JPH06322351A - Cold-curable adhesive composition - Google Patents

Abstract

PURPOSE:To provide a cold-curable adhesive composition which comprises a polymer where the main chain is polyether and the cross-linkable chain terminals are hydrolyzable silyl groups and a compound represented by a specific formula and is useful as an adhesive or sealing agent of high adhesion. CONSTITUTION:The adhesive composition is composed of (A) 100 pts.wt. of a polymer where the main chain is essentially polyether (preferably polyoxypropylene) and the cross-linkable chain terminals have hydrolyzable silyl groups (preferably alkoxysilyl groups) and (B) 0.2 to 10 pts.wt. of a compound of the formula (R<1> is methyl, ethyl; R<2> is methyl, ethyl; R<3> is H, 2- aminoethyl; R<4> is divalent organic group of 1 to 6 carbon atoms; n is 1 to 3), preferably N,N-bis-[3-(trimethoxysilyl)propyl]ethylenediamine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive room temperature curable composition which reacts with moisture in the atmosphere and cures into a rubber at room temperature, and is particularly excellent in adhesiveness and useful as an adhesive. It relates to a composition.

[0002]

2. Description of the Related Art As a polymer which reacts with moisture in the atmosphere to cure into a rubber, for example, an oxyalkylene polymer having an ether type allyl olefin group at the terminal as described in JP-B-58-41291. In the presence of a Group VIII transition metal in the formula X _3-a SiR ⁵ _a H (wherein R ⁵ is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is 0, 1 Or 2, X represents a group or atom selected from a halogen atom, an alkoxy group, an acyloxy group and a ketoximate group.), A hydrolyzable silyl group at the end, which is obtained by reacting with a hydrosilicon compound represented by Polyethers having are disclosed. Such a polyether resin is generally called a modified silicone resin and is useful as a base resin for sealing materials, adhesives and the like. The modified silicone resin generally has low adhesiveness by itself.

Therefore, for the purpose of improving the adhesiveness, for example, Japanese Patent Publication No. 62-35421 and Japanese Patent Laid-Open No. 62-
As described in JP-A-209164, a room temperature curable composition is proposed in which a specific silane coupling agent is added to a polymer having a crosslinkable hydrolyzable silicone functional group and a main chain being essentially a polyether. Has been done.

[0004]

However, just by blending the above-mentioned silane coupling agent, the adhesive force to a difficult-to-be-adhered material such as a vinyl chloride steel plate is not sufficient, and depending on the application, a satisfactory adhesion as an adhesive is obtained. There is a problem that you cannot gain strength.

An object of the present invention is to solve the above-mentioned conventional problems and to provide an adhesive room temperature curable composition which has excellent tensile adhesion and is useful as an adhesive.

[0006]

According to the present invention, 100 parts by weight of a polymer (A) whose main chain is essentially a polyether and which has a crosslinkable hydrolyzable silyl group at its end, and a compound represented by the following general formula ( compounds represented by ^{1) (B) R 3 -N-} [R 4 -Si (R 1 3-n) (oR 2) n] 2 ··· (1) ( in the formula, R ¹ is methyl or ethyl Group, R ² is a methyl group or an ethyl group, R ³ is a hydrogen atom, or a 2-aminoethyl group H ₂ NCH ₂ CH ₂ —, R ⁴ is a divalent organic group having 1 to 6 carbon atoms, and n is 1 to 1. It is an adhesive room temperature curable composition consisting of 0.1 to 15 parts by weight.

In the present invention, the polymer (A) whose main chain has a hydrolyzable silyl group which can be crosslinked at the end with a polyether essentially is, for example, JP-B-58-41291.
An oxyalkylene polymer having an ether type allyl olefin group at the end thereof as described in JP-A No. 1993-264, in the presence of a Group VIII transition metal, represented by the following general formula X _3-a SiR ⁵ _a H

(In the formula, R ⁵ is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is 0, 1 or 2, and X is a halogen atom, an alkoxy group, an acyloxy group or a ketoximate group. A polyether having a hydrolyzable silyl group at a terminal thereof, which is obtained by reacting with a hydrosilicon compound represented by a selected group or atom is shown.

Among them, those having a main chain of polyoxypropylene are particularly preferable from the viewpoint of the characteristics of the cured product obtained. Further, as the hydrolyzable silyl group, an alkoxysilyl group is particularly preferable from the viewpoint of storage stability.

The molecular weight of the above-mentioned polyether having a hydrolyzable silyl group is 4,000 to 3
Those of 10,000 are preferable. If the molecular weight is less than 4,000, the elongation of the cured product will not be sufficient, and if it is greater than 30,000, the viscosity will be too high and the workability of the composition will be reduced.

In the present invention, the compound (B) is
For example, N, N-bis- [3- (trimethoxysilyl)
Propyl] amine, N, N-bis- [3- (triethoxysilyl) propyl] amine, N, N-bis- [3-
(Methyldimethoxysilyl) propyl] amine, N, N
-Bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (triethoxysilyl) propyl] ethylenediamine And the like, and preferably N, N-bis- [3-
(Trimethoxysilyl) propyl] amine and N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine are used.

