JP3144896B2 - Room temperature curable composition - Google Patents

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 at room temperature into a rubbery state by reacting with atmospheric moisture, and more particularly to a room temperature curable composition having excellent adhesiveness and useful as a sealing material or an adhesive. It relates to a curable composition.

[0002]

2. Description of the Related Art Examples of a polymer which reacts with moisture in the atmosphere to cure into a rubbery state include polyethers described in JP-B-58-41291. This polyether is a polyether obtained by reacting an oxyalkylene polymer having an ether type allyl olefin group at a terminal with a hydrosilicon compound represented by the following general formula in the presence of a Group VIII transition metal. .

X _3-a -Si (H) -R _a (where R is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2; Represents a group or an atom selected from a halogen atom, an alkoxy group, an acyloxy group and a ketoxime group.)

[0004] The polyether resin obtained as described above is generally called a modified silicone resin and is useful as a base resin for a sealing material. Such a modified silicone resin generally has low adhesiveness alone. Therefore, for the purpose of improving adhesiveness, for example,
JP-A-35421 and JP-A-62-209164 disclose that a specific silane coupling agent is added to a modified silicone resin.

[0005]

With respect to such a polyether having a hydrolyzable silyl group at the terminal, a polysilane having a bonding agent such as a silane coupling agent can be added to a metal plate such as aluminum to a certain extent. Can be obtained. However, sufficient adhesiveness has not been obtained for hard-to-bond materials such as PVC steel sheets.

An object of the present invention is to solve such a conventional problem and to provide a room-temperature-curable composition which can obtain sufficient adhesiveness even for hard-to-bond materials such as PVC steel sheets. And

[0007]

The room-temperature-curable composition of the present invention comprises (A) a polymer 100 having a main chain of essentially polyether and having a crosslinkable hydrolyzable silyl group at a terminal.
Parts by weight, (B) 0.1 to 100 parts by weight of a compound having two or more (meth) acryloyl groups in one molecule, and (C)
0.1 to 20 parts by weight of an amine compound selected from a primary amine compound having a hydrolyzable silyl group and a secondary amine compound having a hydrolyzable silyl group. However, drying oils and derivatives obtained by denaturing them
Excluding those that include the body.

The polymer (A) having a hydrolyzable silyl group whose main chain is essentially a polyether and has a crosslinkable terminal at the terminal, which is used in the present invention, is exemplified by, for example, JP-B-58-1983.
No. 41291, that is, by reacting an oxyalkylene polymer having an ether type allyl olefin group at a terminal with a hydrosilicon compound represented by the following general formula in the presence of a Group VIII transition metal. The resulting polyether having a hydrolyzable silyl group at the terminal is exemplified.

X _3-a -Si (H) -R _a (where R is a group selected from a monovalent hydrocarbon group and a halogenated monovalent hydrocarbon group, a is an integer of 0, 1 or 2;
Represents a group or an atom selected from a halogen atom, an alkoxy group, an acyloxy group, and a ketoxime group. )

Of these compounds, those having a main chain of polyoxypropylene are particularly preferred in view of the properties of the cured product. As the hydrolyzable silyl group, an alkoxysilyl group is particularly preferable from the viewpoint of storage stability. Also,
The molecular weight of the polyether having a hydrolyzable silyl group at the terminal is preferably from 4,000 to 30,000. If it is less than 4000, the elongation of the cured product is not enough,
If it is larger than 0000, the viscosity is too high, and the workability of the composition is reduced.

In the specification of the present application, the expression of (meth) acryloyl indicates either acryloyl or methacryloyl, and the expressions of (meth) acrylate and (meth) acryl used hereinafter are also acrylate or methacrylic, respectively. Represents methacrylate, acrylic or methacryl. As the compound (B) having two or more (meth) acryloyl groups in one molecule used in the present invention, for example, the following compounds can be used.

Ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate,
1,9-nonanediol di (meth) acrylate,
14-tetradecanediol di (meth) acrylate,
Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) ) Acrylate, propylene oxide modified trimethylolpropane tri (meth)
Acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, dicyclopentanyldi (meth) acrylate, Tris ((Meth) acryloxyethyl) isocyanurate, bis ((meth) acryloxyethyl) hydroxyethyl isocyanurate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, bisphenol S di (meth) acrylate, ethylene Oxide-modified bisphenol A di (meth) acrylate, ethylene oxide-modified bisphenol F di (meth) acrylate, ethylene oxide-modified bisphenol Lumpur S di (meth) acrylate.

