JPH09302331A - Modified silicone mastic-based sealing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a modified silicone mastic-based sealing agent excellent in weather stability, facilitating a coating of a coating material on a cured surface and having a cured surface hardly soiled. SOLUTION: This modified silicone mastic-based sealing agent comprises (A) a polymer having a main chain consisting essentially of a polyether and a molecular terminal of a cross-linkable and hydrolyzable silyl group (e.g. a polymer having a main chain of polyoxypropylene and a molecular terminal of dimethoxysilyl group) and (B) an amine compound [e.g. N-(2-aminoethyl)-3- aminopropyltrimethoxysilane].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mastic-based sealing material having a surface which hardens by reacting with moisture in the atmosphere.

[0002]

2. Description of the Related Art Sealing materials are used for sealing joints of buildings and the like, but they require a primer at the time of construction because of their poor adhesion to adherends. On the other hand, the mastic type sealing material is a non-hardening type which forms a rubber-like film on the surface and hardens but does not harden the inside, and generally adheres to various adherends without using a primer. It is a sealing material. Mastic-based sealing materials are often used for applications requiring flexibility, such as joint seals for glass windows attached to aluminum sash window frames. As such a mastic-based sealing material,
Conventionally, silicone-based sealing materials and oil-based caulking materials have been known. The above-mentioned silicone-based sealing material is a sealing material containing silicone as a main component, but it has a problem that the coating material is repelled even when the coating material is applied to the surface after curing and that the coating material is easily contaminated. The oil-based caulking material is a sealing material containing natural or synthetic dry oil or resin (mainly alkyd resin) as a main component, and its surface is oxidatively polymerized by oxygen in the air. There is a problem that is bad.

Further, examples of the polymer which is surface-cured by reacting with moisture in the atmosphere include, for example, JP-A-50-156599.
VIII, an oxyalkylene polymer having an ether type allyl olefin group at the molecular end, which is described in Japanese Patent No.
In the presence of a group transition metal, in the general formula X _3-a SiR _a H (wherein, R is a monovalent hydrocarbon radical or halogenated monovalent hydrocarbon radical, a is an integer of 0 to 2, X is a halogen atom, Examples thereof include a polyether having a hydrolyzable silyl group at the molecular end, which is obtained by reacting with a hydrosilicon compound represented by an atom or group selected from the group consisting of an alkoxy group, an acyloxy group and a ketoximate group. Curable compositions containing such polymers are known to have excellent performance.

[0004]

SUMMARY OF THE INVENTION The present invention is to solve the above-mentioned problems of conventional mastic type sealing materials, and its purpose is to have good weather resistance and to be able to apply a paint to a cured surface. Another object of the present invention is to provide a mastic-based sealing material in which the cured surface is not easily contaminated.

[0005]

The modified silicone mastic sealant of the present invention comprises a polymer (A) whose main chain is essentially a polyether and which has a crosslinkable hydrolyzable silyl group at the molecular end. , (B) an amine compound.

The mastic-based sealing material in the present invention refers to a sealing material having a cured film thickness of 0.5 to 2 mm after one month under curing conditions of a temperature of 20 ° C. and a relative humidity of 60%.

The main chain is essentially a polyether,
Polymer having a crosslinkable hydrolyzable silyl group at the molecular end, an oxyalkylene polymer having ether type allele olefin group at the molecular end, in the presence of a Group VIII transition metal, the general formula X _3-a SiR _a H (in the formula, R is a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, a is an integer of 0 to 2, X is an atom selected from the group consisting of a halogen atom, an alkoxy group, an acyloxy group and a ketoximate group, or It is a polymer obtained by reacting with a hydrosilicon compound represented by (group).

The backbone is essentially a polyether,
In the polymer having a crosslinkable hydrolyzable silyl group at the molecular end, the oxyalkylene polymer which is the main chain thereof includes, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, etc. From the viewpoint of balance, polyoxypropylene is preferable.
As the crosslinkable hydrolyzable silyl group, a methoxysilyl group is preferable from the viewpoint of reactivity and a product generated after the reaction.
The number average molecular weight of this polymer is 4000 to 3
Those having a number average molecular weight of 100 are especially preferable.
Those having a molecular weight distribution (weight average molecular weight / number average molecular weight) of from 0.00 to 30,000 and 1.6 or less are preferable.

Commercially available products of the above-mentioned polymer are, for example, "MS Polymer S-203", trade name, manufactured by Kaneka Corporation.
"MS Polymer S-303", "MS Polymer S-90"
3 ”and other MS polymers; trade names“ CYRIL SAT-200 ”and“ CYRIL MA-430 ”manufactured by Kaneka Corporation.
Cyryl polymers such as "Cyryl MAX447"; manufactured by Asahi Glass Co., Ltd., trade name "Excester ESS-3620",
"Exestar ESS-3430", "Exestar E
SS-2420 "," Exestar ESS-2410 "
And the like, and these may be used alone or in combination of two or more.

The amine compound used in the present invention is used as a curing catalyst for the above polymer. As the amine compound, an amino group-containing silane compound is preferable, and examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3.
-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 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, N, N-bis- [3-
(Trimethoxysilyl) propyl] ethylenediamine,
N, N-bis- [3- (methyldimethoxysilyl) propyl] ethylenediamine, N, N-bis- [3- (triethoxysilyl) propyl] ethylenediamine, N, N
-Bis- [3- (trimethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3- (methyldimethoxysilyl) propyl] hexamethylenediamine,
N, N-bis- [3- (triethoxysilyl) propyl] hexamethylenediamine, N, N-bis- [3-
(Trimethoxysilyl) propyl] amine, N, N-bis- [3- (triethoxysilyl) propyl] amine,
Examples thereof include N, N-bis- [3- (methyldimethoxysilyl) propyl] amine, and these may be used alone or in combination of two or more kinds.

