JPH0770285A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a composition firmly adhensive to base materials even without primer treatment, capable of suppressing adhesion deterioration to a minimum when immersed in water, thus useful as an elastic sealant, comprising an oxyalkylene polymer and a silicone-modified product of a specific epoxy resin. CONSTITUTION:This curable composition comprises (A) an oxyalkylene polymer having OH or an Si atom-contg. group landed with a hydrolyzable group and crosslinkable by forming siloxane linkage and (B) a silicone-modified product of a hydrogenated bisphenol A-epichlorohydrin-type epoxy resin. It is preferable that the Si atom-contg. group be alkoxysilyl group, its main chain be oxypropylene polymer and the component B be a product modified by a silicon compound bearing hydrolyzable functional group at the Si atom [e.g. H2N(CH2)3 Si(OCH3)3].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly to a curable rubber composition having improved water resistant adhesion to a porous substrate.

[0002]

2. Description of the Related Art Heretofore, in the field of curable compositions, especially in the sealant field, it has been necessary to apply a primer in order to ensure sufficient adhesion between the substrate and the sealant. The application of such a primer requires an accurate selection of a primer suitable for various sealants and various base materials, and is a complicated task. Therefore, sealant performance that firmly adheres to the base material even without primer treatment. Has been requested. Various studies have been made so far on techniques for imparting adhesiveness to the sealant itself.
71 and Japanese Patent Publication No. 62-35421,
It has been proposed to add an amino group-containing hydrolyzable silicon compound or a reaction product of the compound and an epoxy compound. However, even by the techniques of these inventions, when the adherend is a porous substrate, water easily permeates through the pores, and therefore, especially when immersed in water, the water is easily absorbed from the interface. There was a problem that peeling occurred.

As one of the methods for improving the water-resistant adhesion as described above, a method of adding a silicon-modified epoxy resin as an active ingredient has been proposed, as shown in Japanese Patent Publication No. 62-28177. However, also by the technique of the present invention, in a curable composition containing a oxyalkylene polymer having a silicon atom-containing group to which a hydroxyl group or a hydrolyzable group is bonded as a base polymer, for example, modification of a bisphenol A-epichlorohydrin type epoxy resin is performed. However, there is a problem in that the compatibility with the oxyalkylene polymer is not good and that sufficient water-resistant adhesiveness cannot be obtained when the product is used.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a curable composition which adheres strongly to a substrate even without a primer treatment, and which minimizes the deterioration of adhesion even when immersed in water. .

[0005]

The present inventors have a silicon atom-containing group having a hydroxyl group or a hydrolyzable group bonded thereto (hereinafter referred to as "reactive silicon group"), and crosslink by forming a siloxane bond. In a method of adding a silicon-modified epoxy resin as an active ingredient in a possible oxyalkylene polymer, by using hydrogenated bisphenol A-epichlorohydrin type epoxy resin,
Improving the compatibility with the oxyalkylene polymer, and greatly improving the water-resistant adhesive strength as compared with the conventional one, not only to metal / glass / painted surface but also to porous substrates such as mortar / stone. The inventors have found the present invention and have reached the present invention.

That is, the present invention provides (a) an oxyalkylene polymer having a silicon atom-containing group to which a hydroxyl group or a hydrolyzable group is bonded and capable of being crosslinked by forming a siloxane bond, and (b) water. The present invention relates to a curable composition containing a silicon modified product of an added bisphenol A-epichlorohydrin type epoxy resin.

As the oxyalkylene polymer used in the present invention, those having a number average molecular weight of 500 to 50,000 can be used, and those having a number average molecular weight of 3,000 to 30,000 are particularly preferable. The structural units constituting the main chain of the polymer, for _{example, -CH 2 O -, - CH} 2 CH 2 O -, - C
_{H (CH 3) CH 2 O} -, - CH (C 2 H 5) CH 2 O
_{-, - CH 2 CH 2 CH} 2 CH 2 O- and the like specifically. The molecular chain of the oxyalkylene polymer may consist of only one kind of these structural units, or 2
It may be composed of more than one kind, but oxypropylene is particularly preferable.

