JP2001139820A - Moisture-curable composition and poly (dialkylstanoxane) disilicate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide moisture-curable compositions which quickly cure and, excel in adhesion and water-resistant adhesion. SOLUTION: The moisture-curable compositions comprise, as the major components, (A) 100 pts.wt. silyl group-containing organic polymer having at least one silicon atom bonded to a hydrolyzable group at the molecular terminal or in the side chain in the molecule and (B) 0.1-10 pts.wt. curing catalyst which is composed of a reaction product of a poly(dialkylstanoxane) dicarboxylate represented by formula (1) with a silicate compound represented by the formula: R3nSi(OR4)4-n.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable composition which cures quickly and has excellent adhesiveness and water-resistant adhesiveness, and a poly (dialkylstannoxane) disilicate compound.

[0002]

2. Description of the Related Art Silicone rubber, urethane rubber, polysulfide rubber and the like are known as one-pack type moisture curable rubber. One-component moisture-curable rubbers are generally excellent in workability in that they cure quickly and do not require adjustment of mixing of liquids as compared with two-component moisture-curable rubbers.

[0003]

However, silicone rubbers have problems in the possibility of contamination to the surroundings and paintability on the surface, while urethane rubbers have storage stability and weather resistance. There are problems with respect to the properties, foam resistance, discoloration, and the like. Further, polysulfide rubbers also have problems in curability and the possibility of contamination to the surroundings. Modified silicone rubber is a polymer having a crosslinkable hydrolyzable silicone functional group with a polyether backbone, which is stable for a long period of time in a sealed state in the presence of a curing catalyst, but rapidly when exposed to moisture. Is a one-pack type composition which cures to a rubbery substance (Japanese Patent Publication No. Sho 62-35421,
No. 141761, JP-A-1-58219).
This polymer has better storage stability, weather resistance, foaming resistance, and discoloration resistance than polyurethanes, and has better curability and less pollution to the surroundings than polysulfides.
Not toxic. In addition, it has less contamination to the surroundings than ordinary silicone rubber, and has good paintability on the surface. As a curing catalyst for the polymer having a hydrolyzable silicon group, a titanate compound, a tin carboxylate compound,
Although amines and the like are known, these catalysts have remarkably inferior adhesiveness, especially water-resistant adhesiveness, and require the use of a primer or the like. JP-B-59-38989, JP-B-1-58219, JP-B-2-22105, JP-A-58-57460, and JP-B-63-18.
975 and the like, use of a reaction product of a dialkyltin oxide or a carboxylate and an alkoxysilane as a curing catalyst for a polymer having a hydrolyzable silicon group is disclosed. It has been proposed to use bis (triethoxysilicate) as a curing catalyst. The use of these organotin silicate compounds increases the curing speed as compared with the use of organotin carboxylate, but is not sufficient, and it has been desired to develop a catalyst having a higher curing speed.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
The present inventors have intensively studied to obtain a moisture-curable composition which cures quickly and has excellent adhesiveness and water-resistant adhesiveness, and completed the present invention.

That is, the invention according to claim 1 is characterized in that 100 parts by weight of a silyl group-containing organic polymer (A) having at least one silicon atom bonded to a hydrolyzable group at a molecular terminal or a side chain in one molecule. In a composition containing 0.1 to 10 parts by weight of the curing catalyst (B) as a main component, the curing catalyst (B)
Is the following formula (1):

[0006]

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(Wherein, R ¹ and R ² are each independently a hydrocarbon group having 1 to 12 carbon atoms, and two R ¹ ,
(2m + 2) R ^{2 s} may be the same or different, and m is an integer of 1 or more) and a poly (dialkylstannoxane) dicarboxylate represented by the following formula (2) R ³ _n Si (OR ⁴ ) _4-n (2) (wherein R ³ and R ⁴ each independently represent a carbon atom of 1
To 4 hydrocarbon groups, n R ³ and (4-n) R ⁴ may be the same or different, and n is 0 to 4
A silicate compound represented by the formula:
Alternatively, the present invention relates to a moisture-curable composition comprising a reaction product with a hydrolyzate thereof.

According to a second aspect of the present invention, the curing catalyst (B) comprises a poly (dialkylstannoxane) dicarboxylate represented by the general formula (1) and a silicate compound represented by the general formula (2) And / or a mixture of a reaction product with a hydrolyzate thereof and a silicate compound represented by the general formula (2) and / or a hydrolyzate thereof. Composition.

