JP3356353B2 - Room temperature curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a room temperature curable composition which cures in the presence of moisture.

[0002]

2. Description of the Related Art Conventionally, a method of using a compound having a hydrolyzable silicon group at a terminal, such as a modified silicone resin, by utilizing a curing reaction of the compound for a sealing material, an adhesive or the like is often used. It is a known and industrially useful method.

Known polymers having such a terminal hydrolyzable silicon group are disclosed, for example, in JP-B-45-36319, JP-B-46-17553, and JP-B-61-18.
No. 582.

[0004] Of the polymers having a terminal hydrolyzable silicon group, especially for compounds having an alkoxysilyl group as the hydrolyzable silicon group, a so-called curing catalyst is usually used to impart room-temperature curability. . As such a curing catalyst, a metal salt of a carboxylic acid, an acidic or basic compound, and the like are properly used depending on applications.
Among them, organotin compounds and / or tin carboxylate salts are generally used.

[0005]

However, a tetravalent organotin compound such as dibutyltin dilaurate or dibutyltin diacetate is used as a catalyst, and the polyether compound having a relatively short molecular weight proposed in the above-mentioned known example is used as a diether. br /> halogenoalkyl allowed Awa connected by compounds was high molecular weight, produced by the method of introducing a hydrolyzable silicon group, to cure the polymer having a hydrolyzable silicon group, a mixture of such fillers The curing speed was insufficient.

When a reaction product of a dialkyltin oxide and an ester compound as proposed in Japanese Patent Publication No. 1-58219 is used, the curing speed at ordinary temperature is considerably improved, but the curing speed in winter is improved. Considering usage etc.,
The cure rate at low temperatures was still insufficient.

[0007]

The present inventors have developed a curing catalyst and
And a specific low molecular silicon compound (C) and an organotin compound
The disadvantage of using the reactant with the product (D)
Was found to be eliminated. That is, the present invention
And / or a silicon atom having a hydrolyzable group bonded thereto.
At least one silicon-containing group per molecule on average for all molecules
Organic polymer (A) and 100 weights of organic polymer (A)
Parts by weight, as a curing catalyst (B),Expressed by the following equation (2)
Be doneLow molecular silicon compound (C) and organotin compound
0.01 to 10 parts by weight of a reaction product with (D)
At room temperature.R ^Two _b Six ¹ _4-b ... (2) Where R ^Two Is substituted or unsubstituted having 1 to 20 carbon atoms
A monovalent hydrocarbon group, X ¹ Is an alkoxy group, b is 0, 1 or
Is 2.

[0008] In the present invention, the organic polymer (A), especially
At least one specific silicon-containing group per molecule on average for all molecules
I do. This particular silicon-containing group contains a particular silicon atom.
No. This particular silicon atom has hydroxyl and / or
A decomposable group is attached. The organic polymer (A) is preferably a derivative such as a polydialkylsiloxane polymer, a polyoxyalkylene polymer, an ether-ester block copolymer, a vinyl polymer, and a diene polymer. It is preferably a derivative of an alkylene polymer. Particularly preferred is a derivative of a polyoxyalkylene polymer (F) having a number average molecular weight of 5,000 or more, which is obtained by polymerizing an alkylene oxide with an initiator using a double metal cyanide complex (E) as a catalyst.

[0009] The use of double metal cyanide complex _{(E), M w / M} n is rather less than the polyoxyalkylene polymers prepared using conventional alkali metal catalyst,
A higher molecular weight, lower viscosity polyoxyalkylene polymer (F) is obtained. Here, M _w / M _n is preferably 1.8 or less. Where M _w is the weight average molecular weight,
M _n is the number average molecular weight.

As the double metal cyanide complex (E), those described in JP-B-46-27250 can be used. Particularly, a complex containing zinc hexacyanocobaltate as a main component is preferable, and an ether and / or alcohol complex thereof is particularly preferable. Examples of the ether of ethylene glycol dimethyl ether (glyme), is preferably diethylene glycol dimethyl ether (diglyme) or the like, particularly glyme are preferable in terms of physician handling during production of the complex. T- Bed Chiruaruko Lumpur Hei 4-145123 JP is preferably an alcohol.

The number of functional groups of the polyoxyalkylene polymer (F) is preferably 2 or more, and more preferably 2 to 4. Specifically, a polyoxyethylene compound, a polyoxypropylene compound, a polyoxybutylene compound, a polyoxyhexylene compound, a polyoxytetramethylene compound, and / or a copolymer thereof are exemplified.

The polyoxyalkylene polymer (F) is preferably a polymer obtained by polymerizing at least one alkylene oxide selected from ethylene oxide, propylene oxide and butylene oxide.

[0013] Most preferred are polyoxypropylene diol, polyoxypropylene triol and polyoxypropylene tetraol. When used in the following methods (a) and (d), an olefin-terminated polyoxyalkylene polymer such as an allyl-terminated polyoxypropylene monol is also preferable.

[0014] The silicon-containing group is a silicon-containing group which is the table by the following formula (1) are preferred.

[0015] ^{_{- SiX a R 1 3-a}} ··· (1) where the monovalent hydrocarbon group substituted or unsubstituted wherein R ¹ is from 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable The group a is 1, 2 or 3.

R ¹ in the formula (1) is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group,
Methyl group, ethyl group, propyl group, blanking butyl group, a hexyl group, a cyclohexyl group, and phenyl group is particularly preferred.

X in the formula (1) is exemplified by a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, a carbamoyl group, an amino group, an aminooxy group, a ketoximate group and a hydride group. Among these, the carbon number of the hydrolyzable group having a carbon atom is preferably 6 or less, and particularly preferably 4 or less. Preferred groups are having 4 or less of the lower alkoxy group having a carbon, specifically a methoxy group, an ethoxy group, etc. propoxy. A in Formula (1) is particularly preferably 2 or 3.

Next, a method for producing the organic polymer (A) will be described. The organic polymer (A) in the present invention is obtained by introducing a silicon-containing group into the terminal of a polyoxyalkylene polymer having a functional group, as described in the following (a), (b), (c), and (d). It is preferable to use one manufactured by the following method. Such a compound is liquid at room temperature, and the cured product retains flexibility even at a relatively low temperature, and has preferable characteristics when used as a sealing material, an adhesive or the like.

(A) A method of reacting a polyoxyalkylene compound having a functional group with an olefin group introduced at a terminal thereof with a hydrosilyl compound represented by the following formula (3).

H SiX _a R ¹³ _-a (3) wherein R ¹ , X and a are the same as described above.

Here, as a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene compound, and the compound is bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond, or the like. method for, when polymerizing alkylene oxide, a method of introducing an olefin group in the side chain by copolymerization by adding an olefin group-containing epoxy compound such as allyl glycidyl ether, starting compounds having an unsaturated group and a hydroxyl group process for polymerizing alkylene oxides as agents, and the like.

(B) A method of reacting a compound represented by the following formula (4) with a terminal of a polyoxyalkylene compound having a functional group.

R ¹³ _-a SiX _a -R ³ NCO (4) wherein R ¹ , X and a are the same as above, and R ³ has 1 carbon atom
To 17 divalent hydrocarbon groups.

(C) The terminal of the polyoxyalkylene compound having a functional group is reacted with a polyisocyanate compound such as tolylene diisocyanate to form an isocyanate group terminal, and then the silicon represented by the following formula (5) is added to the isocyanate group. A method of reacting a W group of a compound.

R ¹³ _-a SiX _a -R ³ W (5) wherein R ¹ , R ³ , X and a are the same as above, and W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group An active hydrogen-containing group selected from (primary or secondary).

(D) An olefin group is introduced into the terminal of the polyoxyalkylene compound having a functional group, and the olefin group is reacted with the mercapto group of the silicon compound represented by the above formula (5) wherein W is a mercapto group. How to let.

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

As the organic polymer (A) in the present invention, an organic polymer having a number average molecular weight of 5,000 to 30,000 can be used. The number average molecular weight of the organic polymer (A) is 500
If it is lower than 0, the cured product is hard and the elongation is low. The number average molecular weight is no problem flexibility and elongation of the cured product exceeds 30000, polymer viscosity itself Ri remarkably high practicality is lowered. Number average molecular weight is especially 8
000-3000 is preferred.