Specific examples of the polymer are disclosed in JP-A-50-
156599, 51-73561, 54-609.
6, the same 55-82123, the same 55-123620, the same 5
5-125121, 53-131022, 55-1
No. 35135, No. 55-137129 and the like are proposed, and JP-A No. 61-1976.
31, the same 61-215622, the same 61-215623,
The number average molecular weights of 6,000 or more and Mw / Mn of 1.6 or less, which are disclosed in the respective publications such as 61-218632.
It is also possible to use an oxyalkylene polymer having a high molecular weight and a narrow molecular weight distribution.

Examples of the hydrolyzable group bonded to a silicon atom include an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group and an alkenyloxy group. . Among these, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an aminooxy group, a mercapto group, and an alkenyloxy group are preferable, but from the viewpoint of mild hydrolyzability and easy handling, an alkoxy group such as a methoxy group is preferable. Groups are particularly preferred.

In the present invention, hydrogenated bisphenol A-
A silicon-modified product of an epichlorohydrin type epoxy resin can react with a hydrogenated bisphenol A-epichlorohydrin type epoxy resin having an average of two or more epoxy functional groups in one molecule, and the epoxy group. It is a reaction product of a silicon compound having a functional group, and can effectively act on the water-resistant adhesion between the curable composition and the porous substrate. Here, as the silicon compound capable of reacting with the epoxy resin, a silicon compound having an amino group, a mercapto group, a carboxylic acid group or the like is used, and a silicon compound containing an amino group is particularly effective.

The silicon compound has a hydrolyzable functional group on the silicon atom, and examples of the hydrolyzable functional group include an alkoxy group, an acyloxy group, a ketoximate group, an amino group and an aminooxy group. , Amide group, alkenyloxy group, etc., but alkoxy group is particularly preferable. As the silicon compound having the hydrolyzable functional group on the silicon atom, specifically, H ₂ N (C
_{H 2) 3 Si (OCH 3} ) 3, H 2 N (CH 2) 2 NH
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₃
Si (OC ₂ H ₅ ) ₃ , H ₂ N (CH ₂ ) ₂ NH (CH
₂ ) ₃ Si (OC ₂ H ₅ ) ₃ , HS (CH ₂ ) ₃ Si
(OCH ₃ ) ₃ , HO ₂ C (CH ₂ ) ₃ Si (OC
H ₃ ) ₃ and the like can be exemplified, but the present invention is not limited thereto.

The modification of the hydrogenated bisphenol A-epichlorohydrin type epoxy resin with the silicone compound capable of reacting with the epoxy functional group is 0 in terms of an equivalent ratio of the functional group capable of reacting with the epoxy functional group to the epoxy functional group. 1 to 4.
It can be performed at a ratio of 0, but a range of 1.0 to 2.0 is preferable. The epoxy equivalent of the epoxy resin is 150.
It is desirable that it is ˜300.

The reaction may be carried out without solvent or in a solvent. The reaction condition is room temperature to 10 under anhydrous condition.
It is desirable to carry out at 0 ° C. for 30 minutes to 3 hours. The silicon-modified product of the hydrogenated bisphenol A-epichlorohydrin type epoxy resin has a reactive silicon group, and is 0. 0% based on 100 parts by weight of an oxyalkylene polymer which can be crosslinked by forming a siloxane bond. It is desirable to use 1 to 30 parts by weight. This is because if the amount is less than 0.1 parts by weight, the expected adhesiveness is difficult to develop, and if it exceeds 30 parts by weight, the rubber elasticity of the cured product is adversely affected.

Further, in the composition of the present invention, various hydrolyzable silicon compounds can be used for the purpose of adjusting physical properties, reinforcing adhesion, and the like. As a specific example, H ₂ N (C
_{H 2) 3 Si (OCH 3} ) 3, H 2 N (CH 2) 2 NH
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂
NH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ , (C
₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ , H ₂ N (CH ₂ ) ₂
Amino group-substituted alkoxysilane such as NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ and CH ₂ (O) CHCH ₂ O
(CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

[0015]

[Chemical 1]