Further, according to a third aspect of the present invention, the curing catalyst (B) is represented by the following formula (3):

[0010]

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Wherein R ² , R ⁴ and m are the same as defined above, or a poly (dialkylstannoxane) disilicate compound represented by the following formula: 2. The moisture-curable composition according to claim 1, which is a mixture with a hydrolyzate thereof.

Further, according to a fourth aspect of the present invention, there is provided the following formula (3):

[0013]

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Wherein R ² is a hydrocarbon group having 1 to 12 carbon atoms, (2m + 2) R ^{2 s} may be the same or different, and R ⁴ is A poly (dialkylstannoxane) represented by a hydrocarbon group having 1 to 4 atoms, and 6 R ^{4 s} may be the same or different, and m is an integer of 1 or more. It relates to a disilicate compound.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Organic polymer (A) used in the present invention
Is a silyl group-containing organic polymer having at least one silicon atom bonded to a hydrolyzable group (hereinafter, sometimes referred to as a silicon group bonded to a hydrolyzable group) in one molecule at a molecular terminal or a side chain. Wherein the main chain of the polymer is an alkylene oxide polymer or polyether, ether.
Ester block copolymers and the like can be mentioned. 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) p (CHCH ₃ CH ₂ O) p (CHC ₂ H ₅ CH ₂ O) p (CH ₂ CH ₂ CH ₂ CH ₂ O ) P and the like having a repeating unit. Where p
Is an integer of 2 or more.

The polymers of the ethylenically unsaturated compounds and diene compounds include ethylene, propylene, acrylates, methacrylates, 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 is a group that causes a condensation reaction by using a catalyst or the like, if necessary, in the presence of moisture or a crosslinking agent. Specifically, a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group,
Examples include an aminooxysilyl group, an oximesilyl group, and an amidosilyl 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 is
It may be present at the terminal of the polymer molecule or in a side chain. The number of silicon groups bonded to the hydrolyzable group may be at least one per molecule of the polymer.
From the viewpoint of the cured physical properties, it is preferable that the number is 1.5 or more per molecule on average. A known method can be adopted as a method for bonding the silicon group bonded to the hydrolyzable group to the main chain polymer.

The molecular weight of the organic polymer (A) used in the present invention is not particularly limited, but 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 reaction products of the dialkyltin oxydicarboxylate represented by the general formula (1) and the silicate compound represented by the general formula (2) and / or a hydrolyzate thereof are preferably used. You.

In the general formula (1), the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl -Butyl, pentyl, hexyl,
Examples thereof include a linear or branched alkyl group such as heptyl, octyl, 2-ethylhexyl, decyl, and lauryl, and an unsubstituted or substituted phenyl group. Two R ¹ may be the same or different. Also (2m +
2) R ² may be the same or different. m may be an integer of 1 or more, preferably 1 to
It is an integer of 3.