The amount of the compound (B) used in the present invention is 0.1 to 1 with respect to 100 parts by weight of the polymer (A).
5 parts by weight, preferably 0.2 to 10 parts by weight. This is because if the addition amount is less than 0.1 parts by weight, the effect of improving the adhesiveness is small, and conversely, if it is added in excess of 15 parts by weight, there is no further effect of improving the adhesiveness.

Various fillers may be added to the adhesive room-temperature-curable composition of the present invention. As the filler, for example, calcium carbonate, magnesium carbonate, hydrous silicic acid,
Examples thereof include anhydrous silicic acid, calcium silicate, silica, titanium dioxide, clay, talc and carbon black. These fillers may be used alone,
You may use 2 or more types.

By adding a plasticizer to the adhesive room-temperature-curable composition of the present invention, the elongation property after curing can be further enhanced and the modulus can be lowered. Examples of the plasticizer include phosphates such as tributyl phosphate and tricresyl phosphate, phthalates such as dioctyl phthalate, aliphatic monobasic acid esters such as glycerin monooleate, dibutyl adipate, and dioctyl adipate. Group dibasic acid esters and the like can be mentioned. These may be used alone or in combination of two or more.

A known silanol condensation catalyst may be added to the adhesive room temperature curable composition of the present invention in order to accelerate the moisture curing reaction. Examples of silanol condensation catalysts include dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, dibutyltin bisacetylacetonate, dibutyltin bis (monoester malate), tin octylate, dibutyltin dioctoate, Examples thereof include tin compounds such as dioctyltin oxide, titanate compounds such as tetra-n-butyl titanate and tetraisopropyl titanate, amine salts such as dibutylamine-2-ethylhexoate, amine compounds and the like.

An anti-sagging agent such as hydrogenated castor oil or fatty acid bisamide may be added to the adhesive room-temperature-curable composition of the present invention to prevent sagging. In the adhesive room temperature curable composition of the present invention, further, a pigment, an ultraviolet absorber,
It can be modified by adding an antioxidant or the like.

[0017]

The adhesive room-temperature-curable composition of the present invention comprises 100 parts by weight of a polymer (A) whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at the end, A cured product obtained by comprising 0.1 to 15 parts by weight of the compound (B) represented by the formula is a polar group containing a nitrogen atom on the surface of the reaction product of the polymer (A) and the compound (B). It has excellent tensile adhesive strength to various adherends because it has a proper amount.

[0018]

EXAMPLES The present invention will be clarified by giving Examples and Comparative Examples of the present invention. Examples 1 to 4 and Comparative Examples 1 and 2 "Cyryl 5A03" manufactured by Kanegafuchi Chemical Co., Ltd. is used as a polymer (A) whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at its terminal. (Molecular weight 8500) was used and compounded by the following method.

"Cyril 5A03" manufactured by Kanegafuchi Chemical Co., Ltd.
(A) 100 parts by weight, plasticizer dioctyl phthalate 30
Parts by weight, 100 parts by weight of calcium carbonate and titanium oxide 2
After uniformly kneading 0 parts by weight with a three-roll mill, 3 parts by weight of a moisture curing catalyst dibutyltin dilaurate, and a predetermined amount (parts by weight) of the compounds of Examples 1 to 4 and Comparative Examples 1 and 2 shown in Table 1 ( B) and other compounding ingredients were added and uniformly mixed to obtain an adhesive room temperature curable composition. The tensile adhesive strength of the obtained adhesive room temperature curable composition was measured by the following measuring method. The results are also shown in Table 1.

Method for Measuring Tensile Adhesion Strength Using anodized aluminum and a vinyl chloride steel plate as adherends, H-shaped test pieces based on JIS A5758 were prepared,
After curing at 23 ° C 60% RH for 2 weeks and at 30 ° C for 2 weeks, 5
A tensile test was performed at a speed of 0 mm / min, the 50% modulus (M ₅₀ ) and the tensile strength were measured, and the fracture morphology was observed.

[0021]

[Table 1]

As is clear from Table 1, in the case of Examples 1 to 4 of the present invention, high tensile adhesion is obtained not only for the adherend made of aluminum but also for the difficult adherend made of PVC steel plate. It shows a force, and when it sees the form of destruction, it shows cohesive failure. On the other hand, in the case of Comparative Examples 1 and 2, the tensile adhesive strength to the adherend made of aluminum is low, and the tensile adhesive strength is particularly low to the difficult adherend made of the vinyl chloride steel plate.

[0023]

EFFECTS OF THE INVENTION Since the adhesive room temperature-curable composition of the present invention has the above-mentioned constitution, it has excellent tensile adhesion to various adherends and is suitable for use as an adhesive or a sealing material. can do.

Claims (1)

[Claims] 1. 100 parts by weight of a polymer (A) whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at the terminal, and a compound (B) R ³ represented by the following general formula: ^{-N- [R 4 -Si (R 1} 3-n) (oR 2) n] 2 ( wherein, R ¹ represents a methyl or ethyl group, R ² is methyl or ethyl, R ³ is a hydrogen atom, Or a 2-aminoethyl group H ₂ NCH ₂ CH ₂ —, R ⁴ is a divalent organic group having 1 to 6 carbon atoms, and n is an integer of 1 to 3.) 0.1 to 15 parts by weight. An adhesive room temperature curable composition characterized by: