JPH0859961A - Curable composition - Google Patents

Abstract

PURPOSE: To obtain a curable composition which contains, as essential components, a polyether containing reactive silyl groups, a specific polymer (an epoxy resin), a curing agent and a specific silicone, and shows excellent mechanical properties and high adhesion strength. CONSTITUTION: This curable composition comprises, as essential components, (A) a polyether bearing at least one of reactive silyl groups in the molecule, (B) a polymer from a monomer bearing a polymerlzable unsaturated group, (C) an epoxy resin, (D) a curing agent for epoxy resins and (E) a silicone bearing at least one functional group reactive with epoxy group or an epoxy group and at least one reactive silyl group such as γ-(meth)acryloyloxypropyl- methoxysilane. In this composition, it is preferred that component B uniformly disperses in component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified curable composition, and more particularly to a curable composition having remarkably excellent mechanical properties.

[0002]

2. Description of the Related Art Polyether compounds having at least one reactive silyl group in the molecule have been used for coating compositions, sealing compositions, etc. by taking advantage of the fact that cured products have rubber elasticity. In particular, the strength of the cured product is insufficient for applications such as adhesives and waterproofing agents, which poses a practical problem. For example, if you use it as an adhesive,
There is a problem that the shear adhesive strength is insufficient, and when this is used as a waterproofing agent, there is a problem that the strength of the film is insufficient. For such problems,
The inventors have found that a composition comprising a polymer of a polyether compound having a reactive silyl group and a polymerizable unsaturated group-containing monomer has excellent cured physical properties and adhesive strength,
JP-A-5-194677 and JP-A-5-19467
No. 8 and Japanese Patent Laid-Open No. 5-194679.

[0003]

These compositions have excellent cured physical properties and adhesive properties, but higher strength is required depending on the application. An object of the present invention is to solve the above-mentioned drawbacks and to provide a curable composition whose cured product has remarkably excellent adhesive strength.

[0004]

Means for Solving the Problems That is, the present invention provides a polyether (A) having at least one reactive silyl group in the molecule, a polymer (B) of a polymerizable unsaturated group-containing monomer, and an epoxy resin ( C), a curing agent for epoxy resin (D), and a silicon compound (E) containing at least one functional group or epoxy group capable of reacting with an epoxy group and at least one reactive silyl group in the molecule (E) It is a curable composition as a component.

The polyether (A) containing at least one reactive silyl group in the molecule used in the present invention is disclosed in JP-B-45-36319 and JP-B-46.
-12154, Japanese Patent Publication No. 49-32673,
JP-B-50-156599, JP-B-51-735
61, Japanese Patent Publication 54-6096, Japanese Patent Publication 55
-13767 publication, Japanese Patent Publication No. 55-13768 publication,
JP-B-55-82123, JP-B-55-1236
20, Japanese Patent Publication No. 55-125121, Japanese Patent Publication No. 55-131021, Japanese Patent Publication No. 55-131022.
JP-B, JP-B-55-135135, JP-B-55
-137129, JP-A-3-47825,
It is proposed in JP-A-3-72527, JP-A-3-43449, JP-A-3-79627 and the like.

The polyether (A) is obtained by, for example, ring-opening polymerization of a monoepoxide having 3 or more carbon atoms in the presence of an initiator, and then converting some or all of the hydroxyl groups at the molecular terminals into reactive silyl groups. Obtained by

Examples of the catalyst include alkali catalysts such as KOH catalyst, porphyrin catalysts, and complex metal cyanide complex catalysts such as zinc hexacyanocobaltate catalyst.

As the monoepoxide having 3 or more carbon atoms,
Examples thereof include propylene oxide, 1,2-butylene oxide, aliphatic alkylene oxides such as epichlorohydrin, and aromatic alkylene oxides such as styrene oxide. Aliphatic alkylene oxides are preferable, and propylene oxide is particularly preferable. It is also possible to use a small amount of ethylene oxide together with this.

The initiator used in the present invention includes polyhydric alcohols, polyhydric phenols, polyhydric carboxylic acids, polyhydric active hydrogen-containing compounds such as polyhydric amines, unsaturated alcohols,
An unsaturated group-containing active hydrogen-containing compound such as unsaturated phenol or unsaturated carboxylic acid may be used.

