; monoalkyltin mercaptan compounds such as monobutyltin tris (laurylmercapto) and monobutyltin tris (isooctylthioglycolate) And the like. Of these, monoalkyltin fatty acid salts are particularly preferred.

Examples of the monoalkyltin compound represented by the general formula (2) include, for example, 1,3-dimethyl-1,1
1,3,3-tetraacetyloxydistannoxane,
1,3-dimethyl-1,1,3,3-tetrapivaloyloxydistannoxane, 1,3-dimethyl-1,1,
3,3-tetraoctanoyloxydistannoxane,
1,3-dimethyl-1,1,3,3-tetrakis (2-
Ethylhexanoyloxy) distanosan, 1,3-dimethyl-1,1,3,3-tetranedecanoyloxydistannoxane, 1,3-dimethyl-1,1,3,3-
Tetralauroyloxydistannoxane, 1,3-dimethyl-1,1,3,3-tetrastearoyloxydistannoxane, 1,3-dibutyl-1,1,3,3-tetraacetyloxydistannoxane, , 3-dibutyl-
1,1,3,3-tetrapivaloyloxydistannoxane, 1,3-dibutyl-1,1,3,3-tetraoctanoyloxydistannoxane, 1,3-dibutyl-1,
1,3,3-tetrakis (2-ethylhexanoyloxy) distannoxane, 1,3-dibutyl-1,1,3,
3-tetranedecanoyloxydistannoxane, 1,
3-dibutyl-1,1,3,3-tetralauroyloxydistannoxane, 1,3-dibutyl-1,1,3,3
-Tetrastearoyloxydistannoxane, 1,3-
Dioctyl-1,1,3,3-tetraacetyloxydistannoxane, 1,3-dioctyl-1,1,3,3-
Tetrapivaloyloxydistannoxane, 1,3-dioctyl-1,1,3,3-tetraoctanoyloxydistannoxane, 1,3-dioctyl-1,1,3,3-
Tetrakis (2-ethylhexanoyloxy) distannoxane, 1,3-dioctyl-1,1,3,3-tetraneodecanoyloxydistannoxane, 1,3-dioctyl-1,1,3,3-tetralauroyl Dialkyldistannoxane fatty acid salts such as oxydistannoxane, 1,3-dioctyl-1,1,3,3-tetrastearoyloxydistannoxane, 1,3-dibutyl-1,1,1
3,3-tetrakis (butylmalenoyloxy) distannoxane, 1,3-dibutyl-1,1,3,3-tetrakis (benzylmalenoyloxy) distannoxane,
Dialkyldistanos such as 1,3-dioctyl-1,1,3,3-tetrakis (butylmalenoyloxy) distannoxane and 1,3-dioctyl-1,1,3,3-tetrakis (benzylmalenoyloxy) distannoxane Xanmonoalkyl malate salts, 1,3-dibutyl-
1,1,3,3-tetrakis (triethoxysilyloxy) distannoxane, 1,3-dioctyl-1,1,
And dialkyldistannoxane alkoxysilicates such as 3,3-tetrakis (triethoxysiloxy) distannoxane. Further, 1,3-dibutyl-
1,1,3,3-tetrachlorodistannoxane, 1,3
Dialkyldistannoxane halides such as dioctyl-1,1,3,3-tetrachlorodistannoxane;
1,3-dibutyl-1,1,3,3-tetra (laurylmercapto) distannoxane, 1,3-dioctyl-
And dialkyldistannoxane mercaptos such as 1,1,3,3-tetra (laurylmercapto) distannoxane and 1,3-dibutyl-1,1,3,3-tetrakis (isooctylthioglycolate) distannoxane. Among these, dialkyldistannoxane fatty acid salts are particularly preferred.