Specific examples of the dialkyltin oxydicarboxylate represented by the general formula (1) include 1,1,1
3,3-tetramethyl-1,3-bis (acetoxy) distannoxane, 1,1,3,3-tetramethyl-1,3
-Bis (butyryloxy) distannoxane, 1,1,
3,3-tetramethyl-1,3-bis (octanoyloxy) distannoxane, 1,1,3,3-tetramethyl-1,3-bis (2-ethylhexanoyloxy) distannoxane, 1,1,3 , 3-Tetramethyl-1,3-
Bis (lauroyloxy) distanoxane, 1,1,
3,3-tetrabutyl-1,3-bis (acetoxy) distannoxane, 1,1,3,3-tetrabutyl-1,3
-Bis (butyryloxy) distannoxane, 1,1,
3,3-tetrabutyl-1,3-bis (octanoyloxy) distannoxane, 1,1,3,3-tetrabutyl-1,3-bis (2-ethylhexanoyloxy) distannoxane, 1,1,3,3 -Tetrabutyl-1,3-
Bis (lauroyloxy) distanoxane, 1,1,
3,3-tetraoctyl-1,3-bis (acetoxy)
Distanoxane, 1,1,3,3-tetraoctyl-
1,3-bis (butyryloxy) distanoxane, 1,
1,3,3-tetraoctyl-1,3-bis (octanoyloxy) distannoxane, 1,1,3,3-tetraoctyl-1,3-bis (2-ethylhexanoyloxy) distannoxane, 1,1 , 3,3-tetraoctyl-1,3-bis (lauroyloxy) distannoxane,
1,1,3,3-tetralauryl-1,3-bis (acetoxy) distannoxane, 1,1,3,3-tetralauryl-1,3-bis (butyryloxy) distannoxane, 1,1,3,3- Tetralauryl-1,3-bis (octanoyloxy) distannoxane, 1,1,3,
Tetraalkyldistannoxane dicarboxylates such as 3-tetralauryl-1,3-bis (2-ethylhexanoyloxy) distannoxane and 1,1,3,3-tetralauryl-1,3-bis (lauroyloxy) distannoxane , 1,1,3,3,5,5-hexamethyl-
1,5-bis (acetoxy) tristanoxane, 1,
1,3,3,5,5-hexamethyl-1,5-bis (butyryloxy) tristanoxane, 1,1,3,3
5,5-hexamethyl-1,5-bis (octanoyloxy) tristanoxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane 1,1,3,3,5,5-hexamethyl-1,5-bis (lauroyloxy) tristanoxane, 1,1,3,3,5,5-hexabutyl-
1,5-bis (acetoxy) tristanoxane, 1,
1,3,3,5,5-hexabutyl-1,5-bis (butyryloxy) tristanoxane, 1,1,3,3
5,5-hexabutyl-1,5-bis (octanoyloxy) tristanoxane, 1,1,3,3,5,5-hexabutyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane 1,1,3,3,5,5-hexabutyl-1,5-bis (lauroyloxy) tristanoxane, 1,1,3,3,5,5-hexaoctyl-1,5-bis (acetoxy ) Tristanoxane, 1,
1,3,3,5,5-hexaoctyl-1,5-bis (butyryloxy) tristanoxane, 1,1,3,3
3,5,5-hexaoctyl-1,5-bis (octanoyloxy) tristanoxane, 1,1,3,3,5
5-hexaoctyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane, 1,1,3,3
5,5-hexaoctyl-1,5-bis (lauroyloxy) tristanoxane, 1,1,3,3,5,5-hexalauryl-1,5-bis (acetoxy) tristanoxane, 1,1 , 3,3,5,5-hexalauryl-
1,5-bis (butyryloxy) tristanoxane,
1,1,3,3,5,5-hexalauryl-1,5-bis (octanoyloxy) tristanoxane, 1,1,
3,3,5,5-hexalauryl-1,5-bis (2-
Ethylhexanoyloxy) tristanoxane, 1,
Hexaalkyl tristanoxane dicarboxylates such as 1,3,3,5,5-hexalauryl-1,5-bis (lauroyloxy) tristanoxane and the like can be mentioned. Of these, tetrabutyldiacyloxydistannoxane and tetraoctyldiacyloxydistannoxane are preferable, and carboxylate having 4 or less carbon atoms is more preferable from the viewpoint of easy removal of the generated carboxylic acid ester. More preferably, it is 1,1,3,3-tetrabutyl-1,3-bis (acetoxy) distannoxane or 1,1,3,3-tetraoctyl-1,3-bis (acetoxy) distannoxane.

In the general formula (2), the hydrocarbon groups having 1 to 4 carbon atoms represented by R ³ and R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include an alkyl group such as s-butyl and t-butyl. n pieces of R ³ may be the same or different. Also the (4-n) pieces of R ⁴ may be the same or different.

As the silicate compound to be reacted with the poly (dialkylstannoxane) dicarboxylate represented by the general formula (1), a silicate compound represented by the general formula (2) and / or a hydrolyzate thereof is used. it can. Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane or hydrolysates thereof, triethoxymethylsilane, triethoxyethylsilane, triethoxypropylsilane , Triethoxyisopropylsilane, trialkoxymonoalkylsilane such as triethoxybutylsilane or a hydrolyzate thereof, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydipropylsilane, diethoxydiisopropylsilane, diethoxydibutylsilane, etc. Dialkoxydialkylsilane or its hydrolyzate, ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytripropylsilane, ethoxytriisopropylsilane Emissions, monoalkoxysilane trialkylsilane or hydrolysates thereof such as ethoxy tributyl silane. Of these, tetraalkoxysilane or its hydrolyzate is preferred. More preferably, it is tetraethoxysilane.

