JP2002241684A - Polyisobutylene-based primer composition for sealant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyisobutylene-based primer composition for sealant capable of exhibiting sufficiently satisfactory adhesive primer performances even to executed members especially having a porous surface. SOLUTION: This polyisobutylene-based primer composition for sealant comprises a solid epoxy resin and an alkyl alkoxysilane as primer ingredients. Preferably, an amino alkoxysilane is formulated as a curing agent of the solid epoxy resin and one or more compounds selected from the group consisting of an organopolysiloxane resin containing hydroxyl group or an alkoxyl group bonded with Si, an isobutylene-based polymer containing hydrolyzable silyl group and a silicate compound are added as the third primer ingredient. The solid epoxy resin is in an amount of 1-50 wt.% and the alkyl alkoxysilane is in an amount of 0.01-25 wt.% based on the total amount of the primer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition for a polyisobutylene-based sealing material, and more particularly, to a polyisobutylene-based sealing material containing a hydrolyzable silyl group-containing isobutylene-based polymer as a building sealing material as a main component. And a primer composition containing a solid epoxy resin and an alkylalkoxysilane as a primer component and capable of exhibiting a sufficiently satisfactory adhesive primer performance even on a workpiece having a porous surface.

[0002]

2. Description of the Related Art Conventionally, silicone-based sealing materials have been used as architectural sealing materials, in particular, because of their excellent durability and weather resistance. Polyisobutylene-based sealing materials have been attracting attention as those having the following. By the way, in general, primers for building sealing materials are roughly divided into silane primers and urethane resin primers. In particular, in the construction of the periphery of the window glass, the effect of ultraviolet rays near the bonding interface can be considered, so that the primer is required to have high weather resistance. For this reason, at present, a silane-based primer containing a silicone-based compound having excellent weather resistance as a main component is used (see JP-A-2-219885). However, when a polyisobutylene-based sealing material is used instead of the above-mentioned silicone-based sealing material, in such a silane-based primer, the silicone compound has a different polarity from that of the polyisobutylene-based sealing material. I can't get it.

[0003] On the other hand, when the member to be processed has a porous surface, even if various kinds of painted surfaces or primers for window glass are applied, the ability to prevent permeation of the porous surface and water permeation to the bonding interface is not achieved. Since it is low, a primer dedicated to the porous surface is required separately. Therefore, if the types of members to be processed are different, it is necessary to apply different types of primers separately at joints where these members are to be joined, and it is inevitable that the process of the process is difficult.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
After diligent studies to provide general-purpose primers that can contribute to good adhesion (including adhesion weather resistance) to window glass, painted surfaces and porous members,
The present inventors have found that if two specific primer components are used in combination, they can be used as intended general-purpose primers, and have completed the present invention. That is, the present invention provides a primer composition for a polyisobutylene-based sealing material, which comprises a solid epoxy resin and an alkylalkoxysilane as primer components.

In the present invention, the above-mentioned solid epoxy resin refers to an epoxy resin which exhibits a film-forming property when applied in a solution state within a temperature range of use environment of a primer, and which is solid at a temperature of, for example, 60 ° C. or lower. Specific examples include bisphenol A type and bisphenol F type, and usually have a molecular weight of 400 to 6000 and an epoxy equivalent of 400 to 600.
It is about 0, and there is no limitation on the type.

In the present invention, when a solid epoxy resin is used, as a curing agent thereof, an aminoalkoxysilane such as γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (α-aminoethyl) aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, N-
(Β-aminoethyl) -γ-aminopropyltrimethoxysilane, ureidopropyltriethoxysilane, N-
Normally, (n-butyl) -γ-aminopropyltrimethoxysilane, N- (cyclohexyl) -γ-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, etc. are mixed with the solution of the solid epoxy resin immediately before use. , A so-called two-pack type. The amount to be used may be usually selected in the range of 1 to 50 parts, preferably 5 to 40 parts with respect to 100 parts (parts by weight, hereinafter the same) of the solid epoxy resin. If the amount is less than 1 part, curing is insufficient and a sufficient coating film cannot be formed, and if it exceeds 50 parts, the curing is insufficient and only a brittle coating film can be formed, and sufficient adhesive water resistance cannot be obtained. It is in. On the other hand, in order to form a one-pack type, a ketone block of the amino group of the aminoalkoxysilane, that is, the amino group is converted to a carbonyl compound (ketone compound, aldehyde compound, dicarbonyl compound, etc.)
Can be used. For example, N- (1,
3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is commercially available.

In the present invention, the alkylalkoxysilanes include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane And the like.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The primer composition for a polyisobutylene-based sealing material according to the present invention is characterized by containing the above-mentioned solid epoxy resin and alkylalkoxysilane as primer components. It is composed of a system dissolved in an organic solvent. Here, the amount of each primer component is usually 1 to 50% (wt%, the same applies hereinafter), preferably 3 to 40%, and 0.01 to 25% of alkylalkoxysilane in the total amount of the primer composition. %, Preferably 1 to 15%. 1% solid epoxy resin
If it is less than 50%, the adhesiveness after immersion in water is insufficient.
%, The primer tends to be difficult to apply. When the amount of the alkylalkoxysilane is less than 0.01%, the adhesion to the polyisobutylene-based sealing material is weak, and when it exceeds 25%, the adhesion to the porous member or the metal member tends to be weak.

Examples of the catalyst include tin catalysts such as tin dioctylate, dibutyltin dilaurate, dibutyltin bisacetylacetonate, dibutyltin diacetate, dibutyltin diethylhexanoate, dibutyltin dioctate, dibutyltin oxide, and dioctyltin oxide. Titanium-based catalysts such as isopropyl titanate, tetra n-butyl titanate and partially hydrolyzed condensates thereof, titanium diisopropyl bisacetyl acetate, titanium diisopropyl bisethyl ethyl acetoacetate, and the like. Usually, the amount of the catalyst may be selected in the range of 0.01 to 10% of the total amount of the primer composition.

Examples of the organic solvent include toluene, xylene, methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, ligroin, ethyl acetate, tetrahydrofuran, n
-Hexane, heptane and the like.

If necessary, a third primer component may be an organopolysiloxane resin containing a hydroxyl group or an alkoxy group bonded to a silicon atom (hereinafter simply referred to as an organopolysiloxane resin), or an isobutylene resin containing a hydrolyzable silyl group. At least one selected from the group consisting of a polymer (hereinafter simply referred to as an isobutylene-based polymer) and a silicate compound, or two or more, preferably three may be added in an appropriate amount range.

The above-mentioned organopolysiloxane resin has, for example, an average unit of the formula:

Embedded image [In the formula, R ¹ is a monovalent hydrocarbon group (e.g. methyl, ethyl, alkyl groups such as propyl; those substituted with and halogen or cyano group these hydrogen atoms; vinyl, alkenyl groups such as allyl); R ² Is a hydrogen atom or an alkyl group (methyl, ethyl, propyl, etc.);
1.8; and b is a value such that the number of hydroxyl groups or alkoxy groups bonded to silicon atoms in one molecule is one or more], and is usually 0.8 to 0.8 per silicon atom. Hydrochloride or a mixture of two or more chlorosilanes or alkoxysilanes each having ~ 1.8 monovalent hydrocarbon groups is hydrolyzed in water or a mixture of water and an organic solvent to produce hydrochloric acid, alcohol, and the like as a by-product. It can be manufactured by removing. Particularly, a hydroxyl group-containing organopolysiloxane resin is desirable.

The above-mentioned isobutylene-based polymer means that the main chain skeleton is composed of at least an isobutylene unit [If necessary, in addition to the isobutylene unit, a monomer copolymerizable with isobutylene (for example, an olefin having 4 to 12 carbon atoms, vinyl ether) , Aromatic vinyl compounds, vinylsilanes,
Allyl silanes)],
Hydrolyzable silyl groups at both ends of the molecule, for example of the formula:

Embedded image [Wherein R and R ′ are the same or different and each have 1 to 1 carbon atoms.
A lower alkyl of 5; and c is an integer of 1 to 3], and preferably has a molecular weight of 100
A wax having a viscosity of from 0 to 40,000 at room temperature or a high-viscosity liquid is generally referred to as a terminal-functional isobutylene-based polymer obtained by a cationic polymerization method called an inifer method.
No. 31758). As a typical commercial product, the formula

Embedded image [Wherein n is 5-400 and m is 5-400]
"Epion" series manufactured by Kanegafuchi Chemical Industry Co., Ltd. having the chemical structure of

Examples of the above silicate compound include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane; and ethyl polysilicate, propyl polysilicate, butyl polysilicate, methyl cellosolve orthosilicate, n-propyl orthosilicate, tetramethylsilicate and the like. Silicates. Further, if necessary, appropriate amounts of ordinary inorganic fillers (such as fumed silica and colloidal silica) and coloring agents (such as red iron oxide, titanium oxide, carbon black, and dye) may be added.

