JP3445764B2 - Moisture curable composition and poly (dialkylstannoxane) disilicate compound - Google Patents

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 and a poly (dialkylstannoxane) disilicate compound which cure rapidly and are excellent in adhesiveness and water-resistant adhesion.

[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. The one-pack type moisture curable rubber is generally quicker to cure, and is superior in workability to the two-pack type because it does not require adjustment of mixing of liquids.

[0003]

However, the silicone rubber has a problem in the possibility of contamination to the surroundings and the coating property on the surface, and the urethane rubber has the problems of storage stability and weather resistance. There are problems with respect to properties, foaming resistance, discoloration, etc. Further, the polysulfide rubber also has problems in curability and the possibility of contamination of the surroundings. Modified silicone rubber is a polymer having a cross-linkable hydrolyzable silicone functional group that has a polyether as its main chain, and is stable for a long period of time under sealing in the coexistence state of a curing catalyst, but it rapidly increases when exposed to moisture. It is a one-pack composition which is cured into a rubber-like substance (Japanese Patent Publication No. 62-35421, Japanese Patent Laid-Open No. 61-
No. 141761, JP 1-58219 A).
This polymer has better storage stability, weather resistance, foaming resistance and discoloration resistance than the polyurethane type, and has excellent curability and less contamination to the surroundings than the polysulfide type.
Not toxic. In addition, it has less pollution to the surroundings than ordinary silicone rubber and has good coatability 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 poor adhesiveness, particularly water-resistant adhesiveness, and it is necessary to use a primer or the like. Japanese Patent Publication No. 59-38989, Japanese Patent Publication No. 1-58219, Japanese Patent Publication No. 2-22105, Japanese Patent Laid-Open No. 58-57460, Japanese Patent Publication No. 63-18.
The use of a reaction product of a dialkyltin oxide or a carboxylate with an alkoxysilane as a curing catalyst for a polymer having a hydrolyzable silicon group is disclosed in Japanese Patent Application Laid-Open No. 7-11155 and dibutyltin. It has been proposed to use bis (triethoxysilicate) as a curing catalyst. By using these organotin silicate compounds, the curing rate becomes faster than that when organotin carboxylate is used, but it is not sufficient, and the development of a catalyst having a faster curing rate has been desired.

[0004]

Therefore, the present inventors have
The present invention has been completed by earnestly studying to obtain a moisture-curable composition which is rapidly cured and has excellent adhesiveness and water-resistant adhesiveness.

That is, the invention according to claim 1 is 100 parts by weight of a silyl group-containing organic polymer (A) having at least one silicon atom bonded to a hydrolyzable group in one molecule at its molecular end or side chain. A composition containing 0.1 to 10 parts by weight of a curing catalyst (B) as a main component (however, polyfluorocarbon
Do not contain (meth) acrylate compound having hydrogen group
In the above , the curing catalyst (B) has the following general formula (1):

[0006]

[Chemical 4]

(In the formula, 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 is a poly (dialkylstannoxane) dicarboxylate 1
Mol and the following general formula (2): R ³ _n Si (OR ⁴ ) _4-n (2) (In the formula, R ³ and R ⁴ each independently have 1 carbon atom.
~ 4 hydrocarbon groups, n R ³ and (4-n) R ⁴ may be the same or different, and n is 0 to
Is an integer of 3) and /
Or by reacting with 2 to 6 mol of the hydrolyzate
The reaction product thus obtained , or the reaction product and the general
The silicate compound represented by the formula (2) and / or the silicate compound
The present invention relates to a moisture-curable composition comprising a mixture with a hydrolyzate of

The invention according to claim 2 is based on the general formula (1):
Poly (dialkylstannoxane) dicarbox represented by
A silate and a silicate compound represented by the general formula (2)
And / or the reaction with a hydrolyzate thereof,
Specially, it is performed by heating at 0 ° C for 1 to 3 hours.
The present invention relates to the moisture-curable composition according to claim 1.