The poly (dialkylstannoxane) dicarboxylate and the poly (dialkylstannoxane) disilicate compound, which is a reaction product of the silicate compound and / or its hydrolyzate, are represented by the general formula (1): The (dialkylstannoxane) dicarboxylate is reacted with the silicate compound represented by the general formula (2) and / or the hydrolyzate thereof at 100 to 130 ° C. for about 1 to 3 hours, and the generated carboxylic acid ester is removed under reduced pressure. It is obtained by doing. The reaction ratio is preferably such that 1 equivalent or more of an alkoxy group is reacted with 1 equivalent of a carboxyl group to completely eliminate the carboxyl group. If the carboxyl group remains, the catalytic activity decreases. The above reaction can be carried out in the presence or absence of a solvent, but is preferably carried out usually in the absence of a solvent.

The structure of the obtained reaction product varies depending on the charging ratio of the poly (dialkylstannoxane) dicarboxylate and the silicate compound and / or its hydrolyzate, and the like. Is to react 2 mol or more, preferably 2 to 6 mol of the silicate compound represented by the general formula (2) with 1 mol of the poly (dialkylstannoxane) dicarboxylate represented by the general formula (1). The following general formula (4) obtained by:

[0027]

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(Wherein, R ² , R ³ , R ⁴ , m and n are the same as those described above).

A more preferred reaction product is represented by the general formula (1)
Is reacted with 2 mol or more, preferably 2 to 6 mol of a tetraalkyl silicate compound among the silicate compounds represented by the general formula (2) with respect to 1 mol of the poly (dialkylstannoxane) dicarboxylate represented by The following general formula (3) obtained by:

[0030]

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(Wherein R ² , R ⁴ and m are the same as described above). The poly (dialkylstannoxane) disilicate compound represented by the general formula (3) is a novel compound.

Although the reaction product of the present invention has a very high catalytic activity as compared with the conventional dialkyltin compound, the silicate compound represented by the general formula (2) is preferred because of the stability and easy handling of the catalyst. And / or a mixture of the hydrolysates thereof is preferably used, and the mixing ratio is such that when the total amount of both is 100 parts by weight, the reaction product is 99 to 100 parts by weight.
The silicate compound and / or its hydrolyzate is preferably 1 to 99 parts by weight per 1 part by weight, more preferably 90 to 50 parts by weight of the silicate compound and / or its hydrolyzate 10 to 50 parts by weight. 50 parts by weight. These mixtures can be obtained by synthesizing a reaction product and then mixing a silicate compound and / or a hydrolyzate thereof, or a mixture of a dialkyltin oxydicarboxylate and a large excess of a silicate compound and / or a hydrolyzate thereof. It can also be obtained by reaction.

In the moisture-curable composition of the present invention, the content of the curing catalyst (B) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the silyl group-containing organic polymer (A). When the amount of the curing catalyst (B) is less than the above range, the curing performance is insufficient. On the other hand, when the amount exceeds the above range, physical properties such as a recovery rate of the cured product after curing and weather resistance may be deteriorated.

In the moisture-curable composition of the present invention, various known amino group-substituted alkoxysilane compounds or condensates thereof can 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 moisture-curable composition of the present invention further comprises a filler, a coloring agent, a plasticizer, a curing accelerator, a curing retarder,
Additives usually added to the curable composition, such as an anti-sagging agent, an anti-aging agent, and a solvent, may be added. For example, 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,
Examples include ground quartz, diatomaceous earth, aluminum silicate, aluminum hydroxide, zinc oxide, magnesium oxide, and titanium dioxide. 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 dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate; and aliphatic carboxylic acids such as dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and butyl oleate. Acid esters, glycol esters such as pentaerythritol ester, phosphate esters such as trioctyl phosphate and tricresyl phosphate, epoxidized soybean oil, epoxy plasticizers such as benzyl epoxystearate, and chlorinated paraffin. . As the anti-sagging agent, specifically, hydrogenated castor oil,
Silicic anhydride, organic bentonite, colloidal silica and the like can be mentioned. Examples of other additives include an adhesion-imparting agent such as a phenol resin and an epoxy resin, an ultraviolet absorber, a radical chain inhibitor, a peroxide decomposer, and various antioxidants.