Examples of the monoalkyltin compound represented by the general formula (3) include, for example, monomethyltin oxyacetate, monomethyltin oxypivalate, monomethyltin oxyoctoate, monomethyltin oxy (2-ethylhexanoate), monomethyltin Oxyneodecanate,
Monomethyltin oxylaurate, monomethyltin oxystearate, monobutyltin oxyacetate, monobutyltin oxypivalate, monobutyltin oxyoctoate, monobutyltinoxy (2-ethylhexanoate), monobutyltin oxyneodecanate, monobutyltin oxyneodecanate Rate, monobutyltin oxystearate, monooctyltin oxyacetate, monooctyltin oxypivalate, monooctyltin oxyoctoate, monooctyltinoxy (2-ethylhexanoate), monooctyltin oxyneodecanate, monooctyltin Monoalkyltin fatty acid salts such as oxylaurate, monooctyltin oxystearate, monolauryltin oxyacetate; monobutyltin oxybutyl malate;
Monoalkyltin monoalkyl malate salts such as monobutyltin oxybenzylmalate; and monoalkyltin alkoxysilicates such as monobutyltin oxytriethoxysilicate. Further, monoalkyltin halides such as monomethyltin oxychloride, monobutyltin oxychloride and monooctyltin oxychloride; and monoalkyltin mercaptan compounds such as monobutyltin oxylauryl mercapto and monobutyltin oxyisooctylthioglycolate. . Of these, monoalkyltin fatty acid salts are particularly preferred.

In the thermosetting composition of the present invention, the monoalkyltin compound (B) as a curing catalyst is used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the silyl group-containing organic polymer (A).
It is preferable to mix by weight. If the amount of the monoalkyltin compound (B) is less than the above range, the curing performance is insufficient, while if it exceeds the above range, physical properties such as resilience and weather resistance of the cured product after curing become poor.

For the thermosetting composition of the present invention, various known amino group-substituted alkoxysilane compounds or condensates thereof may be used in order to promote curing and improve adhesion to a substrate. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N′-bis (Trimethoxysilylpropyl) ethylenediamine and partial hydrolysates thereof.

The thermosetting composition of the present invention may further contain various known fillers, coloring agents, plasticizers, anti-sagging agents,
Additives and the like can be included. As the filler, specifically, calcium carbonate, kaolin, talc, fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, clay, calcined clay, glass, bentonite, organic bentonite, shirasu balloon, glass fiber, Asbestos, glass filament, crushed quartz, diatomaceous earth, aluminum silicate,
Aluminum hydroxide, zinc oxide, magnesium oxide, titanium oxide and the like are used. Specific examples of the coloring agent include iron oxide, carbon black, phthalocyanine blue, and phthalocyanine green. Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and butyl benzyl phthalate, dioctyl adipate, dioctyl succinate, isodecyl succinate, isodecyl sebacate, and butyl oleate. Glycol esters such as erythryl ester, phosphates such as trioctyl phosphate and tricresyl phosphate, epoxidized soybean oil, epoxy plasticizers such as benzyl epoxy stearate, and chlorinated paraffin are used. As the anti-sagging agent, specifically, hydrogenated castor oil, silicic anhydride, organic bentonite,
Colloidal silica or the like is used. Further, as other additives, an adhesion imparting agent such as a phenol resin and an epoxy resin, an ultraviolet absorber, a radical chain inhibitor, a peroxide decomposer, various antioxidants and the like are used.

Since the curable composition of the present invention is stable at room temperature for a long period of time and exhibits sufficient curing performance when heated, it is widely used as a sealing agent, a coating agent, an elastic adhesive and the like in various industrial fields. Can be used.
Although the method of using the curable composition of the present invention is not particularly limited,
For example, after filling or applying to desired places,
By heating at 150 ° C. for 0.1 to 1 hour, a cured product having sufficient cured physical properties can be obtained.

[0026]

EXAMPLES The present invention will now be described specifically with reference to examples, but the scope of the present invention is not limited by these examples.

Production Example 1 125.3 g (0.6 mol) of monobutyltin oxide and 108.1 g of acetic acid were placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
(1.8 mol) and 400 g of toluene were charged and reacted at 114 ° C. for 2 hours while azeotropically dehydrating generated water. Then, toluene was distilled off under reduced pressure to obtain 190.6 g of a light yellow liquid monobutyltin triacetate (yield: 90%).
%). According to the results of the following elemental analysis,
It was confirmed to be monobutyltin triacetate. C (%) H (%) O (%) Sn (%) measured 33.9 5.3 27.3 33.5 theoretical 34.0 5.2 27.2 33.6