In the invention according to claim 3 , 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 Ri mixture der of the reaction product, generally represented by silicate compound with formula (2) and / or a hydrolyzate thereof with hydrolyzate,
When the total amount of both is 100 parts by weight, the reaction product 9
Shi Riketo compound against 0-50 parts by weight and / addition
Is 10 to 50 parts by weight of the hydrolyzate thereof, and relates to the moisture-curable composition according to claim 1 or 2 .

Further, in the invention according to claim 4 , the curing catalyst (B) has the following general formula (3):

[0011]

[Chemical 5]

(Wherein R ² , R ⁴ and m are the same as above), or the poly (dialkylstannoxane) disilicate compound and tetraalkoxysilane and / or Alternatively, the present invention relates to the moisture-curable composition according to any one of claims 1 to 3, which is a mixture with a hydrolyzate thereof.

Further, the invention according to claim 5 is the general formula
Poly (dialkylstannoxane) dica represented by (1)
Ruboxylate 1 mol and tetraalkoxysilane 2-6
The following general formula (3) obtained by reacting with mol :

[0014]

[Chemical 6]

(In the formula, 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 carbon atom. A poly (dialkylstannoxane) which is 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. Disilicate compound , or the poly (dialkylstannoxane) disi
Cate compound and tetraalkoxysilane and / or
Refers to the mixture with its hydrolyzate .

Further, the invention according to claim 6 has the general formula
Poly (dialkylstannoxane) dica represented by (1)
1 mol of ruboxylate and the liquor represented by the general formula (2)
2 to 6 mol of a salt compound and / or its hydrolyzate
A reaction product obtained by reacting
The silicate compound represented by the formula (2) and / or the silicate compound
With a hydrolyzate of.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION 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, may be referred to as a silicon group bonded to a hydrolyzable group) in a molecule at a molecular end or a side chain. The main chain of the polymer is alkylene oxide polymer or polyether, ether.
Examples thereof include ester block copolymers. Moreover, the polymer of an ethylenically unsaturated compound and a diene compound is mentioned.

Examples of the alkylene oxide polymer or polyether include (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). ) Those having a repeating unit such as p 1 are exemplified. Where p
Is an integer of 2 or more.

The polymers of ethylenically unsaturated compounds and diene compounds include ethylene, propylene, acrylic acid esters, methacrylic acid esters, vinyl acetate,
Examples thereof include homopolymers of acrylonitrile, styrene, isobutylene, butadiene, isoprene, chloroprene and the like, and copolymers of two or more kinds of these. More specifically, polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-butadiene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer. Polymer, polyisoprene, styrene-isoprene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-chloroprene copolymer, acrylonitrile-chloroprene copolymer, polyisobutylene, polyacrylic acid ester, polymethacrylic acid ester, etc. Is mentioned.

The silicon group bonded to the hydrolyzable group is a group which causes a condensation reaction in the presence of moisture or a cross-linking agent, if necessary, by using a catalyst or the like. Specifically, a halogenated silyl group, an alkoxysilyl group, an alkenyloxysilyl group, an acyloxysilyl group, an aminosilyl group,
Examples thereof include aminooxysilyl group, oxime silyl group, and 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. 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 from the viewpoint of easy handling. The silicon group bonded to the hydrolyzable group is
It may be present at the end of the polymer molecule or in the side chain. The silicon group bonded to the hydrolyzable group may be at least one per one molecule of the polymer, but the curing rate,
From the viewpoint of cured physical properties, it is preferable that the average number of molecules per molecule is 1.5 or more. As a method for bonding the silicon group bonded to the hydrolyzable group to the main chain polymer, a known method can be adopted.