[0036]

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

Production Example 1 Dibutyltin oxide 4 was placed in a 500 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer under a nitrogen stream.
9.8 g (0.2 mol), 10.4 g of acetic anhydride (0.
1 mol) and 200 g of toluene at 112 ° C.
After reacting for 2 hours, toluene was distilled off under reduced pressure.
1,1,3,3-Tetrabutyl-1,3-bis (acetoxy) distannoxane was obtained (the compound was obtained quantitatively). Next, tetraethoxysilane (ethyl silicate)
41.7 g (0.2 mol) was charged and reacted at 120 ° C. for 3 hours. Ethyl acetate generated under reduced pressure was distilled off.
79.8 g (yield 95%, value based on tin oxide, hereinafter the same) of tin compound A as a pale yellow liquid were obtained. This compound has a tin carbonyl absorption (1638 cm
^-1 and 1559 cm ^-1 ) and the absorption of Sn-O-Sn (477 cm ^-1 ) and the results of the following elemental analysis,
It was confirmed to be 1,3,3-tetrabutyl-1,3-bis (triethoxysiloxy) distannoxane. C (%) H (%) O (%) Si (%) Sn (%) measured 40.1 7.7 17.0 6.9 28.3 theoretical 40.0 7.9 17.1 6. 7 28.3

Preparation Example 2 Dibutyltin oxide 7 was placed in the same four-necked flask as in Preparation Example 1.
4.7 g (0.3 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene.
To give 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristanoxane, and then 41.7 g (0.2 mol) of ethyl orthosilicate
l) was charged and reacted and treated in the same manner as in Production Example 1 to obtain 102.4 g (94% yield) of a tin compound B as a pale yellow liquid. This compound showed disappearance of absorption of tin carbonyl (1638 cm ⁻¹ , 1559 cm ⁻¹ ) by FT-IR and Sn
Based on the absorption of —O—Sn (477 cm ⁻¹ ) and the following elemental analysis, 1,1,3,3,5,5-hexabutyl-1,
It was confirmed to be 5-bis (triethoxysiloxy) tristanoxane. C (%) H (%) O (%) Si (%) Sn (%) measured 39.9 7.7 14.6 5.1 32.9 theoretical 39.7 7.8 14.7 5. 1 32.7

Production Example 3 In the same four-necked flask as in Production Example 1, 72.2 g (0.2 mol) of dioctyltin oxide and 10.2 g of acetic anhydride
(0.1 mol) and 200 g of toluene, and reacted and treated in the same manner as in Production Example 1 to obtain 1,1,3,3-tetraoctyl-1,3-bis (acetoxy) distannoxane, and then ethyl orthosilicate 41.7 g (0.2 mol)
And reacted at 120 ° C. for 3 hours to obtain 101.2 g (97% yield) of a tin compound C as a pale yellow liquid. This compound has a tin carbonyl absorption (1638) by FT-IR.
cm ^-1, absorption loss and Sn-O-Sn of 1559 cm ^-1) and (477cm ^-1) From the results of the following elemental analysis, 1,
It was confirmed to be 1,3,3-tetraoctyl-1,3-bis (triethoxysiloxy) distannoxane. C (%) H (%) O (%) Si (%) Sn (%) measured value 49.6 9.4 13.6 5.2 22.2 theoretical value 49.6 9.3 13.5 5. 3 22.3

Production Example 4 In the same four-necked flask as in Production Example 1, 108.3 g (0.3 mol) of dioctyltin oxide and 10.2 g of acetic anhydride
(0.1 mol) and 200 g of toluene, and reacted and treated in the same manner as in Production Example 1 to prepare 1,1,3,3,5,5
-Hexaoctyl-1,5-bis (acetoxy) tristanoxane was obtained, followed by 41.7 g of ethyl orthosilicate (0.
2mol), reacted and treated in the same manner as in Production Example 1 to obtain 135.5 g of a tin compound D as a pale yellow liquid (yield: 95%).
I got From the results of disappearance of tin carbonyl absorption (1638 cm ^-1 , 1559 cm ^-1 ) and Sn-O-Sn absorption (477 cm ^-1 ) and the following elemental analysis by FT-IR, this compound was identified as 1,1, It was confirmed to be 3,3,5,5-hexaoctyl-1,5-bis (triethoxysiloxy) tristanoxane. C (%) H (%) O (%) Si (%) Sn (%) measured 50.4 9.5 11.2 3.8 25.1 theoretical 50.5 9.4 11.2 3. 9 25.0

