JPH0796606B2 - Method for producing curable composition - Google Patents

Description

The present invention relates to a rubber-based organic polymer containing at least one reactive silicon group in a molecule, a hexahydrophthalic acid diglycidyl ester compound and an epoxy group. The present invention relates to a method for producing a curable composition containing a silicon compound containing a reactive functional group and a reactive silicon group in the molecule, which gives a cured product having improved toughness and strength.

[Prior Art] A rubber-based organic polymer having a reactive silicon group has an interesting property that it cures at room temperature to become a rubber elastic body, but usually has a weak point that the strength of a cured product is small. Have and have limited uses.

[Problems to be Solved by the Invention] The present invention has been made to improve the insufficient strength of the cured product of the rubber-based organic polymer having a reactive silicon group as described above.

[Means for Solving Problems] According to the present invention, a silicon compound containing a functional group capable of reacting with an epoxy group and a reactive silicon group in a molecule is used as a rubber-based organic polymer having a reactive silicon group. It was found that when added to a system composed of a hexahydrophthalic acid diglycidyl ester compound and cured, the drawback of insufficient strength of a rubber-based organic polymer cured product having a reactive silicon group can be greatly improved. (A) rubber organic polymer having at least one reactive silicon group in the molecule (B) hexahydrophthalic acid diglycidyl ester compound (C) capable of reacting with an epoxy group The present invention relates to a process for producing a curable composition, which comprises blending a silicon compound containing a functional group and a reactive silicon group in the molecule and (D) a silanol condensation catalyst. .

[Examples] Examples of the polymer forming the skeleton of the rubber-based organic polymer having at least one reactive silicon group in the molecule which is the component (A) used in the present invention include propylene oxide, ethylene oxide and tetrahydrofuran. Polyether polymers obtained by polymerization of cyclic ethers such as; polyester polymers obtained by condensation of dibasic acids such as adipic acid with glycols or ring-opening polymerization of lactones; ethylene-propylene copolymers; Polyisobutylene or a copolymer of isobutylene and isoprene; polychloroprene; a copolymer of polyisoprene or isoprene and butadiene, styrene, acrylonitrile, etc .;
Polybutadiene or a copolymer of butadiene and styrene, acrylonitrile, etc .; Polyisoprene, a polyolefin-based polymer obtained by hydrogenating a copolymer of polybutadiene or isoprene and butadiene; radical polymerization of monomers such as ethyl acrylate and butyl acrylate Polyacrylic acid ester obtained or a copolymer of the acrylic acid ester with vinyl acetate, acrylonitrile, styrene, ethylene or the like; obtained by polymerizing a vinyl monomer in the presence of the rubber organic polymer used in the present invention Graft polymers; polysulfide polymers and the like. Among these, general formulas such as polypropylene oxide-based polyethers: -RO-
(In the formula, R represents a divalent alkylene group having 2 to 4 carbon atoms) In the presence of a polyether having a repeating unit represented by the formula, a polyether such as polypropylene oxide, acrylate, styrene, acrylonitrile, vinyl acetate A polymer or copolymer such as a graft polymer obtained by polymerizing a vinyl monomer such as is compatible with the hexahydrophthalic acid glycidyl ester compound which is the component (B) and has a reactive silicon group. It is preferable in that it can be easily introduced at the molecular end and a liquid polymer can be easily produced without using a solvent. Furthermore, it has good water resistance, is inexpensive,
Polypropylene oxide is particularly preferable because it is easy to handle as a liquid.

Examples of the reactive silicon group contained in the rubber-based organic polymer include a hydrolyzable silicon group and a silanol group.

The hydrolyzable silicon group referred to in the present specification means a group in which a hydrolyzable group that is hydrolyzed by moisture in the presence or absence of a silanol condensation catalyst is bonded to a silicon atom. Specific examples of the functional group include commonly used groups such as hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amido group, aminooxy group, mercapto group and alkenyloxy group. . Of these, alkoxy groups are particularly preferable because they have mild hydrolyzability and are easy to handle. The hydrolyzable group may be bonded to one silicon atom in the range of 1 to 3.

The number of silicon atoms forming the hydrolyzable silicon group may be one or two or more, but in the case of silicon atoms connected by a siloxane bond or the like, the number is up to 20. Is preferred.

Examples of the method of introducing the hydrolyzable silicon group into the rubber-based organic polymer include the following methods.