The molecular weight of the organic polymer (A) used in the present invention is not particularly limited, but an excessively high molecular weight one has a high viscosity and is difficult to use when it is used as a curable composition. The number average molecular weight is preferably 30,000 or less. Such an organic polymer can be produced by a known method, but a commercially available product such as Kaneka MS Polymer manufactured by Kanegafuchi Chemical Industry Co., Ltd. may be used.

The curing catalyst (B) used in the present invention is
One or more reaction products of a dialkyltin oxydicarboxylate represented by the general formula (1) and a silicate compound represented by the general formula (2) and / or a hydrolyzate thereof are preferably used. It

In the general formula (1), the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t. -Butyl, pentyl, hexyl,
Examples thereof include linear or branched alkyl groups such as heptyl, octyl, 2-ethylhexyl, decyl and lauryl, and unsubstituted or substituted phenyl groups. The two R ^1's may be the same or different. Also (2m +
2) The two R ^{2 s} 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 1,1,3,3-tetramethyl-1,3-bis (acetoxy) distannoxane, 1,1,1. 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) distannoxane, 1,1,3,3-tetrabutyl-1, 3-bis (acetoxy) distannoxane, 1,1,3,3-tetrabutyl-1,3-bis (butyryloxy) distannoxane, 1,1,3,3-tetrabu Ru-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) distannoxane, 1,1,3,3-tetraoctyl-1,3-bis (acetoxy) distannoxane, 1,1,3,3-tetraoctyl-1,3-bis (butyryloxy) Distannoxane, 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 3-tetralauryl-1,3-bis (2-
Tetraalkyldistannoxane dicarboxylates such as ethylhexanoyloxy) distannoxane, 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) tristannoxane, 1,1,3,3,5, 5-hexamethyl-1,5-bis (octanoyloxy) tristannoxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (2-ethylhexanoyloxy) tristannoxane, 1 , 1,3,3,5,5-hexamethyl-1,5-bis (lauroyloxy) tristannoxane, 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) tristannoxane, 1,1,3,3,5,5-hexabutyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane, 1,1,3,3 3,5,5-hexabutyl-1,5-bis (lauroyloxy) tristannoxane, 1,1,3,3,5,5-hexaoctyl-1,5-bis (acetoxy) tristannoxane, 1, 1,3,3,5,5-hexaoctyl-1,5-bis (butyryloxy) tristannoxane, 1,1,3,3,5,5-hexaoctyl-1,5-bis (octanoyloxy) Tristannoxa 1,1,3,3,5,5-hexaoctyl-1,5-bis (2-ethylhexanoyloxy) tristannoxane, 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) tristannoxane, 1,1,3,3,5,5-hexalauryl-1,5-bis (lauroyloxy ) Hexaa such as tristanoxane Examples include ruquil tristanoxane dicarboxylate and the like. Among these, tetrabutyl diacyloxy distannoxane and tetraoctyl diacyloxy distannoxane are preferable, and a carboxylate having 4 or less carbon atoms is more preferable from the viewpoint of easy removal of the produced carboxylic acid ester. More preferably, 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 group having 1 to 4 carbon atoms represented by R ³ and R ⁴ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Examples thereof include alkyl groups such as s-butyl and t-butyl. The n R ^{3 s} may be the same or different. Further, (4-n) R ^{4 s} may be the same or different.

The silicate compound represented by the general formula (2) and / or its hydrolyzate is used as the silicate compound reacted with the poly (dialkylstannoxane) dicarboxylate represented by the general formula (1). it can. Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, and other tetraalkoxysilanes or hydrolysates thereof, triethoxymethylsilane, triethoxyethylsilane, triethoxypropylsilane. Trialkoxy monoalkylsilanes such as triethoxyisopropylsilane and triethoxybutylsilane or hydrolysates thereof, such as diethoxydimethylsilane, diethoxydiethylsilane, diethoxydipropylsilane, diethoxydiisopropylsilane and diethoxydibutylsilane. Dialkoxydialkylsilane or its hydrolyzate, ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytripropylsilane, ethoxytriisopropylsilane Emissions, monoalkoxysilane trialkylsilane or hydrolysates thereof such as ethoxy tributyl silane. Among these, tetraalkoxysilane or its hydrolyzate is preferable. More preferably, it is tetraethoxysilane.