CH ₂ = C (CH ₃ ) COO (C ₃ H ₆ ).
Si (OCH ₃ ) ₃ , CH ₂ = CHSi (OC
_{H 3) 3, HSC 3 H} 6 Si (OCH 3) 3, silane compound and the like. Further, the above-mentioned amino group-substituted alkoxysilane and CH ₂ (O) CHCH ₂ O (CH ₂ ) ₃ S
i (OCH ₃ ) ₃ or a reaction product with an epoxysilane compound as shown in the above chemical formula 1, or CH ₂ ═C (CH ₃ ) CO
O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CH ₂ ═C (CH
₃ ) COO (CH ₂ ) ₃ Si (OCH ₂ CH ₂ OC
A reaction product with a methacryloylsilane compound such as H ₃ ) ₃ may be mentioned. The reaction between the amino group-substituted alkoxysilane and the epoxysilane compound or the methacryloylsilane compound is carried out by reacting 1 mol of the amino group-substituted alkoxysilane with
It can be easily obtained by mixing 0.2 to 5 mol of the silane compound and stirring the mixture at room temperature or 180 ° C. for 1 to 8 hours.

The above-mentioned amino group-substituted alkoxysilane, or
The amino group-substituted alkoxysilane derivative compound is preferably used in the range of 20 parts by weight or less with respect to 100 parts by weight of the oxyalkylene polymer having a reactive silicon group. This is because if it exceeds 20 parts by weight, the physical properties of the rubber after curing are adversely affected. In curing the polymer of the present invention, a silanol condensation catalyst (curing catalyst) is used. When the silanol condensation catalyst is used, conventionally known ones can be widely used. Specific examples thereof include titanic acid esters such as tetrabutyl titanate and tetotapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; dibutyltin oxide and phthalate ester. Reaction product; dibutyltin diacetylacetonate; amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, or salts of these amine compounds with carboxylic acid; excess polyamine and polyamine Low molecular weight polyamide resin obtained from basic acid; reaction product of excess polyamine and epoxy compound; γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)
Examples thereof include silanol condensation catalysts such as silane coupling agents having an amino group such as aminopropylmethyldimethoxysilane; and known silanol condensation catalysts such as other acidic catalysts and basic catalysts. These catalysts
They may be used alone or in combination of two or more.

The amount of these silanol condensation catalysts used is
Oxyalkylene-based polymer having reactive silicon group 10
The amount is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 0 parts by weight. If the amount of the silanol condensation catalyst used is too small with respect to the oxyalkylene polymer, the curing rate will be slow and the curing reaction will not proceed sufficiently, which is not preferable. On the other hand, if the amount of the silanol condensation catalyst used is too large with respect to the oxyalkylene polymer, local heat generation and foaming will occur during curing, which makes it difficult to obtain a good cured product, which is not preferable.

The composition of the present invention may further contain various fillers, plasticizers, additives and the like, if necessary.
As the filler, reinforcing fillers such as fume silica, precipitated silica, silicic acid anhydride and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth,
Calcined clay, clay, kaolin, talc, titanium oxide,
Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil, silas balloons and glass balloons; fibrous fillers such as asbestos, glass fibers and filaments are exemplified. .
These fillers can be used in an amount of about 3 to 300 parts by weight based on 100 parts by weight of the oxyalkylene polymer having a reactive silicon group.

As the plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate and butyl benzyl phthalate; epoxy plasticizers such as epoxidized soybean oil, epoxidized linseed oil and benzyl epoxy stearate; polyesters such as polyesters of dibasic acids and dihydric alcohols Plasticizers; polyethers such as polypropylene glycol and its derivatives; polystyrenes such as poly-α-methylstyrene and polystyrene; polybutadiene, butadiene-acrylonitrile copolymers, polychloroprene, polyisoprene, polybutene, chlorinated paraffins, etc. The plasticizer of the single or 2
It can be optionally used in the form of a mixture of more than one kind. The amount of the plasticizer is 100 parts by weight of the oxyalkylene polymer,
When used in the range of 0 to 100 parts by weight, favorable results are obtained.