If the amount of the amine compound is small, poor curing will occur, and if it is large, the curing will be quick and problems such as workability will occur. Therefore, the main chain is essentially a polyether, and a hydrolyzable compound capable of crosslinking to the molecular end. The amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymer having a degradable silyl group.

The modified silicone mastic type sealing material of the present invention includes a dehydrating agent, a filler, a plasticizer, an anti-sagging agent,
Light stabilizers, anti-aging agents, antioxidants, UV absorbers, pigments, fragrances, solvents, etc. are used as necessary, but tin-based catalysts ordinarily added to modified silicone sealing materials that are not mastic-based. Is not used.

The dehydrating agent is used to remove invading water during storage of the sealing material of the present invention. For example, vinyltrimethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, methyltrimethoxysilane. Silane compounds such as methyltriethoxysilane, tetramethoxysilane, phenyltrimethylsilane, and diphenyldimethoxysilane; hydrolyzable ester compounds such as methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate. These may be used alone or in combination of two or more.

The above-mentioned filler is used for the purpose of reinforcing the sealing material of the present invention, and for example, calcium carbonate, magnesium carbonate, calcium oxide, hydrous silicic acid, silicic anhydride, finely divided silica, silicic acid. calcium,
Examples thereof include titanium dioxide, clay, talc, carbon black, glass balloons, and the like, which may be used alone or in combination of two or more kinds.

The above-mentioned plasticizer is used for increasing the elongation of the cured product of the sealing material of the present invention or for lowering the modulus. For example, phosphoric acid esters such as tributyl phosphate and tricresyl phosphate; dioctyl phthalate. Phthalates such as; glycerol monooleate esters such as fatty acid monobasic esters; dibutyl adipate,
Dibasic acid esters of fatty acids such as dioctyl adipate;
And polypropylene glycol, which may be used alone or in combination of two or more kinds.

The anti-sagging agent is used for preventing sagging of the sealing material of the present invention, and examples thereof include hydrogenated castor oil, fatty acid bisamide, fumed silica and the like.

The above-mentioned modified silicone mastic-based sealing material is a polymer whose main chain is essentially polyether and has a crosslinkable hydrolyzable silyl group at the molecular end, an amine compound, and, if necessary, a dehydrating agent. , Filler, plasticizer, anti-sagging agent, light stabilizer, anti-aging agent, antioxidant,
It can be obtained by mixing a predetermined amount of an ultraviolet absorber, a pigment, a fragrance, a solvent and the like, and kneading them with a roll, a planetary mixer or the like.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples and comparative examples of the present invention are shown below. The following materials were used in the following examples. -Polymer whose main chain is polyoxypropylene and has a dimethoxysilyl group at the molecular end Kanebuchi Chemical Co., Ltd., trade name "MS Polymer S-303" Asahi Glass Co., Ltd., trade name "Exester ESS-2420"
(Number average molecular weight 17,000, molecular weight distribution (weight average molecular weight / number average molecular weight) 1.4) -Amine compound manufactured by Toshiba Silicone Co., Ltd., trade name "TSL 8340" [N
-(2-Aminoethyl) -3-aminopropyltrimethoxysilane]

Dehydrating agent, manufactured by Toshiba Silicone, trade name "TSL 8310" (vinyl trimethoxysilane), plasticizer, manufactured by Mitsui Toatsu Chemicals, Inc., trade name "diol 2000" (polypropylene glycol)

Filler Shiraishi Kogyo Co., Ltd., trade name "CCR" (calcium carbonate) Light stabilizer Sankyo Co., trade name "Sanol LS770" Nippon Ciba Geigy Co., trade name "Tinubin 327"

(Examples 1 and 2) With the composition (unit: parts by weight) shown in Table 1, the above polymer and dried calcium carbonate were put into a planetary mixer and mixed, and then,
About 6 including plasticizer, amine compound, dehydrating agent and light stabilizer
A modified silicone mastic type sealing material was obtained by vacuum kneading for 0 minutes.

[0022]

[Table 1]

(Comparative Example 1) "SE909", a product of Toray Silicone Co., Ltd., which is a silicone mastic type sealing material in which unmodified silicone is used.
0 ”was used.

(Comparative Example 2) "Bond oily coke" manufactured by Konishi Co., Ltd. was used.

Performance Evaluation The sealing materials obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were evaluated for weather resistance and paintability as follows, and the results are shown in Table 1. -Weather resistance According to JIS A1415, the surface condition of the sunshine weatherometer for 1000 hours was visually observed. In addition, as a sample, a plate-like body having a thickness of 3 mm was prepared using the sealing material to be tested, and the temperature was 20 ° C.
The one cured for 2 weeks under the condition of relative humidity of 60% was used.
The criteria were as follows. ：: No problem. X: Many cracks were generated or whitening occurred.

-Paintability As a sample, a plate-like body having a thickness of 3 mm was prepared using the sealing material to be tested, and the temperature was 20 ° C and the relative humidity was 6
A solvent type acrylic paint was applied to the surface of the sample, which was aged for 2 weeks under the condition of 0%, and the applicability was tested. The criteria were as follows. ◯: Can be painted without problems. X: The paint does not repel when it is repelled.

[0027]

The structure of the modified silicone mastic-based sealing material of the present invention is as described above and has good weather resistance.
(EN) Provided is a mastic-based sealing material which can be applied with a coating material on a cured surface and is unlikely to be contaminated on the cured surface.

Claims (1)

[Claims] 1. A modification characterized in that (A) the main chain is essentially a polyether, and it comprises a polymer having a crosslinkable hydrolyzable silyl group at the molecular end and (B) an amine compound. Silicone mastic type sealing material.