The reactive silyl group is condensed with moisture or a curing agent, like a silanol group or a hydrolyzable silyl group,
It can react to accelerate the increase in the molecular weight of the polyether and is represented by the following general formula (1).

X _3-m -Si (R ⁰ ) _m − (1) In the formula, R ⁰ is a monovalent hydrocarbon group or a halogenated hydrocarbon group, and X is a hydroxyl group, a halogen atom, an alkoxy group or an acyloxy group. Hydrolyzable groups such as groups, amide groups, amino groups, aminoxy groups or ketoximate groups. m is 0, 1 or 2.

The method for introducing the reactive silyl group can be specifically exemplified by the following methods, but the method is not limited to these methods.

(A) A specific organosilicon compound having at least one, preferably only one isocyanate group and at least one reactive silyl group in the molecule, as represented by the general formula (2), has a hydroxyl group. React with the terminal hydroxyl groups of the polyether compound.

X _3-m -Si (R ⁰ ) _m -R ¹ -NCO (2) In the formula, R ⁰ , X and m are the same as above. R ¹ is a divalent hydrocarbon group or a halogenated hydrocarbon group.

The following compounds can be shown as specific organic silicon compounds.

(C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NCO, (CH ₃ O) ₃ Si (CH ₂ ) ₃ NCO, (CH ₃ O) ₂ (CH ₃ ) Si (CH ₂ ) ₃ NCO _{, (CH 3 O) 3 SiNCO} , (CH 3 O) 2 Si (NCO) 2.

(B) A terminal unsaturated group obtained by reacting a terminal unsaturated group-containing isocyanate compound or a terminal unsaturated group-containing halogen compound with a terminal hydroxyl group of a polyoxyalkylene compound, or a polyoxyalkylene compound derived from an initiator. The terminal unsaturated group is reacted with the hydrosilicon compound represented by the general formula (3) in the presence of a catalyst containing a Group 8 metal such as platinum or a compound thereof.

X _3-m -Si (R ⁰ ) _m H (3) In the formula, R ⁰ , X and m are the same as above.

Specific examples include allyl isocyanate as the terminal unsaturated group-containing isocyanate compound and allyl chloride as the terminal unsaturated group-containing halogen compound.
In addition to the above methods, the methods described in JP-A-5-194678 and the like can be mentioned.

The polyether (A) used in the present invention thus obtained has a molecular weight of preferably from 1,000 to 50,000, particularly preferably from 4,000 to 30,000.

The polymer of component (B) used in the present invention is obtained by polymerizing a polymerizable unsaturated group-containing monomer. The polymerizable unsaturated group-containing monomer is preferably a polymerizable unsaturated group-containing monomer represented by the general formula (4), or a mixture of two or more kinds.

CH ₂ = CR ² R ³ (4) In the formula, R ² is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group. R ³ is a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a carboxyl group, an alkoxycarbonyl group, a glycidyloxycarbonyl group, a nitrile group, an alkenyl group,
Glycidyloxy group, acyloxy group, amide group or pyridyl group.

Examples of the polymerizable unsaturated group-containing monomer represented by the general formula (4) include styrene-based monomers such as styrene, α-methylstyrene and chlorostyrene; (meth) acrylic acid (acrylic acid and methacrylic acid are shown. .
The same applies below. ), Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth)
Esters of (meth) acrylic acid such as 2-ethylhexyl acrylate and benzyl (meth) acrylate, (meth)
Acrylic monomers such as acrylic acid amide; cyano group-containing monomers such as acrylonitrile and 2,4-dicyanobutene-1; vinyl ester monomers such as vinyl acetate and vinyl propionate; glycidyl (meth) acrylate, (meth) allyl glycidyl ether Epoxy group-containing monomers such as butadiene, isoprene, chloroprene and other diene-based monomers; and olefins other than these, unsaturated esters, halogenated olefins, vinyl ethers and the like.

If desired, the silicon compound represented by the general formula (5) can also be used as the polymerizable unsaturated group-containing monomer in the present invention.

Y _3-n -SiR ⁴ _n R ⁵ (5) In the formula, R ⁴ is a monovalent hydrocarbon group or a halogenated hydrocarbon group. Y is a hydrolyzable group such as a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. R ⁵ is an organic residue having a polymerizable unsaturated group. n is 0, 1 or 2.