Preparation Example 5 Dimethyltin oxide 3 was placed in the same four-necked flask as in Preparation Example 1.
3.0 g (0.2 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene.
The reaction and treatment were carried out in the same manner as in 1 to obtain 1,1,3,3-tetramethyl-1,3-bis (acetoxy) distannoxane, and then 41.7 g (0.2 mol) of ethyl orthosilicate was charged. The reaction and treatment were conducted in the same manner to obtain 63.8 g (95% yield) of a tin compound E as a pale yellow liquid. This compound has a tin carbonyl absorption (1638 cm
^-1 and 1559 cm ^-1 ) and the absorption of Sn-O-Sn (477 cm ^-1 ) and the results of the following elemental analysis,
It was confirmed to be 1,3,3-tetramethyl-1,3-bis (triethoxysiloxy) distannoxane. C (%) H (%) O (%) Si (%) Sn (%) measured value 28.6 6.2 21.6 8.5 35.1 theoretical value 28.6 6.3 21.4 8. 435.3

Production Example 6 Dibutyltin oxide 7 was placed in the same four-necked flask as in Production Example 1.
4.7 g (0.3 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene.
To give 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristanoxane, and then 41.7 g (0.2 mol) of ethyl orthosilicate
l) was charged and reacted and treated in the same manner as in Production Example 1 to obtain 104.6 g (96% yield) of a tin compound as a pale yellow liquid. This compound shows a tin carbonyl absorption (16
38cm ^-1, disappearance and Sn-O-of 1559 cm ^-1)
From the results of Sn absorption (477 cm ^-1 ) and the following elemental analysis, 1,1,3,3,5,5-hexabutyl-1,5-
After confirming that it is bis (triethoxysiloxy) tristanoxane (the same as the target compound of Production Example 2), 26.2 g of ethyl orthosilicate was further added and dissolved by stirring.
3,8,5,5-hexabutyl-1,5-bis (triethoxysiloxy) tristanoxane and ethyl orthosilicate
A light yellow liquid mixture F which was a mixture of 0:20 (weight ratio) was obtained.

Preparation Example 7 Dibutyltin oxide 7 was placed in the same four-necked flask as in Preparation Example 1.
4.7 g (0.3 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene.
The reaction and treatment were carried out in the same manner as described above to obtain 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristannoxane, and then 62.6 g of ethyl orthosilicate (0.3 mol)
l) was charged and reacted at 120 ° C. for 3 hours to obtain 91.7 g (yield 95%) of a reaction mixture G as a pale yellow liquid. This reaction mixture was analyzed by FT-IR for absorption of tin carbonyl (1
638 cm ^-1 , 1559 cm ^-1 ) disappearance and Sn-O
Confirmation of the absorption of -Sn (477 cm ^-1 ) and gas chromatographic analysis quantified the remaining amount of ethyl orthosilicate, and
It was confirmed that the mixture was a mixture of 5,5-hexabutyl-1,5-bis (triethoxysiloxy) tristanoxane (same as the target compound of Production Example 2) and ethyl orthosilicate at 80:20 (weight ratio).

Production Example 8 Dibutyltin oxide 4 was placed in the same four-necked flask as in Production Example 1.
9.8 g (0.2 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene.
To give 1,1,3,3-tetrabutyl-1,3-bis (acetoxy) distannoxane, and then ethyl silicate 40 (polysilicate ethyl ester (4-5) manufactured by Tama Chemical Industry Co., Ltd.) 49.8 g (corresponding to about 0.2 mol of tetraethoxysilicate in terms of the number of ethoxy groups), and reacted and treated in the same manner as in Production Example 1 to obtain 97.1 g of a tin compound H as a pale yellow liquid.
(95% yield). This compound was found to have an absorption of tin carbonyl by FT-IR (1638 cm ⁻¹ , 1559 c
m ^-1 ) and absorption of Sn-O-Sn (477 cm
^-1 ) was confirmed.

Examples 1 to 8 and Comparative Examples 1 to 3 Silyl group-containing organic polymers (MS Polymer S303 manufactured by Kaneka Chemical Industry Co., Ltd.) were added to Production Examples 1, 2, 3, 4, 5, 6,
Tin compounds A, B, C, D, E, F, obtained in 7, 8
G, H (F and G are a mixture with a silicate compound) or three kinds of conventional tin compounds used as a curing agent for modified silicone and other various additives are added in the proportions shown in Table 1. A curable composition was prepared by kneading at 25 ° C. The obtained curable composition was subjected to the following catalyst activity test and tensile adhesion test. Table 2 shows the results.