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

The reaction product obtained has a different structure depending on the charging ratio of the poly (dialkylstannoxane) dicarboxylate and the silicate compound and / or its hydrolyzate, but the preferred reaction product. Is obtained by reacting 1 to 6 mol of poly (dialkylstannoxane) dicarboxylate represented by the general formula (1) with 2 to 6 mol of the silicate compound represented by the general formula (2). Formula (4):

[0029]

[Chemical 7]

A poly (dialkylstannoxane) disilicate compound represented by the formula (wherein R ² , R ³ , R ⁴ , m and n are the same as above).

A more preferred reaction product is represented by the general formula (1)
Among the silicate compounds represented by the general formula (2), tetraalkyl silicate compound 2 is used per 1 mol of poly (dialkylstannoxane) dicarboxylate represented by
The following general formula (3) obtained by reacting ~ 6 mol:

[0032]

[Chemical 8]

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

The reaction product of the present invention has a very high catalytic activity as compared with the conventional dialkyltin compound, but the silicate compound represented by the general formula (2) is preferable because of the stability of the catalyst and the ease of handling. It is preferable to use a mixture of a hydrolyzate and / or a hydrolyzate thereof, and the mixing ratio is such that when the total amount of the two is 100 parts by weight, the reaction product 99 to
Is preferably a silicate compound and / or its hydrolyzate 1-99 parts by weight per 1 part by weight, more preferably silicate compound to the reaction product 90 to 50 parts by weight and / or its hydrolyzate 10 ˜50 parts by weight. These mixtures, after synthesis of the reaction product,
It can also be obtained by mixing the silicate compound and / or its hydrolyzate, or by reacting the dialkyltin oxydicarboxylate with a large excess of the silicate compound and / or its hydrolyzate.

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 with respect to 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, while when it exceeds the above range, the cured product after curing may have poor recovery properties, weather resistance and other physical properties.

In the moisture-curable composition of the present invention, various known amino group-substituted alkoxysilane compounds or their condensates can be used in order to accelerate curing and improve adhesion to a substrate. Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) ethylenediamine, δ-aminobutyl (methyl) diethoxysilane, N, N′-bis ( Examples thereof include trimethoxysilylpropyl) ethylenediamine and partial hydrolysates thereof.

The moisture-curable composition of the present invention further comprises a filler, a colorant, a plasticizer, a curing accelerator, a curing retarder,
Additives that are usually added to curable compositions, such as anti-sagging agents, anti-aging agents, and solvents, may be added. For example, as the filler, specifically, calcium carbonate, kaolin, talc,
Fumed silica, precipitated silica, silicic acid 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, titanium dioxide and the like. Specific examples of the colorant include iron oxide, carbon black, phthalocyanine blue, phthalocyanine green and the like. Specific examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate and butylbenzyl phthalate, dioctyl adipate, dioctyl succinate, diisodecyl succinate, diisodecyl sebacate, and aliphatic carboxylic acids such as butyl oleate. Acid esters, glycol esters such as pentaerythritol ester, trioctyl phosphate, phosphate esters such as tricresyl phosphate, epoxidized soybean oil, epoxy plasticizers such as benzyl epoxystearate, chlorinated paraffin, and the like. . As the anti-sagging agent, specifically, hydrogenated castor oil,
Examples thereof include silicic acid anhydride, organic bentonite, colloidal silica and the like. Examples of other additives include adhesion promoters such as phenol resins and epoxy resins, ultraviolet absorbers, radical chain inhibitors, peroxide decomposers, and various antiaging agents.

[0038]

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), acetic anhydride 10.4 g (0.
1 mol) and 200 g of toluene were charged, and the temperature was 112 ° C.
After reacting for 2 hours, the toluene is distilled off under reduced pressure,
1,1,3,3-Tetrabutyl-1,3-bis (acetoxy) distannoxane was obtained (the compound was obtained quantitatively). Then tetraethoxysilane (orthosilicate)
41.7 g (0.2 mol) was charged and reacted at 120 ° C. for 3 hours, and the ethyl acetate produced under reduced pressure was distilled off,
79.8 g (yield 95%, value based on tin oxide, the same applies hereinafter) of tin compound A as a pale yellow liquid was obtained. This compound showed absorption of tin carbonyl by FT-IR (1638 cm
⁻¹ , 1559 cm ⁻¹ ) disappearance and Sn—O—Sn absorption (477 cm ⁻¹ ) and the result 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 value 40.1 7.7 17.0 6.9 28.3 Theoretical value 40.0 7.9 17.1 6. 7 28.3

Production Example 2 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 were charged, and Production Example 1
Was treated and treated in the same manner as above to obtain 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristannoxane, and then 41.7 g (0.2 mo of ethyl orthosilicate).
1) was charged and reacted and treated in the same manner as in Production Example 1 to obtain 102.4 g (yield 94%) of tin compound B as a pale yellow liquid. This compound showed disappearance of tin carbonyl absorption (1638 cm ^-1 , 1559 cm ^-1 ) and Sn in FT-IR.
From the absorption of -O-Sn (477 cm ^-1 ) and the results of the following elemental analysis, 1, 1, 3, 3, 5, 5-hexabutyl-1,
It was confirmed to be 5-bis (triethoxysiloxy) tristannoxane. C (%) H (%) O (%) Si (%) Sn (%) Measured value 39.9 7.7 14.6 5.1 32.9 Theoretical value 39.7 7.8 14.7 5. 1 32.7

Production Example 3 72.2 g (0.2 mol) of dioctyltin oxide and 10.2 g of acetic anhydride were placed in the same four-necked flask as in Production Example 1.
(0.1 mol) and 200 g of toluene were charged 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)
Was charged and reacted at 120 ° C. for 3 hours to obtain 101.2 g (yield 97%) of a tin compound C as a pale yellow liquid. This compound showed absorption of tin carbonyl by FT-IR (1638).
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 4 108.3 g (0.3 mol) of dioctyltin oxide and 10.2 g of acetic anhydride were placed in the same four-necked flask as in Production Example 1.
(0.1 mol) and 200 g of toluene were charged 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) tristannoxane was obtained, then 41.7 g of ethyl orthosilicate (0.
(2 mol) and charged and reacted in the same manner as in Production Example 1 to give 135.5 g (yield 95%) of tin compound D as a pale yellow liquid.
Got This compound was ¹ , ¹ , from the disappearance of tin carbonyl absorption (1638 cm ^-1 , 1559 cm ^-1 ) and Sn-O-Sn absorption (477 cm ^-1 ) by FT-IR and the results of the following elemental analysis. It was confirmed to be 3,3,5,5-hexaoctyl-1,5-bis (triethoxysiloxy) tristannoxane. C (%) H (%) O (%) Si (%) Sn (%) Measured value 50.4 9.5 11.2 3.8 25.1 Theoretical value 50.5 9.4 11.2 3. 9 25.0

Production Example 5 Dimethyltin oxide 3 was placed in the same four-necked flask as in Production Example 1.
3.0 g (0.2 mol), acetic anhydride 10.2 g (0.
1 mol) and 200 g of toluene were charged, and Production Example 1
Reaction and treatment were conducted 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 orthoethyl silicate was charged, and Production Example 1 was prepared. The same reaction and treatment were carried out to obtain 63.8 g (yield 95%) of tin compound E which was a pale yellow liquid. This compound showed absorption of tin carbonyl by FT-IR (1638 cm
⁻¹ , 1559 cm ⁻¹ ) disappearance and Sn—O—Sn absorption (477 cm ⁻¹ ) and the result 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. 4 35.3