Specific examples of the silicon compound represented by the formula (5) include a reactive silyl group such as γ- (meth) acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropylmethyldimethoxysilane ( (Meth) acryloyloxyalkyl compounds such as vinylmethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl (β-methoxyethoxy) silane, isopropenylmethyldimethoxysilane, isopropenyltrimethoxysilane, and isopropenyltriethoxysilane. is there.

These polymerizable unsaturated group-containing monomers are
Although it may be appropriately selected as necessary, glycidyl acrylate, an epoxy group-containing monomer such as glycidyl methacrylate alone or when used in a copolymerization with a cyano group-containing monomer such as acrylonitrile or a styrene-based monomer such as styrene, It is particularly preferable because it can exhibit excellent adhesiveness and mechanical strength.

The amount of the polymerizable unsaturated group-containing monomer used is not particularly limited, but the polyether (A) 100 may be used.
0.1 to 1000 parts by weight, preferably 0.1.
It is preferably used in the range of 1 to 100 parts by weight from the viewpoint of workability and the like.

The polymerization of the polymerizable unsaturated group-containing monomer is carried out by a method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the polyether (A) having at least one reactive silyl group in the molecule, in a solvent. And a method of polymerizing the polymerizable unsaturated group-containing monomer in the presence of the polyether (G).

The polyether (G) is a polyether compound before introducing the reactive silyl group in the above-mentioned method for producing the polyether (A), and is a polyether having a hydroxyl group or an unsaturated group at the terminal. is there.

The polyether (G) may be a polyether (F) having a polymerizable unsaturated group in the molecule. In this case, in particular, the polymer (B) of the polymerizable unsaturated group-containing monomer
It is possible to ensure excellent storage stability when coexisting with the polyether (A) having at least one reactive silyl group in the molecule. Even when the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polyether (A) or in a solvent, the same effect can be obtained by coexisting the polyether (F) having the polymerizable unsaturated group. Is obtained.

The polyether (F) having a polymerizable unsaturated group is a polymer having one or more polymerizable unsaturated groups in one molecule and the main chain consisting essentially of a polyether chain. Examples of the polymerizable unsaturated group in this case include the groups shown below. These polymerizable unsaturated groups may be present at the ends or side chains of the polyether. In the following, φ represents a phenylene group.

-OCH ₂ CH = CH ₂ , -OC (CH ₃ ) = CH ₂ , -OCH ₂ CH ₂ CH = CH ₂ , -OCOCH ₂ CH = CH ₂ , -OCOCH = CH ₂ , -OCOC (CH _{3 ) = CH 2, -OCH 2 -φ} -CH = CH 2.

As the method for producing the polyether (F) having a polymerizable unsaturated group, a method of converting a terminal hydroxyl group of a hydroxyl group-terminated polyether obtained by ring-opening addition polymerization of monoepoxide into a polymerizable unsaturated group, A method of ring-opening addition-polymerizing a monoepoxide with an active hydrogen-containing compound containing a polymerizable unsaturated group, or a method of copolymerizing a mono-epoxide containing a polymerizable unsaturated group such as allyl glycidyl ether during the ring-opening addition polymerization of a monoepoxide. By polymerizing,
Examples thereof include a method of introducing a polymerizable unsaturated group into a side chain or a terminal. As a specific method, the method previously proposed by the inventor (Japanese Patent Laid-Open No. 3-72527) and the like can be mentioned.

The polyether (F) having a polymerizable unsaturated group may be a polyether having a reactive silyl group together with a polymerizable unsaturated group in the molecule. In this case, a cured product having excellent mechanical properties can be obtained. The reactive silyl group, like a silanol group and a hydrolyzable silyl group,
It causes condensation and reaction with moisture, curing agent, etc.
It is represented by the general formula (6).

Z _3−p —Si (R ⁶ ) _p − (6) In the formula, R ⁶ is a monovalent hydrocarbon group or a halogenated hydrocarbon group. Z is a hydrolyzable group such as a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminoxy group or a ketoximate group. p is 0, 1 or 2.

The polyether having a reactive silyl group together with a polymerizable unsaturated group in such a molecule is, for example, a part of the terminal allyl group of the allyl group terminated polyether and the hydrosilicon compound represented by the general formula (7). Can be produced by reacting in the presence of a catalyst composed of a Group 8 metal such as platinum or a compound thereof, but is not particularly limited thereto.

[0038] ^{_{Z 3-p -Si (R 6}} ) p H ··· (7) formula R ^6, Z and p are as defined above.