Epoxy (meth) acrylates obtained by reacting an epoxy group of an epoxy resin with (meth) acrylic acid. Having a hydroxy group after reacting a polyol with a polyisocyanate to introduce an isocyanate group (meth)
A method of reacting an acrylic acid ester, a method of reacting a (meth) acrylic acid ester having a hydroxy group with a polyisocyanate, a method of reacting a (meth) acrylic acid ester having a hydroxy group so that the isocyanate group remains with the polyisocyanate, Urethane (meth) acrylates obtained by a method such as a method of reacting a polyol with an isocyanate group.

Polyester (meth) acrylates obtained by subjecting a hydroxy group remaining in a polyester synthesized from a polyol and a polybasic acid to a condensation reaction with (meth) acrylic acid or a transesterification reaction with (meth) acrylic acid ester. Polyether (meth) acrylates obtained by subjecting a polyether polyol to a transesterification reaction with a (meth) acrylate.

Among the above compounds, epoxy (meth) acrylates, from the viewpoint of low volatility and low toxicity,
Urethane (meth) acrylates, polyester (meth) acrylates, and polyether (meth) acrylates are preferably used. (Meta) used in the present invention
The amount of the compound (B) having two or more acryloyl groups in one molecule is 0.1 to 100 parts by weight based on 100 parts by weight of the polymer (A). If the amount is less than 0.1 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 100 parts by weight, there is no effect of improving the adhesiveness, but rather the adhesiveness is reduced. Preferably the amount used is 0.5 to 70
Parts by weight.

The amine compound (C) used in the present invention, which is selected from a primary amine compound having a hydrolyzable silyl group and a secondary amine compound having a hydrolyzable silyl group, includes alkoxysilyl as a hydrolyzable silyl group. An amine compound selected from a primary amine compound and a secondary amine compound having a group is preferred. Such compounds include, for example, 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N-
(2-aminoethyl) -3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N-bis- [3-
(Trimethoxysilyl) propyl] amine, N, N-bis- [3- (triethoxysilyl) propyl] amine,
N, N-bis- [3- (methyldimethoxysilyl) propyl] amine, 3- [N-allyl-N- (2-aminoethyl)] aminopropyltrimethoxysilane, p- [N
-(2-aminoethyl) aminomethyl] phenethyltrimethoxysilane, N, N-bis- [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis-
[3- (methyldimethoxysilyl) propyl] ethylenediamine, N- [3- (trimethoxysilyl) propyl] diethylenetriamine, N- [3- (methyldimethoxysilyl) propyl] diethylenetriamine, N-
[3- (trimethoxysilyl) propyl] triethylenetetramine, N- [3- (methyldimethoxysilyl) propyl] triethylenetetramine, and the like.

The amount of the amine compound (C) used in the present invention is based on 100 parts by weight of the polymer (A).
0.1 to 20 parts by weight. If the amount is less than 0.1 part by weight, the effect of improving the adhesiveness is small, and if it exceeds 20 parts by weight, there is no further effect of improving the adhesiveness. Preferably, the amount used is 0.5 to 10 parts by weight. Various fillers can be added to the room temperature curable composition of the present invention for the purpose of modification. For example, calcium carbonate, magnesium carbonate, hydrated silicic acid, silicic anhydride, calcium silicate, silica, titanium oxide, clay, talc, carbon black and the like can be added. These fillers may be used alone or in combination of two or more.

In the present invention, by adding a plasticizer, the elongation properties after curing can be further improved and the modulus can be reduced. Examples of the plasticizer include phosphoric esters such as tributyl phosphate and tricresyl phosphate; phthalic esters such as dioctyl phthalate; aliphatic monobasic esters such as glycerin monooleate; and aliphatic dibasic esters such as dibutyl adipate and dioctyl adipate. Basic acid esters and the like can be mentioned. These can be used alone or in combination of two or more.

In the present invention, a known silanol condensation catalyst may be added to accelerate the moisture curing reaction. For example, tin such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate, dibutyltin bisacetylacetonate, dibutyltin bis (monoester maleate), tin octylate, dibutyltin octoate, and dioctyltin oxide Examples thereof include compounds, titanate compounds such as tetra-n-butyl titanate and tetraisopropyl titanate, amine salts such as dibutylamine-2-ethylhexoate, and amine compounds.

In the present invention, an anti-sagging agent such as hydrogenated castor oil and fatty acid bisamide may be added to prevent sagging. Furthermore, in the present invention, a pigment, an ultraviolet absorber,
Modification is possible by adding an antioxidant or the like.

[0021]

According to the present invention, the polymer (A) whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at the terminal, and a (meth) acryloyl group in one molecule. By mixing the compound (B) having two or more and the amine compound (C) selected from a primary amine compound having a hydrolyzable silyl group and a secondary amine compound having a hydrolyzable silyl group, various types of compounds can be obtained. It is a room temperature curable composition that shows good adhesiveness to the adherend. The room temperature-curable composition of the present invention exhibits good adhesiveness to various adherends as described above, and is therefore useful as a sealing material and an adhesive.