(1) Ethylene, a monomer having a copolymerizable unsaturated group and a hydrolyzable silicon group in its molecule, such as vinyltrialkoxysilane, methacryloyloxypropylmethyldialkoxysilane and methacryloyloxypropyltrialkoxysilane, is used. Copolymerize with polymerizable monomers such as propylene, isobutylene, chloroprene, isoprene, butadiene, acrylic ester,
Copolymerization of a monomer having a copolymerizable epoxy group such as γ-glycidoxypropyltrimethoxysilane and γ-glycidoxypropylmethyldimethoxysilane with a hydrolyzable silicon group in the molecule with propylene oxide or ethylene oxide. How to make.

By these methods, a hydrolyzable silicon group can be introduced into the side chain of the molecule.

(2) A chain of silicon compounds having a hydrolyzable silicon group and a mercapto group such as mercaptopropyltrialkoxysilane and mercaptopropylmethyldialkoxysilane capable of causing a chain transfer reaction in radical polymerization and a hydrolyzable silicon group in the molecule. A method of polymerizing a radically polymerizable monomer by using it as a transfer agent.

(3) Radical-polymerizable monomer using an azo-based or peroxide-based polymerization initiator containing a hydrolyzable silicon group such as azobis-2- (6-methyldiethoxysilyl-2-cyanohexane) A method of polymerizing.

In the methods (2) and (3), a hydrolyzable silicon group is introduced at the polymer molecule terminal.

(4) A hydroxyl group on the side chain and / or terminal of the polymer,
A polymer having a functional group such as a carboxyl group, a mercapto group, an epoxy group, an isocyanate group (hereinafter referred to as a Y functional group) is used, and a Y ′ functional group capable of reacting with the Y functional group is contained in the molecule, A method of reacting a silicon compound having a hydrolyzable silicon group with a Y functional group.

Specific reaction examples are shown in the following table, but not limited thereto.

In particular, as a polymer having a Y functional group used as a starting material and an intermediate material in the table, a main chain such as polypropylene polyol, oriethylene polyol, polytetramethylene diol, etc. is essentially represented by the general formula:-
Polyether polyols comprising a repeating unit represented by R-O- (wherein R represents a divalent alkylene group having 2 to 4 carbon atoms); a condensation of a dibasic acid such as adipic acid with a glycol or a lactone. Polyols obtained by ring-opening polymerization of polyisobutylene; polyisobutylene polyols or polycarboxylic acids; polybutadiene or copolymers of butadiene with styrene, acrylonitrile, etc., or polycarboxylic acids; hydrogenated polyisoprene or polybutadiene Obtained polyols of polyolefins; Isocyanate functional group-containing polymers obtained by reacting the polyols or polycarboxylic acids with polyisocyanates; Reacting the polyols with vinyl type unsaturated group-containing halogen compounds, etc. Binni Is particularly preferable, type unsaturated group-containing the polymer compound, further Y functional group is more preferable in the polymer molecular terminal. Further, the polyols may be those whose molecular weight is increased by a polyfunctional compound such as a polyvalent halide.

The silicon compound having the Y ′ functional group is N-β.
Amino group-containing silanes such as-(aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane and γ-aminopropyltriethoxysilane; γ-
Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane; γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl)
Epoxysilanes such as ethyltrimethoxysilane; vinyl type unsaturated group-containing silanes such as vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-acryloyloxypropylmethyldimethoxysilane; γ-chloro Chlorine atom-containing silanes such as propyltrimethoxysilane; γ-
Isocyanate-containing silanes such as isocyanatopropyltriethoxysilane and γ-isocyanatopropylmethyldimethoxysilane; hydrosilanes such as methyldimethoxysilane, trimethoxysilane, and methyldiethoxysilane can be specifically exemplified. However, the present invention is not limited to these.

In the combination of a polymer having a Y functional group and a silicon compound having a Y ′ functional group, particularly, (i) a polymer having an isocyanate group and an amino group-containing silane or a mercapto group-containing silane In addition, a combination of (ii) a vinyl-type unsaturated group-containing polymer and hydrosilanes is preferable. Further, in (ii), a combination of polypropylene oxide having an allyl ether group at the molecular end and hydrosilanes is particularly preferable. In (ii), a vinyl group and a hydrosilyl group may be reacted with each other by a hydrosilylation reaction using a platinum compound as a catalyst to introduce a silyl group into the polymer.