Other additives include dehydrating agents,
Storage stability improver, ultraviolet absorber, metal deactivator, ozone deterioration inhibitor, light stabilizer, amine radical chain inhibitor, phosphorus peroxide decomposer, anti-sagging agent, colorant, anti-aging agent, etc. Can be used as needed. The composition obtained as described above can be applied not only to a two-pack type curing composition but also to a one-pack type curing composition. In the latter case, the composition of the present invention is obtained by preparing the composition of the present invention in a substantially water-free state, and can be stored for a long time if stored in a closed state, and can be rapidly cured from the surface when exposed to the atmosphere. Start.

According to the present invention, a curable composition having excellent water-resistant adhesion to not only metal, glass and painted surfaces but also porous substrates such as mortar and stone is obtained. , The adherend is not only metal, glass, painted surface, but also mortar, concrete, lightweight foam concrete,
When joining the same type of material, such as stone,
And, it is highly useful in joining these dissimilar materials.

The composition of the present invention is useful as an elastic sealing material in the fields of construction, civil engineering, etc., and can also be used as a paint, an adhesive, an injecting agent, and a coating material.

[0024]

EXAMPLES Hereinafter, the composition of the present invention will be described in more detail with reference to Examples. Reference Example 1 Epolite 4000 (hydrogenated bisphenol A diglycidyl ether, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) was added with 1.0 equivalent of A-1100 (γ-aminopropyltriethoxysilane, Nippon Unicar) based on the epoxy group thereof. In addition, N
_The mixture was stirred at 70 ° C. for 2 hours under ₂ seals. It was confirmed by infrared absorption spectrum that the peak derived from the epoxy group had decreased, and a silicon-modified product of hydrogenated bisphenol A-epichlorhydrin type epoxy resin was obtained.

Examples 1 and 2 Oxypropylene polymer having a number average molecular weight of 8000 and containing a methyldimethoxysilyl group at 80% of all terminals 10.
0 parts by weight of surface-treated calcium carbonate colloid (average particle size
0.08 μm) 120 parts by weight, dioctyl phthalate
55 parts by weight, titanium oxide 20 parts by weight, hydrogenated castor oil
2 parts by weight, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 3 parts by weight, and dibutyltin diacetylacetonate 3 parts by weight, and further the hydrogenated bisphenol A-epichlorich obtained in Reference Example 1. The silicone modified product of the drin type epoxy resin was added in the number of parts by weight shown in Table 1 and kneaded in a substantially water-free state. The curable composition obtained as described above was applied in a bead shape on the adherend shown in Table 1. Then, it was left to stand at room temperature for 7 days for curing (curing), and then immersed in 50 ° C. water for 7 days.
A hand peeling test was performed on the test pieces after curing and water immersion to test the adhesiveness.

Comparative Examples 1 and 2 Instead of the silicon modified product of the hydrogenated bisphenol A-epichlorohydrin type epoxy resin of Example 1, Epicoat 828 (bisphenol A-epichlorohydrin type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) and A- 1100
Was added in the same manner as in Reference Example 1 by adding a silicon modified product of a bisphenol A-epichlorohydrin type epoxy resin in the number of parts shown in Table 1.

Comparative Example 3 Instead of the hydrogenated bisphenol A-epichlorhydrin type epoxy resin of Example 1, which was modified with silicon, Epolite 4000 and A-1100 were added individually.
The results are shown in Table 1.

[0028]

[Table 1]

In Table 1, CF and AF are cohesive failure and interface failure, respectively.
Indicates. From Table 1, it can be seen that the composition of the present invention has good water-resistant adhesion even on porous substrates such as mortar and slate.

Claims (4)

[Claims] 1. An oxyalkylene polymer having (a) a silicon atom-containing group to which a hydroxyl group or a hydrolyzable group is bonded and which can be crosslinked by forming a siloxane bond, and (b) hydrogenated bisphenol A-. A curable composition containing a silicon modified product of an epichlorohydrin type epoxy resin. 2. The composition according to claim 1, wherein the silicon atom-containing group to which a hydroxyl group or a hydrolyzable group in (a) is bonded is an alkoxysilyl group. 3. The composition according to claim 1, wherein the main chain of (a) is an oxypropylene polymer. 4. The composition according to claim 1, wherein (b) is a modified product of a silicon compound having a hydrolyzable functional group on a silicon atom.