Production Example 2 In the same four-necked flask as in Production Example 1, 83.5 g (0.4 mol) of monobutyltin oxide and 122.5 g of pivalic acid
(1.2 mol) and 400 g of toluene were reacted and treated in the same manner as in Production Example 1 to obtain 182.0 g of a light yellow liquid, monobutyltin tripivalate (95% yield).
I got This compound was confirmed to be monobutyltin tripivalate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 43.5 8.1 21.8 26.7 theoretical 43.4 8.2 21.7 26.8

Production Example 3 In the same four-necked flask as in Production Example 1, 62.7 g (0.3 mol) of monobutyltin oxide and 180.3 g of lauric acid
(0.9 mol) and 400 g of toluene were reacted and treated in the same manner as in Production Example 1 to obtain 213.5 g of a light yellow liquid, monobutyltin trilaurate (92% yield).
I got This compound was confirmed to be monobutyltin trilaurate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) Measured value 62.3 10.1 12.4 15.2 Theoretical value 62.1 10.2 12.4 15.3

Production Example 4 In the same four-necked flask as in Production Example 1, 41.8 g (0.2 mol) of monobutyltin oxide and 170.7 stearic acid were added.
g (0.6 mol) and 400 g of toluene were reacted and treated in the same manner as in Production Example 1 to obtain 184.7 g of monobutyltin tristearate as a pale yellow liquid (yield 9).
0%). This compound was confirmed to be monobutyltin tristearate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 67.9 11.4 9.2 11.5 theoretical 67.9 11.2 9.3 11.6

Production Example 5 144.2 lauric acid was placed in the same four-necked flask as in Production Example 1.
g (0.72 mol) using monobutyltin oxide 7
5.2 g (0.36 mol), lauric acid 144.2 g
(0.72 mol) and 400 g of toluene,
The reaction and treatment were conducted in the same manner as in Production Example 1 to obtain 190.8 g (yield: 91%) of monobutyltin oxydilaurate as a pale yellow liquid. This compound was confirmed to be monobutyltin oxydilaurate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 57.8 9.4 12.5 20.3 theoretical 57.7 9.5 12.4 20.4

Production Example 6 49.4 g (0.14 mol) of the monobutyltin triacetate obtained in Production Example 1 was placed in a 200 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
l) and 87.5 g (0.42 mol) of orthoethyl silicate were charged and reacted at 116 ° C. for 2 hours. Ethyl acetate produced was distilled off under reduced pressure, and light yellow liquid monobutyltin tris (triethoxysilicate) 97 was removed. 9.9 g (98% yield)
I got This compound was confirmed to be monobutyltin tris (triethoxysilicate) from the results of the following elemental analysis. C (%) H (%) O (%) Si (%) Sn (%) measured 37.0 7.6 26.8 11.9 16.7 theoretical 37.1 7.6 26.9 11. 8 16.6

Production Example 7 63.6 g of monooctyltin oxide was placed in a four-necked flask.
(0.24 mol), 144.2 g of lauric acid (0.7
2 mol) and 400 g of toluene, and reacted and treated in the same manner as in Production Example 1 to obtain 181.2 g of a light yellow liquid monooctyltin trilaurate (yield: 91%). This compound was confirmed to be monooctyltin trilaurate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 63.9 10.3 11.7 14.1 theoretical 63.7 10.4 11.6 14.3

Production Example 8 In the same four-necked flask as in Production Example 1, 79.5 g (0.3 mol) of monooctyltin oxide, 120.2 g of lauric acid
g (0.6 mol) and 400 g of toluene,
The reaction and treatment were conducted in the same manner as in Production Example 1 to obtain 174.3 g of monooctyltin oxydilaurate as a pale yellow liquid (yield: 91%).
I got This compound was confirmed to be monooctyltin oxydilaurate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 60.1 9.8 11.4 18.7 theoretical 60.2 9.9 11.3 18.6

Production Example 9 In the same four-necked flask as in Production Example 1, 50.0 g (0.3 mol) of monomethyltin oxide and 180.3 g of lauric acid
(0.9 mol) and 400 g of toluene were charged and reacted and treated in the same manner as in Production Example 1 to obtain 197.5 g (yield: 90%) of monomethyltin trilaurate as a pale yellow liquid.
This compound was confirmed to be monomethyltin trilaurate from the results of the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 60.8 9.7 13.2 16.3 theoretical 60.8 9.9 13.1 16.2