At least 1 in the molecule which is the component (A) used in the present invention
The rubber-based organic polymer having one, preferably 1.2 to 6 reactive silicon groups has a molecular weight of about 500 to 50,000, and is particularly preferably about 1000 to 20,000 from the viewpoint of easy handling. If the number of reactive silicon groups contained in the molecule is less than 1, the curing effect will be insufficient and the modifying effect will be unclear.

In the present invention, a silanol group can be preferably used as the reactive silicon group in addition to the hydrolyzable silicon group, but the silanol group can also be obtained by hydrolyzing the hydrolyzable silicon group.

In the rubber-based organic polymer having at least one reactive silicon group in the molecule used in the present invention, the reactive silicon group is preferably present at the molecular end. When a reactive silicon group is present at the terminal of the molecule, the amount of effective network chains of the component (A) contained in the cured product to be formed is large, so rubber elasticity is likely to be effectively exhibited, and therefore a high strength product is obtained. It is easy to get it.

Specific examples of the component (A) as described above include, for example, JP-B-45-36319, JP-B-46-12154, JP-B-49-32673, and JP-A-Sho.
50-156599, 51-73561, 54-6096, 55-13767
No. 54-13768, No. 55-82123, No. 55-123620, No. 5
5-125121, 55-131021, 55-131022, 55-135
No. 135, No. 55-137129, No. 57-179210, No. 58-191703
Issue 59-78220, Issue 59-78221, Issue 59-78222, Issue 59
-78223, 59-152923, 59-168014, etc. are mentioned, and these can be used effectively, but are not limited to these.

Examples of the hexahydrophthalic acid diglycidyl ester compound used as component (B) in the present invention include compounds represented by the following formulas (1) to (3).

When these components (B) are used, the compatibility of the components (A), (B) and (C) becomes very good. In particular, when the component (A) is a polyrate-based polymer having a reactive silicon group, the compatibility becomes good. For example, when the composition of the present invention is used as an adhesive, peeling and shearing are caused due to good compatibility. Both strengths are good.

On the other hand, the component (B) is not used at all, and other epoxy resins such as the most general-purpose epichlorohydrin-
When the bisphenol A type epoxy resin is used, the compatibility with other components (A) and (C) is not always sufficient, and when it is used as an adhesive, the peel strength is smaller than in the case of the present invention. In particular, in the case of (A) component / (B) component = 100/75 to 100/125 (weight ratio), this effect is remarkable.

Among the above-mentioned components (B), hexahydrophthalic acid diglycidyl ester represented by the formula (1) is particularly preferable.

When using the component (B), if necessary, an epoxy resin or an epoxy compound (component (E)) other than the component (B) may be used in combination. Specific examples of such component (E) include, for example, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, water. Bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, glycidyl ester type epoxy resin such as diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, m- Aminophenol epoxy resin,
Diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, etc. Examples include polyglycidyl ethers of polyhydric alcohols, hydantoin type epoxy resins, epoxidized unsaturated polymers such as petroleum resins, and the like.

In the present invention, it goes without saying that a curing agent may be used in combination to cure the component (B) and optionally the component (E) used. As the epoxy resin curing agent that can be used, a generally used curing agent for epoxy resin can be used. As such a curing agent,
For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris (dimethyl). Amines such as aminomethyl) phenol; tertiary amine salts; polyamide resins; imidazoles; dicyandiamides; boron trifluoride ternary compounds; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylene Examples thereof include compounds such as carboxylic anhydrides such as tetrahydrophthalic anhydride, dodecenyl succinic anhydride, pyromellitic anhydride, and chlorenic anhydride; alcohols; phenols; carboxylic acids. , But is not limited to these.

When the above-mentioned curing agent is used, its amount varies depending on the types of the epoxy resin and the curing agent, but it is 100 parts by weight of the component (B) or ((B) component + (E) component) (the same applies hereinafter). On the other hand, the curing agent may be used in the range of 0.1 to 300 parts depending on the purpose.

In the present invention, a silicon compound containing a functional group capable of reacting with an epoxy group and a reactive silicon group in the molecule,
Used as an essential component (C).

The functional group capable of reacting with the epoxy group in the silicon compound is specifically a primary, secondary, or tertiary amino group;
Examples include mercapto group; epoxy group: carboxyl group. As the reactive silicon group, the same hydrolyzable silicon group or silanol group as that used in the component (A) may be optionally used, but an alkoxysilyl group is particularly preferable from the viewpoint of easy handling. preferable.