[0022]

EXAMPLES Preparation of curable composition Polymer (A) whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at the end, and a (meth) acryloyl group in one molecule. The following compounds were used as the compound (B) having at least one compound, the primary amine compound having a hydrolyzable silyl group, and the secondary amine compound (C) having a hydrolyzable silyl group, and the mixing ratio shown in Table 1 ( The composition is shown in parts by weight) to prepare a room temperature curable composition.

(A) Polyether polymer: Kanebuchi Chemical Co., trade name; Cyril 5A03 (molecular weight 8500). (B) Epoxy acrylate: Kyoeisha Yushi Co., trade name; Epoxy ester 1600A (1,6- Reaction product of diglycidyl ether of hexanediol and acrylic acid)

(B) Epoxy methacrylate: manufactured by Nagase & Co., trade name; Denacol DM-851 (reacted product of diglycidyl ether of diethylene glycol and methacrylic acid). (B) Urethane acrylate: manufactured by Kyoeisha Yushi Co., Ltd. AH400 (1-acryloxy-3-phenoxy-
Urethane reaction product of 2-propanol and hexamethylene diisocyanate)

(B) Polyester acrylate (1): manufactured by Toagosei Co., Ltd., trade name: ARONIX M-80
60 ・ (B) Polyether acrylate (1): manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name: NK ester A-600 (polyethylene glycol diacrylate) ・ (B) 1,6-hexanediol diacrylate: manufactured by Shin-Nakamura Chemical Co. NK Ester A-HD

(B) Tetradecanediol diacrylate: manufactured by Sartomer, trade name: Chemlink20
00 ・ (B) Polyester acrylate (2): manufactured by Toagosei Co., Ltd .; trade name: Aronix M-6200 ・ (B) Polyether acrylate (2): manufactured by Shin-Nakamura Chemical Co., Ltd .; trade name: NK ester APG-400 (polypropylene) Glycol 400 diacrylate)

(C) aminosilane (1): 3- [N-
(2-aminoethyl)] aminopropylmethyldimethoxysilane • (C) aminosilane (2): 3-aminopropyltrimethoxysilane • (C) aminosilane (3): N, N-bis- [3-
(Triethoxysilyl) propyl] amine

For comparison, a room temperature curable composition was prepared at the compounding ratio shown in Table 2. In Comparative Examples 4 and 5, the following monoacrylate was used instead of the compound (B). -Monoacrylate (1): 2-ethylhexyl acrylate-Monoacrylate (2): N, N-dimethylaminoethyl acrylate

Calcium carbonate and titanium oxide at 120 ° C.
After pre-drying for 2 hours, silyl 5A03 as the above polyether polymer (A) and dioctyl phthalate as a plasticizer are put into a sealed mixing stirrer together with the dried calcium carbonate and titanium oxide and uniformly kneaded. After further adding the compound (B), the amine compound (C) and the remaining additives, the mixture was uniformly mixed and stirred to obtain a room temperature curable composition.

Method of measuring physical properties Tensile adhesiveness An H-shaped test piece was prepared from the obtained curable composition in accordance with JIS A5758, and after curing at 23 ° C. and 60% RH for 2 weeks and at 30 ° C. for 2 weeks, 50 mm / min. The tensile test was performed at the following speed. An anodized aluminum plate and a PVC steel plate were used as adherends.

Tensile Properties of Cured Product Each of the obtained curable compositions was formed into a sheet having a thickness of 2 mm, and cured at 23 ° C. and 60% RH for one week.
A No. 3 dumbbell test piece was prepared in accordance with IS K6301, and a tensile test was performed at a speed of 50 mm / min. The obtained results are shown in Tables 1 and 2.

[0032]

[Table 1]

[0033]

[Table 2]

As is clear from the results in Tables 1 and 2,
The curable compositions of the examples according to the present invention show a high tensile strength not only to the adherend of aluminum but also to the adherend of a PVC steel sheet, and cause cohesive failure.

Claims (1)

(57) [Claims] (A) 100 parts by weight of a polymer whose main chain is essentially a polyether and has a crosslinkable hydrolyzable silyl group at a terminal, and (B) a (meth) acryloyl group in one molecule. 0.1 to 100 parts by weight of a compound having two or more amines, and (C) an amine compound 0.1 to 100 selected from a primary amine compound having a hydrolyzable silyl group and a secondary amine compound having a hydrolyzable silyl group. Room temperature curable composition (provided that a drying oil and
Excluding those containing derivatives obtained by modifying this).