The curing catalyst (B) used in the present invention is specified
Of a low molecular silicon compound (C) and an organotin compound (D).

[0030] The low-molecular silicon compound (C), the low molecular silicon compound der having a silicon-containing group containing bound silicon atoms hydrolyzable group is, represented by the following formula (2)
You.

R ² _b SiX ¹⁴ _-b (2) wherein R ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X ¹ is an alkoxy group, and b is 0, 1 or
Is 2 .

R ² in the formula (2) is preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group.
Methyl group, ethyl group, propyl group, blanking butyl group, a hexyl group, a cyclohexyl group, and phenyl group is particularly preferred.

X ¹ in the formula (2) is an alkoxy group ,
Particularly preferred are lower alkoxy groups having 4 or less carbon atoms, especially methoxy, ethoxy and propoxy groups.

Specific low molecular silicon compounds (C) include tetraalkoxysilanes such as tetraethylsilicate; trialkoxysilanes such as trimethoxymethylsilane, triethoxymethylsilane and trimethoxyvinylsilane; dimethoxydimethylsilane and diethoxydimethyl Jiarukokishishira emissions such as silane; or their hydrolyzates or partial hydrolysis products thereof.

[0035] and ease of handling, considering the effect on the physical properties of the cured product, particularly dialkoxysilane is preferred.

Examples of the organotin compound (D) include tin oxides such as dibutyltin oxide and dioctyltin oxide; carboxylates such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate and butyltin bisalkyl maleate esters; dibutyltin dimethoxide Tin alkoxides; tin chelates such as dibutyltin bisacetylacetonate;
A known compound such as a reaction product of a dialkyltin oxide and an ester compound , such as # 918 of Sankyoki Gosei Co., Ltd., can be used. Further, the present inventors disclosed in Japanese Patent Laid-Open No. 6-168.
68 No. as suggested in Japanese, such as asymmetric tin alkoxides can also be used.

The reaction between the low molecular silicon compound (C) and the organotin compound (D) can be carried out, for example, by stirring the mixture in a N ₂ -substituted flask at room temperature to 180 ° C. for 1 to 10 hours. Until now, depending on the application, similar silicon compounds were sometimes added during compounding as a dehydrating agent or modulus regulator, but in such cases, those silicon compounds do not have an effect of greatly promoting curing. . That is, by preliminarily mixing or heating and mixing with a tin compound, a high catalytic activity (particularly at a low temperature) as shown in the present invention can be obtained.

The reaction molar ratio of the low molecular silicon compound (C) and the organotin compound (D) can be arbitrarily selected. In order to remarkably improve the low-temperature curability, (D) / (C) = 1 / 0.1
範 囲 1/10 is preferable, and (D) / (C) = 1 /
0.5 to 1/5 is particularly preferred.

The curing catalyst (B) is used in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the organic polymer (A) . It is particularly preferred to use 0.01 to 5 parts by weight.

The composition of the present invention may contain fillers, reinforcing agents, anti-sagging agents, adhesives and the like. As a filler, talc, clay, silica, etc., as a reinforcing agent, carbon black, fine powder silica, etc., as a pigment, iron oxide,
Inorganic pigments such as chromium oxide and titanium oxide, and organic pigments such as phthalocyanine blue and phthalocyanine green, and as an anti-sagging agent, organic acid-treated calcium carbonate, hydrogenated castor oil, calcium stearate, zinc stearate, and fine powdered silica are closely adhered. Examples of the agent include aminosilane and epoxysilane.

In the present invention, a plasticizer can be optionally used. As the plasticizer, known plasticizers can be used, and specifically, phthalic esters such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and oleic acid etc. pentaerythritol esters; aliphatic carboxylic acid esters such as butyl phosphate, trioctyl phosphate esters such as tricresyl phosphate;
Epoxidized soybean oil, epoxy plasticizers such as epoxy stearic acid benzyl; and chlorinated paraffins may be used singly or in combination.

The composition of the present invention may further contain various known additives. Examples of the additives include phenol resins, adhesiveness imparting agent such as an epoxy resin, various antioxidants, ultraviolet absorbers, etc. can be used.

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

[0044]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. First, Reference Examples 1 to
3 shows a production example of the organic polymer (A). Next, Reference Examples 4 to 8 show production examples of the curing catalyst (B).

Reference Example 1 Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a diethylene glycol-propylene oxide adduct having a molecular weight of 1,000 as an initiator according to the method described in JP-A-3-72527, and the number average A polyoxypropylene diol having a molecular weight of 19000 and _Mw / _Mn of 1.38 was obtained, a terminal hydroxyl group was converted to an allyloxy group, and methyldimethoxysilane was added and reacted with chloroplatinic acid as a catalyst to give an average molecular weight of 1.38 per molecule. Six
An organic polymer (P1) having a silicon-containing group was obtained.

Reference Example 2 Propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex using a glycerin-propylene oxide adduct having a molecular weight of 1,000 as an initiator according to the method described in JP-A-3-72527, and number averaged. Molecular weight 1
5000, a polyoxypropylene triol having an M _w / M _n of 1.42 was obtained, the terminal hydroxyl group was converted to an allyloxy group, and methyldimethoxysilane was added and reacted with chloroplatinic acid as a catalyst to give an average of 1.4 per molecule. Pieces of silicon
An organic polymer (P2) having a containing group was obtained.

Reference Example 3 A polyoxypropylene diol having a number average molecular weight of 4000 was reacted with bromochloromethane based on the method described in JP-B-61-49332, and the terminal hydroxyl group was further reacted with allyl chloride. After the allyloxy group was formed, methyldimethoxysilane was subjected to an addition reaction using chloroplatinic acid as a catalyst to obtain an organic polymer (P3). The number average molecular weight of this organic polymer in terms of polyoxypropylene diol was 11,000, and M _w / M _n was 2.3.

Reference Example 4 10.0 g (0.01 g) of di-n-butyltin dilaurate
3.3 g (0. 5 mol) of tetraethoxysilane.
015 mol) and reacted at 130 ° C. for 3 hours while stirring under a N ₂ atmosphere in a glass reactor to obtain a curing catalyst (B
1) was obtained.

Reference Example 5 10.0 g (0.022 mol) of di-n-butyltin (acetylacetonate) (2-ethylhexyl oxide) (structure shown in Chemical formula 1 ) described in JP-A-6-16868 2.60 g of dimethyldimethoxysilane
(0.022 mol) was added thereto and reacted at 60 ° C. for 3 hours while stirring under a N ₂ atmosphere in a glass reactor to obtain a curing catalyst (B2).

[0050]

Embedded image

Reference Example 6 Di-n-butyltin bisacetylacetonate 10.0
g (0.023 mol), 2.78 g (0.023 mol) of dimethyldimethoxysilane was added thereto, and the mixture was reacted at 60 ° C. for 3 hours while stirring under a N ₂ atmosphere in a glass reactor to obtain a curing catalyst (B3 ) Got.

Reference Example 7 Dimethyldimethoxysilane was added to 0.0 g (0.022 mol) of di-n-butyltin (acetylacetonate) (2-ethylhexyl oxide ) described in JP-A-6-16868. .30 g (0.011 mol)
The mixture was reacted at 60 ° C. for 3 hours while stirring under a N ₂ atmosphere in a glass reactor to obtain a curing catalyst (B7).

Reference Example 8 Vinyl trimethoxysilane was added to 10.0 g (0.022 mol) of di-n-butyltin (acetylacetonate) (2-ethylhexyl oxide ) described in JP-A-6-16868. 1.63 g (0.011 mol) was added,
The mixture was reacted at 60 ° C. for 3 hours while stirring under a N ₂ atmosphere in a glass reactor to obtain a curing catalyst (B8).