Specific examples of such a silicon compound include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. Methoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ
-Aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane and other amino group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-
Mercapto group-containing silanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, β
Epoxy bond-containing silanes such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane; β-carboxylethyltriethoxysilane, β-carboxylethylphenylbis (2-methoxyethoxy) silane, N
-Β- (N-carboxylmethylaminoethyl) -γ-
Examples thereof include carboxysilanes such as aminopropyltrimethoxysilane. These silicon compounds may be used alone or in combination of two or more.

In the present invention, the silanol condensation catalyst as the component (D) is used to cure the component (A).
As the component (D), any commonly used component can be used.

In the present invention, a hexahydrophthalic acid diglycidyl ester-based compound as the component (B), a rubber-based organic polymer having a reactive silicon group as the component (A), and (C)
A curable composition is prepared using a silicon compound as a component and a silanol condensation catalyst as a component (D) as active components.

The ratio of the component (B) used to the component (A) is preferably in the range of (A) component / (B) component = 100/1 to 100/200 by weight ratio. If the ratio of (A) / (B) exceeds 100/1, the strength of the cured product of the rubber-based organic polymer becomes insufficient, and 100/20
If it is less than 0, the cured product tends to have insufficient rubber-like properties. The more preferable ratio of the component (A) and the component (B) to be used is different depending on the use of the curable composition and therefore cannot be determined unconditionally, but the rubber of the rubber-based organic polymer cured product having a reactive silicon group. If sufficient properties are exhibited and the strength of the cured product is sufficiently improved,
The component (B) is preferably used in an amount of 10 to 150 parts, particularly preferably 20 to 120 parts, per 100 parts of the component (A).

In the present invention, the silicon compound which is the component (C) is
The weight ratio of the component (A) and the component (B) ((A)
The component + (B) component) / (C) component is used in the range of 100 / 0.1 to 100/20, preferably 100 / 0.2 to 100/10.

The ratio of the component (B) and the component (E) which is optionally used in combination is the ratio of the component (A) / the component (B) and the ratio of the component (A).
Part of the component (B) may be replaced with the component (E) as long as the ratio of (component + (B) component) / (C) component is maintained in a preferable range, but part of the (B) component may be replaced. When the component (E) is replaced with another component, it is preferable that the above-mentioned preferred use ratio be established among the components (A), (B) and (C).

Examples of the method for producing a curable composition containing the component (A), the component (B), the component (C) and the component (D) as active ingredients include, for example, the component (A), the component (B), the component (C) and Examples of the method include blending with the component D) and kneading at room temperature or under heating using a mixer, a roll, a kneader, or the like, or using a small amount of a solvent to dissolve the components and mixing.
Further, by appropriately combining these components, a one-pack type or a two-pack type compound can be prepared and used.

The curable composition according to the present invention contains the active ingredient (A).
In addition to the component, the component (B), the component (C) and the component (D), various fillers, plasticizers, antioxidants, ultraviolet absorbers, lubricants, pigments, foaming agents and the like are added as necessary.

When using a filler as the additive, for example, wood flour, pulp, cotton chips, asbestos, glass fiber,
Carbon fiber, mica, walnut flour, rice flour, graphite, diatomaceous earth, clay, fume silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate,
Clay, talc, titanium oxide, magnesium carbonate, quartz, fine aluminum powder, flint powder, zinc dust and the like can be used. These fillers may be used alone or in combination of two or more.

The curable composition according to the present invention can be cured even at a low temperature of room temperature, and can also be rapidly cured at a high temperature of about 100 to 150 ° C., so that a wide temperature range from a low temperature to a high temperature can be obtained depending on the purpose. It can be cured and used.
In particular, when an epoxy resin curing agent that can be cured at room temperature is selected, the curable composition of the present invention has an interesting feature that a high-strength cured product can be obtained by curing at room temperature. Further, since the component (B) is a liquid type epoxy compound, there is a feature that a solventless curable composition can be easily prepared.

The method for molding the curable composition according to the present invention is not particularly limited, but it is preferably molded by a method usually used for molding a solid rubber such as natural rubber or a rubber liquid polymer such as polyurethane, When molded by such a method, a rubber molded product having improved strength and the like, a rubber foam and the like can be obtained. It can also be suitably used as a rubber-based adhesive, a sealant, an adhesive, a potting agent, and the like.

Next, a method for producing the curable composition of the present invention will be described based on examples.

Production Example 1 Average molecular weight with allyl ether groups introduced at 97% of all terminals
800 g of 8000 polypropylene oxide was placed in a pressure resistant reactor equipped with a stirrer, and 19 g of methyldimethoxysilane was added. Then, chloroplatinic acid catalyst solution (8.9 g of H ₂ PtCl ₆ .6H ₂ O was added to 18 ml of isopropyl alcohol and 160 m of tetrahydrofuran).
0.34 ml of a solution dissolved in 1) was added, and the mixture was reacted at 80 ° C. for 6 hours.

When the amount of residual silicon hydride groups in the reaction solution was quantified by the IR spectrum analysis method, almost no residue remained. In addition, when the silicon group was quantified by the NMR method, A polypropylene oxide having about 1.7 per molecule was obtained.

Production Example 2 75 g of the polymer obtained in Production Example 1 was placed in a reaction vessel, devolatilized under reduced pressure, nitrogen substitution was carried out, and then the mixture was heated to 90 ° C. and stirred. Then, a separately prepared mixture of 24.5 g of n-butyl acrylate, 0.4 g of γ-mercaptopropylmethyldimethoxysilane and 0.1 g of AIBN was added dropwise over 1 hour under a nitrogen atmosphere. 15 minutes and 30 minutes after the completion of the dropping, 0.0025 g of each AIBN was dissolved in 4 times by weight acetone and added. After the addition was completed, stirring was continued for 30 minutes to terminate the polymerization reaction.

The obtained reaction product was a clear yellow viscous liquid with a residual monomer content of 0.9% by GC analysis and a viscosity of 260 voise (23 ° C, B
Type viscometer). Also, the obtained polymer GP
From the number average molecular weight of 10,000 by C analysis and the amount of methyldimethoxysilane and γ-mercaptopropylmethyldimethoxysilane charged in the manufacturing process, the average is about 2 per molecule.
It was found that a number of methyldimethoxysilyl groups were introduced.

Example 1 100 parts of the polymer obtained in Production Example 1, hexahydrophthalic acid diglycidyl ester (Mitsui Petrochemical Epoxy Co., Ltd.)
Made, product name EPOMIK R-540) 75 parts, Nocrac NS-6
(Bisphenol type antioxidant manufactured by Ouchi Shinko Chemical Co., Ltd.) 1 part, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane (silicon compound which is the component (C) in the present invention) 1 Part, water 0.4 part, # 918 (an organotin compound manufactured by Sansha Machine Synthesis Co., Ltd., used as a silanol condensation catalyst) 2 parts, 2,4,6-tris (dimethylaminomethyl) phenol (epoxy resin curing) The composition was obtained by thoroughly mixing 7.5 parts (used as an agent). After that, the mixture was carefully poured into a polyethylene mold frame so as not to contain air bubbles, cured at 23 ° C. for 1 day, and further cured at 50 ° C. for 3 days to obtain a cured product sheet having a thickness of 3 mm.

A No. 3 type dumbbell was punched out from the cured product sheet according to JIS K 6301, and the breaking strength (T _B ) and elongation at break (E _B ) were measured at a pulling speed of 500 mm / min. T _B = 50 kg / cm ² , E _B =
A cured rubber with a high strength of 570% was obtained.

Comparative Examples 1-2 A cured product was prepared in the same manner as in Example 1 except that N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane was not used, and T _B was measured to be 8 kg / cm ^2. (Comparative Example 1) Further, a cured product was prepared in the same manner as in Example 1 except that hexahydrophthalic acid diglycidyl ester was not used, and T _B measurement showed 5 kg / cm ² (Comparative Example 2). Only a hardened product was obtained.

Examples 2-7 The above composition was prepared, a cured product sheet was prepared in the same manner as in Example 1, and T _B and E _B were measured. The results are shown in Table 1.

The types of polymers and the types and amounts of epoxy resins in the above composition are shown in Table 1, and the amount of 2,4,6-tris (dimethylaminomethyl) phenol was X / Y = 10/1.
It was used as follows. Also, Epicoat # 82 in Table 1
8 is an epichlorohydrin-bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.