Catalyst activity test Immediately after the preparation of each of the above curable compositions, the composition was cured at 25.degree.
, And the snap time (the time until the gel became semi-gelled and the fluidity disappeared) and the tack free time (the time until the surface tack disappeared) were measured.

Tensile Adhesion Test Immediately after preparing each of the above-mentioned curable compositions, JIS A 57
It was subjected to a tensile adhesion test according to No. 58. An aluminum plate was used as an adherend. The breaking conditions are indicated by the following abbreviations. CF: material fracture TCF: material thin layer fracture AF: adherend-material interface peeling

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

As is clear from Table 2, Examples 1, 2, 3, 4, 5, and 6 using the specific tin-based curing catalyst of the present invention.
It can be seen that the curable compositions of Nos. 6, 7, and 8 have better curing performance than the curable compositions of Comparative Examples 1, 2, and 3 using a conventional tin-based curing catalyst. Examples 1, 2, 3, 4,
The curable compositions of 5, 6, 7, and 8 are not only excellent in ordinary adhesiveness but also excellent in water-resistant adhesiveness as compared with the curable compositions of Comparative Examples 1, 2, and 3.

The moisture-curable composition of the present invention has a faster curing speed than conventional curable compositions, and furthermore has excellent adhesiveness, especially excellent water-resistant adhesiveness. Such moisture-curable compositions are useful as sealants, coatings, elastic adhesives.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/10 C09K 3/10 GZ (72) Inventor Hitoshi Tabuchi 3-chome Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka 17-14 Nitto Kasei Co., Ltd. (72) Inventor Kiyomi Mohri 3-17-14 Nishiawaji, Higashiyodogawa-ku, Osaka-shi, Osaka F-term (reference) 4F070 AA52 AB07 AC53 AC67 AE08 4H017 AA04 AA31 AC01 AC04 AC05 AC17 4J002 CP181 EZ046 FD146 GJ01 GJ02 4J005 AA04 BD08 4J035 AB03 AB07 BA04 BA14 CA04U CA06U CA25U CA29U GA08 LB02 LB03

Claims (4)

[Claims] 1. 100 parts by weight of a silyl group-containing organic polymer (A) having at least one silicon atom bonded to a hydrolyzable group at a molecular terminal or a side chain in one molecule and a curing catalyst (B). In the composition containing 1 to 10 parts by weight as a main component, the curing catalyst (B) has the following formula (1): (Wherein, R ¹ and R ² each independently represent 1 carbon atom)
~ 12 hydrocarbon groups, two R ¹ , (2m + 2)
R ² may be the same or different, and m is an integer of 1 or more) and a poly (dialkylstannoxane) dicarboxylate represented by the following formula (2): R ³ _n Si (OR ⁴ ) _4-n (2) (wherein, R ³ and R ⁴ each independently represent a carbon atom of 1
To 4 hydrocarbon groups, n R ³ and (4-n) R ⁴ may be the same or different, and n is 0 to 4
A silicate compound represented by the formula:
Or a moisture-curable composition comprising a reaction product with a hydrolyzate thereof. 2. A curing catalyst (B) comprising a poly (dialkylstannoxane) dicarboxylate represented by the general formula (1) and a silicate compound represented by the general formula (2) and / or
Or a reaction product with a hydrolyzate thereof, and a compound represented by the general formula (2)
The moisture-curable composition according to claim 1, which is a mixture with a silicate compound represented by the following formula and / or a hydrolyzate thereof. 3. The curing catalyst (B) is represented by the following formula (3): (Wherein R ² , R ⁴ , and m are the same as those described above), or the poly (dialkylstannoxane) disilicate compound and a tetraalkoxysilane and / or a hydrochloride thereof. The moisture-curable composition according to claim 1, which is a mixture with a decomposition product. 4. The following formula (3): (Wherein, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and even if (2m + 2) R ² are the same,
R ⁴ may be a hydrocarbon group having 1 to 4 carbon atoms, and 6 R ⁴ may be the same or different, and m is an integer of 1 or more. A poly (dialkylstannoxane) disilicate compound represented by the formula: