JPH07310006A - Room temperature curing composition - Google Patents

Abstract

PURPOSE:To obtain a composition providing a curing material for a sealing material having excellent elongation and adhesiveness, reacting with water in the air at room temperature, comprising a specific hydrolyzable silyl group- containing polymer, a bissilyl compound and a monosilyl compound. CONSTITUTION:(A) 100 pts.wt. of a polymer comprising a polyalkylene oxide as a main chain and a cross-linkable hydrolyzable silyl group at the end is blended with (B) 0.5-5 pts.wt. of a bissilyl compound of formula I to formula III (R<1> and R<6> are methyl or ethyl; (n), (m) and (1) are 1 to 3; (p) and (q) are 2 to 6) and (C) 0.2-7 pts.wt. of a monosilyl compound of formula IV (R<7> is hydrogen or 2-aminoethyl; R<8> and R<9> are methyl or ethyl; (k) is 1 to 3). Polypropylene oxide is preferable as the component A, N,N-bis-[3-(trimethoxysilyl) propyl]ethylenediamine is used as the component B and 3- aminopropyltrimethoxysilane is used as the component C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature curable composition which cures into a rubber-like composition when reacted with atmospheric humidity, and particularly useful as a sealing agent or an elastic adhesive having excellent adhesiveness. Regarding things.

[0002]

2. Description of the Related Art As a polymer which reacts with moisture in the atmosphere to cure into a rubber, it has at least one hydrolyzable silyl group at its terminal, and its main chain is essentially polypropylene oxide. It has been proposed to contain a polyether having a molecular weight of 6300 to 15000 as an active ingredient (Japanese Patent Publication No. 61-18582).

Such a polyether is generally called a modified silicone resin and is useful as a base resin for a sealing material. However, since it does not have adhesiveness, it can be used as a silane coupling agent or a titanium coupling agent. Adhesives are needed. It has been reported that a specific silane coupling agent is added for the purpose of improving such adhesiveness (Japanese Patent Publication No. 62-35421 and Japanese Patent Laid-Open No. 62-42421).
209164).

[0004]

However, although the adhesion to ordinary adherends is improved only by adding an adhesion-imparting agent such as a silane coupling agent or a titanium coupling agent, the outer wall of a building is improved. Adhesive strength to a vinyl chloride steel sheet used for example is not sufficient, and satisfactory adhesiveness as a sealing material or an adhesive cannot be obtained.

The present invention has been made in view of the above problems, and it is an object of the present invention to have sufficient extensibility and tensile strength as a sealing material and to bond a vinyl chloride steel sheet or the like under ordinary circumstances. Provided is an adhesive room temperature curable composition which has sufficient adhesiveness even for difficult adherends and does not impair the adhesiveness and extensibility of the cured product even after closed storage and has excellent storage stability. To do.

[0006]

The adhesive room temperature curable composition of the present invention comprises a polymer (A) whose main chain is essentially a polyalkylene oxide, a bissilyl compound (B) and a monosilyl compound (C). Become.

The polymer (A) whose main chain is essentially a polyalkylene oxide and which contains a crosslinkable hydrolyzable silyl group at the end, which is used in the present invention, means that the main chain is essentially It contains a chemically bonded repeating unit represented by the general formula [-(R-O) _n- , wherein R represents an alkylene group having 1 to 4 carbon atoms], and can be crosslinked at the end. Polymers containing hydrolyzable silyl groups.

The above polymer (A) is synthesized, for example, by reacting a polyalkylene oxide having an allyl group at the terminal with a silicon hydride compound represented by the following chemical formula in the presence of a Group VIII transition metal.

X _3-a SiR ¹⁰ _a H

In the formula, R ¹⁰ is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is 0,
An integer of 1 or 2, X is a halogen atom, an alkoxy group,
It means an atom or group selected from an acyloxy group and a ketoximate group.

Examples of the polyalkylene oxide which is the main chain of the polymer (A) include polyethylene oxide, polypropylene oxide, polybutylene oxide, and the like. The cured product of the room temperature curable composition has excellent water resistance. In addition, polypropylene oxide is preferable because it can ensure elasticity as a sealing material.

The crosslinkable hydrolyzable silyl group is preferably one which does not produce harmful by-products after the reaction, and examples thereof include alkoxysilyl groups such as methoxysilyl group and ethoxysilyl group.

When the number average molecular weight of the polymer (A) is small, the elongation of the cured product is insufficient and the followability to the joint surface is deteriorated, and when it is large, the viscosity before curing is too high and the work in the compounding step is performed. The number average molecular weight is preferably from 4,000 to 30,000 because of poor performance.

Examples of the above-mentioned polymer (A) include those manufactured by Asahi Glass Co., Ltd. under the trade name "Excester 2410", manufactured by Kanefuchi Chemical Co., Ltd. under the trade name "Cyril 5A03", and the like.

The bissilyl compound (B) used in the present invention is a compound selected from the group consisting of the following general formulas (1), (2) and (3).

[Chemical 5] (In the formula, R ¹ and R ² each represent a methyl group or an ethyl group, n represents an integer of 1 to 3, and p represents an integer of 2 to 6.)

[Chemical 6] (In the formula, R ³ and R ⁴ each represent a methyl group or an ethyl group, m represents an integer of 1 to 3, and q represents an integer of 2 to 6, respectively.)

[Chemical 7] (In the formula, R ⁵ and R ⁶ each represent a methyl group or an ethyl group, and l represents an integer of 1 to 3, respectively.)

Examples of the bissilyl compound represented by the general formula (1) include N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N,
N'-bis- [3- (triethoxysilyl) propyl]
Ethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N,
N'-bis- [3- (trimethoxysilyl) propyl]
Hexamethylenediamine, N, N'-bis- [3- (triethoxysilyl) propyl] hexamethylenediamine, N, N'-bis- [3- (methyldimethoxysilyl) propyl] hexamethylenediamine and the like can be mentioned.

Examples of the bissilyl compound represented by the above general formula (2) include N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine and N, N-.
Bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis-
[3- (Trimethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (triethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] Hexamethylenediamine and the like can be mentioned.

Examples of the bissilyl compound represented by the above general formula (3) include N, N-bis- [3- (trimethoxysilyl) propyl] amine and N, N-bis- [3.
-(Triethoxysilyl) propyl] amine, N, N-
Examples thereof include bis- [3- (methyldimethoxysilyl) propyl] amine.

When the amount of the bissilyl compound (B) is small, a sufficient effect of improving the adhesiveness cannot be obtained, and when the amount is large,
Since the elongation of the cured product cannot be obtained after curing, the addition amount is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polymer (A).

The monosilyl compound (C) used in the present invention is a compound represented by the following general formula (4).

[Chemical 8] (In the formula, R ⁷ represents a hydrogen atom or a 2-aminoethyl group,
R ⁸ and R ⁹ each represent a methyl group or an ethyl group, and k represents an integer of 1 to 3, respectively. )

Examples of the monosilyl compound (C) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethordimethoxysilane, 3-aminopropyltriethoxysilane and N- (2-aminoethyl)-.
Examples thereof include 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropyltriethoxysilane.

When the amount of the monosilyl compound (C) becomes small, the adhesiveness and elongation of the cured product of the adhesive room temperature-curable composition after storage are remarkably lowered as compared with those before storage, that is, the storage stability is decreased, and the amount is high. If so, the adhesiveness will be reduced, so the addition amount is 0.2 to 7 parts by weight, preferably 0.5 to 5 parts by weight, relative to 100 parts by weight of the polymer (A).

The essential components of the room temperature curable composition of the present invention are as described above. In addition to the above essential components, silanol condensation catalysts, physical property modifiers, plasticizers, dehydrating agents, fillers, anti-sagging agents, etc. May be added as appropriate.

The silanol condensation catalyst is added for the purpose of promoting the moisture curing reaction. As the silanol condensation catalyst, known ones can be used, for example, dibutyltin dilaurate, dibutyltin maleate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, dibutyltin bisacetylacetonate, dibutyltin bis (monoester). Maleate), dibutyltin octoate, tin octylate, dioctyltin oxide, tin compounds such as tin naphthenate, titanate compounds such as tetra-n-butoxytitanate, tetraisopropoxytitanate, dibutylamine-2-ethylhexoate. Such as amine salts, organic aluminum compounds such as diisopropoxyaluminum ethylacetoacetate, chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate, Le acids lead, and the like. The silanol condensation catalysts may be used alone or in combination of two or more.

When the silanol condensation catalyst is less, the curing rate becomes slower, and when it is more, the curing rate becomes faster and the workability is deteriorated. Therefore, the addition amount is 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer (A). Parts are preferred.

The physical property modifier is added for the purpose of improving tensile properties. Examples of the physical property adjusting agent include silicon compounds having one silanol group in one molecule. Examples thereof include triphenylsilanol, trialkylsilanol, dialkylphenylsilanol, diphenylalkylsilanol, and the like. There is a silicon compound that decomposes to form a compound having one silanol group in one molecule, and examples thereof include triphenylmethoxysilane, trialkylmethoxysilane, dialkylphenylmethoxysilane, diphenylalkylmethoxysilane, triphenylethoxylane, and triphenylethoxysilane. Alkyl ethoxysilane etc. are mentioned. The physical property modifiers may be used alone or in combination of two or more.

The above-mentioned plasticizer is added for the purpose of enhancing the elongation property after curing and lowering the modulus. Examples of the plasticizer include phosphates such as tributyl phosphate and tricresyl phosphate, phthalates such as dioctyl phthalate, fatty acid monobasic acids such as glycerin monooleate, dibutyl adipate and dioctyl adipate. And fatty acid dibasic acid ester, polyethylene glycol (PEG), and the like. The above plasticizers may be used alone or in combination of two or more kinds.

The dehydrating agent is added for the purpose of removing water during storage. Examples of the dehydrating agent include silane compounds such as vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane and methyltriethoxysilane, and octadecyl isocyanate, 4,4′-diphenylmethane diisocyanate, isophorone diisocyanate, 4 , 4 '
Examples of the isocyanate compound include dicyclohexylmethane diisocyanate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, lysine ester triisocyanate, and 1,8-diisocyanate-4-isocyanate octane. The above dehydrating agents may be used alone or in combination of two or more kinds.

When the amount of the dehydrating agent is small, the viscosity becomes thick during storage and gels, so that the storage stability is lowered, and when the dehydrating agent is large, the curing time after construction becomes long, and therefore the addition amount is 100 parts by weight of the polymer (A). 0.1 to 10 parts by weight is preferable.

The above-mentioned filler is added for the purpose of reinforcing the cured product. Examples of the filler include calcium carbonate, magnesium carbonate, hydrous silicic acid, silicic acid anhydride, calcium silicate, silica, titanium dioxide, clay, talc, carbon black and the like. You may use the said filler individually or in combination of 2 or more types.

The above-mentioned anti-dripping agent is added for the purpose of suppressing the sagging during the work. Examples of the anti-sagging agent include hydrogenated castor oil derivatives, fatty acid amide wax, aluminum stearylates, barium stearylates and the like. The anti-sagging agent may be used alone or in combination of two or more kinds.

Furthermore, pigments, ultraviolet absorbers, antioxidants, flame retardants and the like may be added to the room temperature curable composition of the present invention as appropriate.

[0033]

EXAMPLES Next, examples of the present invention will be described.
In the following, "parts" means "parts by weight".

(Examples 1 to 5, Comparative Examples 1 to 9) Tables 1 to 3
According to the compounding composition of "Exestar 2410" as a polymer (Asahi Glass Co., Ltd., trade name, molecular weight 17,
000), N, N'-bis- [3- (trimethoxysilyl) propyl] ethylenediamine (manufactured by Chisso Corporation, trade name "XS951"), N, N'-bis- [3- ( Methyldimethoxysilyl) propyl] ethylenediamine (manufactured by Chisso Corporation, trade name “XS94
6 "), N, N-bis- [3- (trimethoxysilyl)
Propyl] ethylenediamine (manufactured by Toshiba Silicone Co., Ltd., trade name "TSL8212"), N, N-bis- [3
-(Trimethoxysilyl) propyl] amine (Toshiba Silicone Co., Ltd., trade name "TSL8206"), 3-
Aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM602") was used. Furthermore, using dibutyltin dilaurate, vinyltrimethoxysilane, dioctyl phthalate as other additives, calcium carbonate and titanium oxide, by uniformly mixing with a mixing stirrer that is sealed so that moisture does not enter from the outside, A room temperature curable composition was obtained. [Adhesion Test Method] (Adhesion Test Before Storage) Using an anodized aluminum and vinyl chloride steel sheet as an adherend and using an adhesive room-temperature-curable composition immediately after blending as described above, JIS A5758
H-type test piece based on the above, and after curing for 2 weeks in a constant temperature and humidity room of 23 ° C. and 60%, further curing for 2 weeks in a constant temperature room of 30 ° C., and then a tensile test at a speed of 50 mm / min. The maximum tensile strength and the maximum elongation were measured, and the fracture mode was observed. (Adhesion test after storage) Further, the adhesive room temperature curable composition blended as described above was filled and sealed in a moisture-proof aluminum-coated cartridge paper tube for a sealing material, and then stored at 50 ° C for one month. By the same method as the above adhesion test,
An adhesion test was conducted. The evaluation results are shown in Tables 1 to 3.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

The composition of the room temperature curable composition of the present invention is as described above, and by adding a specific silane compound, it has sufficient extensibility as a sealing material and not only aluminum but also vinyl chloride. It exhibits high adhesion to steel sheets and retains high adhesion and sufficient elongation even after closed storage.

Claims (1)

[Claims] 1. A polymer (A) whose main chain is essentially a polyalkylene oxide and which contains a crosslinkable hydrolyzable silyl group at its terminal, 100 parts by weight, the following general formula (1),
0.05 to 5 parts by weight of at least one bissilyl compound (B) selected from the group consisting of (2) and (3), (In the formula, R ¹ and R ² each represent a methyl group or an ethyl group, n represents an integer of 1 to 3, and p represents an integer of 2 to 6.) (In the formula, R ³ and R ⁴ each represent a methyl group or an ethyl group, m represents an integer of 1 to 3, and q represents an integer of 2 to 6.) (In the formula, R ⁵ and R ⁶ each represent a methyl group or an ethyl group, and 1 represents an integer of 1 to 3, respectively) and the monosilyl compound (C) 0.2 to 7 represented by the following general formula (4).
Parts by weight (In the formula, R ⁷ represents a hydrogen atom or a 2-aminoethyl group,
R ⁸ and R ⁹ each represent a methyl group or an ethyl group, and k represents an integer of 1 to 3, respectively. Room temperature curable composition comprising