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 were charged, and Production Example 1
Was treated and treated in the same manner as above to obtain 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristannoxane, and then 41.7 g (0.2 mo of ethyl orthosilicate).
1) was charged and reacted and treated in the same manner as in Production Example 1 to obtain 104.6 g (yield 96%) of a tin compound as a pale yellow liquid. This compound absorbs tin carbonyl by FT-IR (16
38cm ^-1, disappearance and Sn-O-of 1559 cm ^-1)
From the absorption of Sn (477 cm ^-1 ) and the results of the following elemental analysis, ^{1, 1} , 3, 3, 5, 5-hexabutyl-1,5-
After confirming that it was bis (triethoxysiloxy) tristannoxane (the same as the target compound of Production Example 2), 26.2 g of ethyl orthosilicate was further added and dissolved with stirring to give 1,1 ,.
8 of 3,3,5,5-hexabutyl-1,5-bis (triethoxysiloxy) tristannoxane and ethyl orthosilicate
A pale yellow liquid mixture F which is a 0:20 (weight ratio) mixture was obtained.

Production Example 7 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 were charged, and Production Example 1
Was reacted and treated in the same manner as above to obtain 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristannoxane, and then 62.6 g (0.3 mo of ethyl orthosilicate).
1) was charged and reacted at 120 ° C. for 3 hours to obtain a reaction mixture G91.7 g (yield 95%) as a pale yellow liquid. This reaction mixture was analyzed by FT-IR to absorb tin carbonyl (1
638 cm ⁻¹ , 1559 cm ⁻¹ ) disappearance and Sn—O
-The amount of ethyl orthosilicate remaining was quantified by confirming the absorption of Sn (477 cm ^-1 ) and gas chromatographic analysis.
It was confirmed to be a mixture of 5,5-hexabutyl-1,5-bis (triethoxysiloxy) tristannoxane (the 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 were charged, and Production Example 1
1,1,3,3-tetrabutyl-1,3-bis (acetoxy) distannoxane is obtained by reacting and treating in the same manner as described above, followed by ethyl silicate 40 (polysilicic acid ethyl ester (4-5) produced by Tama Chemical Industry Co., Ltd.). 49.8 g (corresponding to about 0.2 mol of tetraethoxysilicate converted from the number of ethoxy groups), reacted and treated in the same manner as in Production Example 1 to obtain 97.1 g of tin compound H as a pale yellow liquid.
(Yield 95%) was obtained. This compound showed absorption of tin carbonyl by FT-IR (1638 cm ⁻¹ , 1559c).
m ⁻¹ ) disappearance and Sn—O—Sn absorption (477 cm
^-1 ) was confirmed.

Examples 1 to 8 and Comparative Examples 1 to 3 A silyl group-containing organic polymer (MS polymer S303 manufactured by Kanegafuchi Chemical Industry Co., Ltd.) was added to Production Examples 1, 2, 3, 4, 5, 6, and 6.
The tin compounds A, B, C, D, E, F obtained in 7 and 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 a mixing ratio shown in Table 1. A curable composition was prepared by kneading at 25 ° C. The obtained curable composition was subjected to the following catalytic activity test and tensile adhesion test. The results are shown in Table 2.

Catalytic activity test Immediately after preparation of each curable composition, 25 ° C., 60% RH
The sample was left to stand in the atmosphere of No. 2 and the snap time (time until half gelation and no fluidity) and tack free time (time until surface tack disappeared) were measured.