Preparation Example 10 In the same four-necked flask as in Preparation Example 1, 79.5 g (0.3 mol) of monooctyltin oxide, 155.0 g (0.9 mol) of monobutyl maleate and 400 g of toluene
, And reacted and treated in the same manner as in Production Example 1 to produce light-yellow liquid monooctyltin tris (butyl ester malate) 2
15.0 g (95% yield) was obtained. This compound was confirmed to be monooctyltin tris (butyl ester malate) by the following elemental analysis. C (%) H (%) O (%) Sn (%) measured 51.6 6.8 25.7 15.9 theoretical 51.4 7.0 25.7 15.9

Examples 1 to 10 and Comparative Examples 1 to 3 Production Examples 1 to 1 are based on 100 parts by weight of a silyl group-containing organic polymer (MS Polymer S303 manufactured by Kaneka Corporation).
0 (Examples 1-1)
0), dibutyltin dilaurate [Neostan U-100, manufactured by Nitto Kasei Co., Ltd.] (Comparative Example 1), dioctyltin dilaurate [Neostan U-810, manufactured by Nitto Kasei Co., Ltd.]
(Comparative Example 2) was added in an amount of 2 parts by weight and mixed for 3 minutes to prepare a curable composition. In Comparative Example 3, a blank was used without adding a catalyst. About the obtained curable composition,
The following stability test and catalyst activity test were performed.

Stability test method Each of the above-mentioned curable compositions (however, temperature 22 ° C., humidity 55 ± 5)
% Prepared in a constant temperature room maintained under the same conditions,
The state change over time was compared with the blank, and the stability was evaluated according to the following criteria. Table 1 shows the results.

：: No change Δ: Thickening ×: Gelation

Catalyst activity test Each of the above curable compositions (air temperature 22 ° C., humidity 55 ± 5)
% In a constant temperature room maintained at 120%).
Was heated in an oven, and the snap time (time until semi-gelling and fluidity disappeared) and tack free time (time until surface tack disappeared) were measured. Table 2 shows the results.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

As is clear from Table 1, the thermosetting composition of the present invention using a monoalkyltin compound as a curing catalyst can maintain a long usable life at room temperature even in the presence of moisture. Further, as shown in Table 2, the thermosetting composition of the present invention exhibits activity equal to or higher than Comparative Examples 1 and 2 when heated. Such a thermosetting composition can be widely used as a sealing agent, a coating agent, and an elastic adhesive in the industrial field.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hitoshi Tabuchi 3-17-14 Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka Inside Nitto Kasei Co., Ltd. (72) Inventor Kiyomi Mohri 3-chome, Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka No. 17-14 Nitto Kasei Co., Ltd. F-term (reference) 4J002 AC111 BG041 CH051 EZ046 EZ076 FD010 FD020 FD200 GJ01 GJ02 4J038 CA001 CA021 CA041 CA071 CA081 CB001 CB031 CB051 CB061 CB091 CB101 GA031 CB101 GA021

Claims (2)

[Claims] 1. A silyl group-containing organic polymer (A) having at least one group having a silicon atom bonded to a hydrolyzable group at a molecular terminal or a side chain per molecule, and a monoalkyltin as a curing catalyst The compound (B) is contained as an essential component, and the amount of the monoalkyltin compound (B) is 0.1 to 10 with respect to 100 parts by weight of the silyl group-containing organic polymer (A).
A thermosetting composition characterized by being in parts by weight. 2. The monoalkyltin compound (B) is represented by the general formula (1), (2) or (3): R ¹ SnX ₃ (1) (R ¹ SnX ₂ ) ₂ O (2) [Wherein, R ¹ is selected from an alkyl group having 1 to 12 carbon atoms, and X is an aliphatic carboxylic acid residue having 1 to 18 carbon atoms, a monoester maleic acid residue, or a compound represented by the general formula (4) ): (Wherein, R ² and R ³ are each selected from an alkyl group having 1 to 4 carbon atoms, and n represents 0, 1 or 3). The thermosetting composition according to claim 1, which is at least one kind.