Example 8 A cured product sheet was obtained in the same manner as in Example 1 except that 1.5 parts of γ-aminopropyltrimethoxysilane was used instead of 1 part of N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. It was manufactured, punched out with a No. 3 type dumbbell, and its physical properties were measured. T _B = 45 kg / cm ² , E _B = 520%
Met.

Next, examples in which the composition of the present invention is used as an adhesive will be shown.

Examples 9 to 16 and Comparative Examples 3 to 5 Using the compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2, adhesive test samples were prepared according to the following method, and the adhesive strength was measured. It was In Comparative Example 5, 100 parts of the polymer obtained in Production Example 1 and Epicoat # 828 100 were used.
Part, Nocrac NS-6 1 part, N-β- (aminoethyl)
-Γ-aminopropyltrimethoxysilane 1 part, water 0.4
Part, # 918 2 parts and 2,4,6-tris (dimethylaminomethyl) phenol 10 parts at room temperature x
A test sample was prepared and the adhesive strength was measured according to the following method, except that curing was performed under the condition of 1 day + 50 ° C. × 3 days.

Sample preparation method and test method for tensile shear strength measurement (according to JIS K 6850) Aluminum plate (100 mm x 2 specified in JIS H 4000)
The surface of 5 mm x 2 mm A-1050P aluminum plate) is lightly wiped with acetone, and then the above composition is spread on this with a spatula to give an area of about 25 mm x 12.5 mm and a thickness of about 0.05 mm. As applied. Next, the coated surfaces of the two aluminum plates coated with the above composition were stuck together and pressed by hand. This sample was fixed on the adhesive surface, cured at 23 ° C. for 1 day, further heat-cured at 50 ° C. for 3 days, and then subjected to a tensile test at a tensile rate of 5 mm / min. The maximum load until the adhesive portion of the test piece was broken was measured, and this was divided by the shear area to obtain the tensile shear strength. The results are shown in Table 2.

Sample preparation method and test method for T-type peel strength measurement (in accordance with JIS K 6854) Aluminum plate (200 mm x 2 specified in JIS H 4000)
The surface of a 5 mm × 0.1 mm A-1050P aluminum plate) was lightly wiped with acetone, and then the above composition was applied with a spatula to an area of about 100 mm × 25 mm with a thickness of about 0.3 mm. . Next, the coated surfaces of the two aluminum plates coated with the above composition were stuck together, and pressed with a 5 kg hand roller repeatedly 5 times so as not to reciprocate in the length direction.
This sample was cured at 23 ° C. for 1 day, further heat-cured at 50 ° C. for 3 days, and then subjected to a tensile test at a tensile speed of 200 mm / min. Attach the sample to the tensile tester in a T shape,
The strength at which the adhesive portion was broken was determined as the T-type peel strength. The results are shown in Table 2.

[Effect of the Invention] When the composition according to the present invention is used, the strength of the rubber-based organic polymer as the component (A) is improved. Especially tensile shear strength and T
It is possible to obtain an adhesive having excellent shape peel strength.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-57458 (JP, A) JP-A-57-47054 (JP, A) JP-A-57-123250 (JP, A) JP-A-58- 34824 (JP, A) Japanese Patent Publication 3-31726 (JP, B2)

Claims (5)

[Claims] 1. A rubber-based organic polymer having (A) at least one reactive silicon group in the molecule (B) Hexahydrophthalic acid diglycidyl ester-based compound (C) Reactive with a functional group capable of reacting with an epoxy group A process for producing a curable composition, which comprises blending a silicon compound containing a soluble silicon group in a molecule and (D) a silanol condensation catalyst. 2. A component (A) / a component (B) is 100/1 to 100/200.
(Weight ratio), ((A) component + (B) component / (C))
The method for producing a curable composition according to claim 1, wherein the components are 100 / 0.1 to 100/20 (weight ratio). 3. The method for producing a curable composition according to claim 1, wherein the reactive silicon groups in the components (A) and (C) are both alkoxysilyl groups. 4. The main chain of the rubber-based organic polymer as the component (A) is
The curability according to claim 1, which is a polyether having a repeating unit represented by the general formula: -R-O- (wherein R represents a divalent alkylene group having 2 to 4 carbon atoms). Method of making the composition. 5. The main chain of the rubber-based organic polymer as the component (A) is
A polymer or copolymer obtained by polymerizing a vinyl monomer in the presence of a polyether.
A method for producing the curable composition according to item.