Tensile Adhesion Test Immediately after preparation of each curable composition described above, JIS A 57
It was subjected to a tensile adhesion test according to 58. An aluminum plate was used as the adherend. The fracture status is indicated by the following abbreviations. CF: Material rupture TCF: Material thin layer rupture AF: Adherend-material interface peeling

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

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

The moisture-curable composition of the present invention has a faster curing rate than conventional curable compositions and is excellent in adhesiveness, particularly water-resistant adhesiveness. Such a moisture-curable composition is useful as a sealing agent, a coating agent or an elastic adhesive.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 3/10 C09K 3/10 G Z (72) Inventor Hitoshi Tabuchi 3-17-14, Nishi-Awaji, Higashiyodogawa-ku, Osaka City, Osaka Prefecture Nitto Kasei Co., Ltd. (72) Inventor Kiyomi Mohri 3-17-14 Nishi-Awaji, Higashiyodogawa-ku, Osaka City, Osaka Prefecture Nitto Kasei Co., Ltd. (56) Reference JP-A-8-143762 (JP, A) JP-A-9 -124922 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 83/00-83/16 C08L 71/00-71/14 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57) [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 in its molecule at its molecular end or side chain and a curing catalyst (B) of 0.1. compositions 1 to 10 parts by weight as a main component (for
However, a (meth) acrylate having a polyfluorohydrocarbon group
( Containing no rate compound) , the curing catalyst (B)
Is represented by the following general formula (1): (In the formula, R ¹ and R ² each independently have 1 carbon atom.
~ 12 hydrocarbon groups, two R ¹ , (2m + 2)
Even number of R ² is each the same or different, m is 1 or more poly represented by integers which) (dialkyl stannoxane) dicarboxylate 1 mol of the following one
General formula _{^{(2): R 3 n Si}} (OR 4) 4-n (2) ( wherein, R ³ and R ⁴ are each independently C 1 -C
~ 4 hydrocarbon groups, n R ³ and (4-n) R ⁴ may be the same or different, and n is 0 to
Is an integer of 3) and /
Or by reacting with 2 to 6 mol of the hydrolyzate
The reaction product thus obtained , or the reaction product and the general
The silicate compound represented by the formula (2) and / or the silicate compound
A moisture-curable composition comprising a mixture with the hydrolyzate of 2. Poly (dialkoxy) represented by the general formula (1)
Rustannoxane) dicarboxylate and general formula (2)
Represented silicate compound and / or its hydrolysis
The reaction with the substance is heated at 100 to 130 ° C. for 1 to 3 hours.
By Moisture according to claim 1, characterized in that
Gas curable composition. 3. 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
Alternatively, the reaction product of the hydrolyzate with the general formula (2)
In Ri mixture der of represented by silicate compound and / or a hydrolyzate thereof, and the total amount of both 100 parts by weight
When added, 90 to 50 parts by weight of the reaction product is added to the silica gel.
Compound and / or its hydrolyzate
The moisture-curable composition according to claim 1 or 2, which is a part by weight . 4. The curing catalyst (B) has the following general formula (3): (Wherein R ² , R ⁴ and m are the same as above), or the poly (dialkylstannoxane) disilicate compound and tetraalkoxysilane and / or its hydration It is a mixture with a decomposed product, and it is characterized by the above-mentioned.
The moisture-curable composition according to any one of items. 5. A poly (dialkoxy) represented by the general formula (1).
Rustanoxane) dicarboxylate 1 mol and tetraa
By reacting with 2-6 mol of lucoxysilane
The following general formula (3) is obtained : (In the formula, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and (2m + 2) R ^{2 s} are the same,
May be different, R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms, 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
Is the poly (dialkylstannoxane) disilicate compound
And tetraalkoxysilane and / or its water content
Mixture with smash . 6. Poly (dialkoxy) represented by the general formula (1)
Rustanoxane) dicarboxylate 1 mol and general formula
A silicate compound represented by (2) and / or the same.
Obtained by reacting with 2 to 6 mol of hydrolyzate
Reaction product and a silicate represented by the general formula (2)
Mixtures of compounds and / or their hydrolysates.