Example 1 100 parts by weight of the organic polymer (P1) obtained in Reference Example 1 was added to colloidal calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.).
75 parts by weight of white luster CCR), 75 parts by weight of heavy calcium carbonate (Whiten SB, manufactured by Shiraishi Calcium Co., Ltd.), K
BM603 (silane coupling agent, see below) .
0 parts by weight, hydrogenated castor oil 3. 0 parts by weight, titanium oxide 20
Parts by weight, and 50 parts by weight of dioctyl phthalate were added and kneaded under the condition that moisture does not enter, and then the curing catalyst (B1) synthesized in Reference Example 4 was used in 2 . 0 parts by weight were added and mixed well to obtain a composition. The mixture was bisected and one was left at room temperature to see the cured state after 3 hours, 6 hours and 12 hours. The other was left at 5 ° C., and the cured state after 3, 6 and 12 hours was observed. Table 1 shows the results.

Examples 2 to 5 and Comparative Examples 1 to 5 Mixtures having the compositions shown in Tables 1 and 2 were prepared in the same manner as in Example 1, and the cured state was checked. However, in Comparative Examples 3 and 5, dimethoxydimethylsilane was used as the curing catalyst ( B5 ) or
( B6 ) was added at the same time. The results are shown in Tables 1 and 2.

The units in the table are all parts by weight.
Further, curing catalysts shown in the text or tables, silane coupling agent, other contents are as follows.

(Curing catalyst) B4: di-n-butyltin dilaurate, B5: di-n-butyltin (acetylacetonate)
(2-ethylhexyl oxide), B6: di-n-butyltin bisacetylacetonate.

[0058] (a silane coupling agent) KBM603: 3- (2-aminoethyl) aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co. (Ltd.)), KBM602: 3- (2-aminoethyl) aminopropyl methyl dimethoxy silane ( Shin-Etsu chemical Co., Ltd.), KBM403: 3- glycine Jiruo trimethoxysilane (manufactured by Shin-Etsu chemical industry Co., Ltd.).

(Others) Epoxy resin: Epicoat 828 (manufactured by Yuka Shell Epoxy).

Examples 1, 2, and 3 were compared with Comparative Example 1,
It is clear that the curability, especially at low temperatures, is improved as compared with 2,4. In Comparative Examples 3 and 5, since dimethoxydimethylsilane was added to the composition, Example 2 was used.
The composition is the same as that of No. 3, but the curability is not improved. That is, according to the present invention, the organotin compound (D) and R ⁰ ₂ Si
It is clear that the reaction product of the silicon compound (C) represented by OR ₂ (R ⁰ and R are monovalent organic groups) is an excellent curing catalyst.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

According to the present invention, the combination of the specific organic polymer having a silicon-containing group of the present invention and the curing catalyst used in the present invention has a composition as compared with a conventionally known one. Cures fast,
In particular curing of the composition at low temperatures it is not fast.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Seiko Hayakawa 1-7-3-211 Nagahama, Kanazawa-ku, Yokohama-shi, Kanagawa (56) References JP-A-62-283158 (JP, A) JP-A-5-222284 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (3)

(57) [Claims] 1. A compound having a hydroxyl group and / or a hydrolyzable group bonded thereto.
1 molecule of silicon-containing group containing silicon atom
Organic polymer (A) having at least one polymer per unit, and organic polymer
A curing catalyst (B) is used for 100 parts by weight of the body (A).
hand,It is represented by the following equation (2)Low molecular silicon compound (C)
The reaction product of the compound with the organotin compound (D) in an amount of 0.01 to 10 times
A room temperature curable composition, characterized in that the composition contains at least one part by weight.R ^Two _b Six ¹ _4-b ... (2) Where R ^Two Is substituted or unsubstituted having 1 to 20 carbon atoms
A monovalent hydrocarbon group, X ¹ Is an alkoxy group, b is 0, 1 or
Is 2. 2. The organic polymer (A) is a derivative of the polyoxyalkylene polymer (F), and the polyoxyalkylene polymer (F) is an initiator using the double metal cyanide complex (E) as a catalyst. The room temperature curable composition according to claim 1, which is a polyoxyalkylene polymer having a number average molecular weight of 5,000 or more obtained by polymerizing an alkylene oxide. 3. The room temperature curable composition according to claim 2, wherein the double metal cyanide complex (E) is a complex containing zinc hexacyanocobaltate as a main component.