The solvent can be appropriately selected depending on the kind of the polymerizable unsaturated group-containing monomer used for the polymerization. The polymerization initiator used for the polymerization is not limited to the radical generator, various compounds capable of polymerizing the polymerizable unsaturated group-containing monomer can be used, and in some cases radiation or radiation without using the polymerization initiator. It can be polymerized by heat. Examples of the polymerization initiator include peroxide-based, azo-based, or redox-based polymerization initiators and metal compound catalysts. Specific examples of the polymerization initiator often used include azobisisobutyronitrile, benzoyl peroxide, t-alkylperoxy ester, acetyl peroxide, diisopropyl peroxy carbonate and the like.

The epoxy resin used as the component (C) in the present invention includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac. Type epoxy resin, bisphenol F novolac type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, resorcin type epoxy resin, and halides thereof. Examples thereof include, but are not limited to, hydrogenated compounds, and commonly used epoxy resins can be used.

The amount of the epoxy resin (C) used is not particularly limited, but the polyether (A) and the polymer (B) are used.
0.1 to 300 parts by weight is preferable with respect to 100 parts by weight as a total amount.

As the epoxy resin curing agent used as the component (D) in the present invention, aliphatic polyamines such as diethylenetriamine and triethylenetetramine, aromatic polyamines such as metaphenylenediamine and secondary amines,
Tertiary amines such as tris (dimethylaminomethyl) phenol, tertiary amine salts, acid anhydrides, polyamide resins, polysulfide resins, boron trifluoride complex compounds,
Examples thereof include imidazoles and dicyandiamides.

Also, latent curing agents such as ketimines represented by the general formulas (8) and (9) and silazanes can be used.

R ⁷ R ⁸ C = N-R ⁹ -NH-R ¹⁰ -N = CR ¹¹ R ¹² (8) In the formula, R ⁷ , R ⁸ , R ¹¹ and R ¹² are a hydrogen atom or a halogen atom. Or a monovalent hydrocarbon group. R ⁹ and R ¹⁰ are divalent hydrocarbon groups.

R ¹³ R ¹⁴ C = N-R ¹⁵ -N = CR ¹⁶ R ¹⁷ (9) In the formula, R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ are hydrogen atom, halogen atom or monovalent carbon. Hydrogen radical. R ¹⁵ is a divalent hydrocarbon group.

Further, a compound obtained by reacting the imino group of the ketimine represented by the general formula (8) with an epoxy group-containing compound such as styrene oxide or butyl glycidyl ether, or a monoisocyanate compound such as phenyl isocyanate can also be used.

In the present invention, the curing agent for epoxy resin which is the component (D) is 0.1 to 100 parts by weight of the component (C).
It is preferable to use 300 parts by weight.

In the present invention, a silicon compound containing at least one functional group capable of reacting with an epoxy group or at least one epoxy group and at least one reactive silyl group in the molecule is used as an essential component (E). .

Specific examples of the silicon compound having at least one epoxy group and at least one reactive silyl group in the molecule include γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxypropylmethyldimethoxysilane, Examples thereof include γ-glycidyloxypropyltriethoxysilane.

Specific examples of the silicon compound having at least one functional group capable of reacting with an epoxy group and at least one reactive silyl group in the molecule include 3-aminopropyltrimethoxysilane and 3 -(2
-Aminoethyl) aminopropyltrimethoxysilane,
Amino group-containing silanes such as 3- (2-aminoethyl) aminopropylmethyldimethoxysilane and 1,4-di (triethoxysilylpropyl) ethylenediamine, γ-
Mercapto group-containing silanes such as mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, β-carboxyethyltriethoxysilane, β-carboxyethyl Phenylbis (2-methoxyethoxy)
Examples thereof include silanes and carboxyl group-containing silanes such as N-β- (N-carboxymethylaminoethyl) -γ-aminopropyltrimethoxysilane. These silicon compounds may be used alone or in combination of two or more.

In the present invention, the component (E) is
The silicon compound containing at least one functional group capable of reacting with an epoxy group or at least one epoxy group and at least one reactive silyl group in the molecule is (A), (B) and (C) in a total amount of 100 parts by weight. On the other hand, it is preferable to use 0.1 to 100 parts by weight.

The composition of the present invention is prepared by mixing the polymer (B) of a monomer having a polymerizable unsaturated group and the polyether (A) having at least one reactive silyl group in the molecule, and then mixing the epoxy resin with the epoxy resin. (C), a curing agent (D) for epoxy resin, and a silicon compound (E) containing at least one functional group capable of reacting with an epoxy group or at least one epoxy group and at least one reactive silyl group in the molecule are added. However, when the polymerization of the polymerizable unsaturated group-containing monomer is carried out in the presence of the polyether (A) containing at least one reactive silyl group in the molecule, after polymerization of the monomer, The desired composition can be obtained without newly mixing with the polyether (A) having at least one reactive silyl group in the molecule. When the polymerizable unsaturated group-containing monomer is polymerized in the presence of the polyether (G), the desired composition can also be obtained by introducing a reactive silyl group into the polyether (G) after the polymerization. Obtainable. When the polymerizable unsaturated group-containing monomer is polymerized in a solvent, it is mixed with a polyether (A) containing at least one reactive silyl group in the molecule, and then a part or all of the solvent is distilled off. You may.

The polymer (B) of the polymerizable unsaturated group-containing monomer in the composition is uniformly dispersed in fine particles in the polyether (A) containing at least one reactive silyl group in the molecule. Although it may be dissolved or uniformly dissolved, it is preferably dispersed uniformly in consideration of workability such as viscosity of the composition.

In the curable composition of the present invention, a curing accelerating catalyst that accelerates the curing reaction of the reactive silyl group may be used in order to accelerate the curing with moisture. As the curing accelerating catalyst, a metal salt of a carboxylic acid such as alkyl titanate, organosilicon titanate, bismuth tris-2-ethylhexoate, tin octylate and dibutyltin dilaurate: dibutylamine-2-ethylhexoate. Amine salts such as ates and the like, as well as other acidic catalysts and basic catalysts such as laurylamine may be used. Further, a dehydrating agent may be added to the curable composition of the present invention in order to further improve storage stability. As the dehydrating agent, a hydrolyzable organic silicon compound such as an alkyl orthoformate: vinyltrimethoxysilane or tetraethylsilicate: a hydrolyzable organic titanium compound may be used.

The curable composition of the present invention may further contain a filler, a plasticizer, etc., if necessary. Known fillers can be used as the filler, and specifically, fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined Clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil, filler such as glass balloon, fibrous filler such as asbestos, glass fiber and filament Can be used.

As the plasticizer, known plasticizers can be used, and specifically, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butylbenzyl phthalate;
Aliphatic carboxylic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, butyl oleate; glycol esters such as pentaerythritol ester; phosphoric acid esters such as trioctyl phosphate, tricresyl phosphate; epoxidized soybean oil , Epoxy plasticizers such as benzyl epoxy stearate; chlorinated paraffins and the like can be used alone or as a mixture of two or more kinds.
Further, polyoxypropylene monool, polyoxypropylene diol, and terminal modified products thereof can also be used.
The terminal modified product, for example, a terminal hydroxyl group is an alkoxy group,
Compounds modified with alkenyloxy groups and urethane bonds,
Examples thereof include compounds which are blocked with a hydrocarbon group via an ester bond, a urea bond or a carbonate bond.

The curable composition of the present invention may further contain various known additives. As an additive,
Aminosilanes, epoxysilanes, phenol resins, adhesion promoters such as epoxy resins, pigments, various antiaging agents, and ultraviolet absorbers can be used.

The curable composition of the present invention cures at room temperature in the presence of moisture and can be used especially for elastic sealants and adhesives.

[0059]

【Example】

[Production Example 1] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol.
Isocyanatopropylmethyldimethoxysilane was added to this to carry out a urethane reaction to convert the hydroxyl groups at both ends into methyldimethoxysilylpropyl groups, with an average molecular weight of 1
30,000 polyethers P1 were obtained.

[Production Example 2] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using glycerin as an initiator to obtain polyoxypropylene triol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into a methyldimethoxysilyl group, and to give an average molecular weight of 2
50,000 polyether P2 was obtained.

[Production Example 3] Polyoxypropylene diol was obtained by polymerizing propylene oxide with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Polyether P3 having an average molecular weight of 17,000 was obtained.

[Production Example 4] Polyoxypropylenediol was obtained by polymerizing propylene oxide with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 50% of the allyl group into a methyldimethoxysilyl group to give a polyether P4 having an average molecular weight of 17,000. Obtained.

Production Example 5 Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol. A methanol solution of sodium methylate was added to this to remove methanol, and then allyl chloride was added to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxyalkylene compound is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert 100% of the allyl group into a methyldimethoxysilyl group, to give a polyether P5 having an average molecular weight of 17,000. Obtained.

[Production Examples 6 to 9] 50 g of the polyether obtained in Production Example 1, Production Example 2 or Production Example 5 was treated with 300c.
The mixture was placed in a 4-necked flask of m ³ and maintained at 110 ° C., and a mixture of 50 g of polyether, 30 g of the monomers shown in Table 1 and 0.6 g of azobisisobutyronitrile was stirred for 2 hours under a nitrogen atmosphere. Was dropped. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, unreacted monomers were removed by degassing under reduced pressure by heating at 110 ° C. and 0.1 mmHg for 2 hours to obtain a mixture of polyether (A) and polymer (B). Table 1 shows the types of polyether and the types of monomers used.

However, in Table 1, the monomers used are shown as follows: AN: acrylonitrile, GMA: glycidyl methacrylate, ST: styrene.

[Production Example 10] Propylene oxide was polymerized with zinc hexacyanocobaltate catalyst using diethylene glycol as an initiator to obtain polyoxypropylene diol having an average molecular weight of 17,000. 50 g of this polyol was put into a 300 cm ³ four-necked flask and
Keeping at ℃, polyether 50g, glycidyl methacrylate 25g, azobisisobutyronitrile 0.6
The mixture of g was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After completion of the reaction, unreacted monomers were removed by degassing under reduced pressure by heating at 110 ° C. and 0.1 mmHg for 2 hours. Then, add isocyanate propylmethyldimethoxysilane to this,
Urethane reaction was carried out to convert the hydroxyl groups at both ends into methyldimethoxysilylpropyl groups to obtain a mixture of polyether (A) and polymer (B).

[Production Example 11] 15 g of the polyether P3 obtained in Production Example 3 was dissolved in 100 g of the polyether P5 obtained in Production Example 5 and placed in a 4-necked flask.
Glycidyl Methacrylate 21
g, 9 g of acrylonitrile, and 0.2 g of azobisisobutyronitrile were added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1
The mixture was heated under a vacuum of mmHg for 2 hours under reduced pressure and degassed to obtain a mixture of polyether (A) and polymer (B).

Production Example 12 15 g of the polyether P4 obtained in Production Example 4 was dissolved in 100 g of the polyether P5 obtained in Production Example 5 and placed in a 4-necked flask for 10
Glycidyl Methacrylate 21
g, 9 g of acrylonitrile, and 0.2 g of azobisisobutyronitrile were added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction is completed, unreacted monomer is heated to 110 ° C. and 0.1
The mixture was heated under a vacuum of mmHg for 2 hours under reduced pressure and degassed to obtain a mixture of polyether (A) and polymer (B).

[Production Example 13] 50 g of the polyether P3 obtained in Production Example 3 was dissolved in 100 g of toluene, placed in a 4-necked flask, and kept at 100 ° C., 70 g of glycidyl methacrylate, 30 g of acrylonitrile and azobis. A mixture of 0.6 g of isobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction was completed, 250 g of the polyether P5 obtained in Production Example 5 was added and mixed with stirring, and then toluene and unreacted monomer were added to 110 g under stirring.
Distilled by heating under reduced pressure degassing at 0.1 mmHg for 2 hours.
A mixture of polyether (A) and polymer (B) was obtained.

[Production Example 14] 50 g of the polyether P4 obtained in Production Example 4 was dissolved in 100 g of toluene, placed in a 4-necked flask, and kept at 100 ° C., 70 g of glycidyl methacrylate, 30 g of acrylonitrile and azobis. A mixture of 0.6 g of isobutyronitrile was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature. After the reaction was completed, 250 g of the polyether P5 obtained in Production Example 5 was added and mixed with stirring, and then toluene and unreacted monomer were added to 110 g under stirring.
Distilled by heating under reduced pressure degassing at 0.1 mmHg for 2 hours.
A mixture of polyether (A) and polymer (B) was obtained.

PRODUCTION EXAMPLE 15 Polyether P3 having the polymerizable unsaturated group obtained in Production Example 3 in 100 g of toluene.
300g of which is melted and put in a four-necked flask at 100 ° C.
Glycidyl methacrylate 70 g, acrylonitrile 30 g, azobisisobutyronitrile 0.
6 g of the mixture was added dropwise over 2 hours with stirring under a nitrogen atmosphere. Then, stirring was continued for 0.5 hours at the same temperature.
After completion of the reaction, methyldimethoxysilane was used to convert the polymerizable unsaturated group of the polyether into a methyldimethoxysilyl group in the presence of a platinum catalyst to obtain a mixture of the polyether (A) and the polymer (B).

[Examples 1 to 13 and Comparative Examples 1 and 2] Epicoat 82 was added to 100 parts by weight of the mixture of the polyether (A) and the polymer (B) obtained in the above Production Examples 6 to 15.
Wet 30 parts by weight of 8 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), 3 parts by weight of curing agent (D) of epoxy resin, 2 parts by weight of silicon compound (E), and 2 parts by weight of dibutyltin dilaurate. Kneading was carried out under the condition of not containing the minutes to obtain a curable composition (Examples 1 to 13).

A curable composition obtained by removing Epicoat 828 from the above composition was used as Comparative Example 1, polyether (A).
Comparative Example 2 was a curable composition in which polyether P3 was used instead of the mixture of the polymer (B) and the polymer (B).

[Curing agent for epoxy resin (D)] a: 2,4,6-tris (dimethylaminomethyl) phenol, b: Epicure H-3 (epoxy resin latent curing by Yuka Shell Epoxy Co., Ltd.) Agent).

[Silicon compound (D)] c: γ-glycidyloxypropyltrimethoxysilane, d: 3- (2-aminoethyl) aminopropyltrimethoxysilane.

Upon exposure to moisture, these compositions immediately started to cure and changed into good rubber elastic bodies.
The composition of each curable composition and the aluminum (JIS H4
000 A1050P) tensile shear strength (unit:
kg / cm ² ) and T-shaped peel strength (unit: kg / 25m
The measurement results of m) are shown in Tables 2 to 4.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

As described above, the polyether (A) containing at least one reactive silyl group in the molecule,
Polymer (B) of polymerizable unsaturated group-containing monomer, epoxy resin (C) curing agent of epoxy resin (D), at least one functional group capable of reacting with an epoxy group or an epoxy group in the molecule, and a reactive silyl group. The present invention has revealed that a curable composition containing a silicon compound (E) having at least one group as an essential component can exhibit remarkably high adhesive strength.

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Claims (7)

[Claims] 1. A polyether (A) having at least one reactive silyl group in the molecule, a polymer (B) of a polymerizable unsaturated group-containing monomer, an epoxy resin (C), a curing agent for an epoxy resin ( A curable composition containing D) and a silicon compound (E) containing at least one functional group or epoxy group capable of reacting with an epoxy group in the molecule and at least one reactive silyl group as an essential component. 2. The curable composition according to claim 1, wherein the polymer (B) is uniformly dispersed in the polyether (A). 3. A polyether (A) and a polymer (B)
The curable composition according to claim 1 or 2, which is obtained by polymerizing a polymerizable unsaturated group-containing monomer in a polyether (A). 4. The polyether (A) and the polymer (B) are
A polymer (A) obtained by polymerizing a polymerizable unsaturated group-containing monomer in the presence of, on average, a polyether (F) having at least one polymerizable unsaturated group in the molecule. The curable composition of claim 1 or claim 2. 5. The polyether (A) and the polymer (B) are
After obtaining a polymer by polymerizing a polymerizable unsaturated group-containing monomer in a polyether (G) having a functional group capable of introducing a reactive silyl group, a reactive silyl group is subsequently added to the polyether (G). A curable composition according to claim 1 or claim 2 obtained by introduction. 6. The polyether (A) and the polymer (B) are
A polymer (B) is obtained by polymerizing a polymerizable unsaturated group-containing monomer in a solvent, then mixed with the polyether (A), and then the solvent is distilled off. Alternatively, the curable composition of claim 2. 7. The polyether (A) and the polymer (B) are
A polymer (B) is obtained by polymerizing a polymerizable unsaturated group-containing monomer in a solvent in the presence of an average polyether (F) having at least one polymerizable unsaturated group in the molecule. Then, the curable composition according to claim 1 or 2, which is obtained by mixing with polyether (A) and then distilling off the solvent.