[0015]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Example 1 and Comparative Examples 1 to 4 (1) Preparation of Primer Composition The components of the number of parts shown in Table 1 below are blended and stirred and mixed to obtain a primer composition. (2) Adhesion test The primer composition of (1) above was applied to various members to be processed shown in Table 2 below with a brush, dried at room temperature, and then subjected to a two-component polyisobutylene-based sealing material (Sunstar Giken Co., Ltd. )
"Penguin Seal 7000") was applied to a thickness of 10 mm, and then cured and cured at 23 ° C. and 50% RH × 7 days. Next, the adhesion of the sealing material is evaluated (simple adhesion test based on JAS S8). The results are also shown in Table 2.

：: Complete adhesion △: Partial peeling between primer and member to be processed ×: Fully peeling between primer and member to be processed ▲: Peeling between sealing material and primer 50% RH x 7
The adhesiveness was evaluated for those cured and cured for 5 days or those immersed in warm water at 50 ° C. for 7 days.

[0017]

[Table 1] In Table 1, Note 1) Bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd.
Epoxy resin, "Epicoat 1007", molecular weight 29
00, epoxy equivalent 1750-2200 Note 2) Bisphenol A type liquid epoxy resin manufactured by the company
"Epicoat 828", molecular weight 380, epoxy equivalent 1
84-194 Note 3) i-butyltrimethoxysilane Note 4) N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine Note 5) Co-polymerization of methyl methacrylate and vinyl acetate Coalescing resin

[0018]

[Table 2]

Example 2 (1) Preparation of primer composition (two-pack type) A main component and a hardener component each having the following composition (parts) are obtained. Main agent component unit solid epoxy resin 10 tetra n- butyl titanate 0.5 dibutyltin bisacetylacetonate 0.5 Toluene 39 Total 50 hardener component part alkylalkoxysilane 2 hydroxyl group-containing organopolysiloxane resin 1.5 isobutylene polymer 1.5 Ethyl polysilicate 5 γ- (2-aminoethyl) aminopropyltrimethoxysilane 4 Toluene 34 Isopropyl alcohol 2 Total 50

(2) Adhesion test The main component / hardener component was mixed at a ratio of 1: 1 and applied to seven types of workpieces in the same manner as in Example 1. Excellent adhesion primer performance was obtained.

[0021]

According to the results shown in Table 2, the present invention (Example 1)
It can be recognized that excellent adhesiveness (including adhesive water resistance) can be exerted not only on various types of coated aluminum but also on a mortar plate having a porous structure. The primer composition of the present invention is useful mainly for application to a polyisobutylene-based sealing material for architectural use, but in addition to this, other sealing materials, further various adhesives, paints, It goes without saying that it can also be used as a primer for coating materials and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J038 CB112 DB061 DL022 DL032 DL052 GA02 GA03 GA15 JC35 KA03 NA03 NA04 NA10 PB05 PC02 PC03 PC04

Claims (6)

[Claims] 1. A primer composition for a polyisobutylene-based sealing material comprising a solid epoxy resin and an alkylalkoxysilane as primer components. 2. The primer composition according to claim 1, wherein an aminoalkoxysilane is blended as a curing agent for the solid epoxy resin. 3. The primer composition according to claim 2, wherein the curing agent is a one-part type using a ketone block of an amino group of aminoalkoxysilane. 4. The primer composition according to claim 2, wherein the primer composition is a two-pack type comprising a main component containing a solid epoxy resin and a curing agent component containing aminoalkoxysila and alkylalkoxysilane. 5. As a third primer component, at least one selected from the group consisting of a hydroxyl group- or alkoxy group-containing organopolysiloxane resin bonded to a silicon atom, a hydrolyzable silyl group-containing isobutylene-based polymer, and a silicate compound is added. The primer composition according to any one of claims 1 to 4. 6. The primer composition according to claim 1, wherein 1 to 50% by weight of a solid epoxy resin and 0.01 to 25% by weight of an alkylalkoxysilane are contained in the total amount of the primer composition.