JPH0762205A - Curable composition - Google Patents

Abstract

(57) [Summary] [Structure] A polymer in which a hydrolyzable silicon group is introduced into 82% of the end of polyoxypropylene triol having an average molecular weight of 20,000 and 60% of the end of polyoxypropylene pentaol having an average molecular weight of 20,000 are hydrolyzed. An epoxy compound and other additives were added to a mixture composed of a degradable silicon group-introduced polymer to obtain a composition. [Effect] A curable composition useful as an elastic adhesive having a low viscosity, excellent workability, excellent adhesion to a substrate and excellent water resistance can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to curable compositions which cure in the presence of moisture.

[0002]

2. Description of the Related Art As a polyether having a hydrolyzable silyl group capable of forming a siloxane bond by hydrolysis and having a high molecular weight or cross-linking, some examples are conventionally known (for example, JP-A-3-47820). JP-A-3-72027, JP-A-3-79627, JP-B-46-30711, and JP-B-45-36.
319, Japanese Patent Publication No. 46-17553).

These polyether compounds are used alone as elastic sealants, elastic adhesives, etc. because they cure at room temperature due to moisture to give an elastic body. Are limited.

On the other hand, epoxy resins are used in a wide variety of applications such as adhesives, paints, and laminated boards, but generally the cured products are fragile, and when used as adhesives, the peel strength is surprisingly small. Have.

Therefore, in order to improve the drawbacks of both, a resin composition prepared by mixing a polyether having reactive silicon and an epoxy resin has been proposed (for example, Japanese Patent Laid-Open Publication No. 6-58242).
JP-A No. 1-247723 and JP-A No. 61-268720).

[0006]

However, this composition is
Since it has a high viscosity before curing and it is difficult to cure it uniformly, its use is limited in practical use.

[0007]

As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a polyether polymer having at least one hydrolyzable silicon group in the molecule. In the polymer, when a part or all of the polyether polymer is a polymer obtained by substituting the terminal hydroxyl group of a tetrafunctional or higher polyoxypropylene polyol with a hydrolyzable silicon group, the viscosity before curing is low and the handling is easy. And, the curing speed is fast, and the curing is easy to proceed uniformly,
Furthermore, the cured product after curing has particularly excellent heat resistance, water resistance,
The present invention has been achieved by finding out that it has weather resistance.

That is, the present invention provides at least 1 in the molecule.
In a composition comprising a polyether polymer having two hydrolyzable silicon groups and an epoxy resin, a part or all of the polyether polymer hydrolyzes at least a part of terminal hydroxyl groups of a tetrafunctional or higher polyoxypropylene polyol. A curable composition characterized by being a polyether polymer (A) substituted with a decomposable silicon group.

The average molecular weight of the polyether polymer (A) used is preferably 500 to 25,000,
Particularly preferably, it is 6000 to 20000. When the average molecular weight of the polyether polymer (A) is larger than 25,000, the effect of improving the viscosity is insufficient.

The polyether polymer (A) is obtained by substituting at least 25% of the terminal hydroxyl groups of a tetra- or higher functional polyoxypropylene polyol with a hydrolyzable silicon group. In particular, it is preferable that 30% to 80% of the terminal hydroxyl groups are substituted with a hydrolyzable group. When the substitution ratio of the hydrolyzable silyl group is less than 25%, not only the strength and physical properties of the cured product are deteriorated but also the rapid curing property and the uniformity of curing are lost, which is not preferable. Further, the hydroxyl group not substituted by the hydrolyzable silicon group may be substituted by another organic group.

The proportion of the polyether polymer (A) in the total polyether polymer varies depending on the required viscosity before curing and the physical properties of the cured product after curing, but is usually 5 to 100.
wt%, preferably 30 to 100 wt%, and particularly preferably 50 to 100 wt%. The proportion of the polyether polymer (A) in all the polyether polymers is 5 wt%
If it is less, the effect of improving the viscosity and physical properties tends to be poor.

The polyether polymer (A) is obtained by reacting propylene oxide with an initiator such as a hydroxy compound having four or more hydroxyl groups in the presence of a catalyst such as an alkali catalyst, a complex metal cyanide complex catalyst and a metal porphyrin. It can be synthesized by introducing a hydrolyzable silicon group into the terminal hydroxyl group of the polyoxypropylene polyol thus produced by a known method.

The polyether polymer other than the polyether polymer (A) is a compound such as an alkali metal catalyst, an acid catalyst, a complex metal cyanide complex catalyst, or a hydroxy compound having at least one hydroxyl group in the presence of a catalyst such as a metal porphyrin. It is preferable to introduce a hydrolyzable silicon group by a known method into a hydroxyl group-terminated polyether compound produced by reacting the agent with a monoepoxide such as alkylene oxide.

Specific examples of these polyether compounds include polyoxyethylene compounds, polyoxypropylene compounds, polyoxybutylene compounds, polyoxyhexylene compounds, polyoxytetramethylene compounds and / or copolymers thereof. Among them, polypropylene oxide, polytetramethylene oxide, and polytetramethylene / polyoxypropylene oxide block copolymer are preferable in view of the physical properties of the cured product, and the molecular weight of 4 is particularly preferable.
Those having a functional group number of 000 to 20,000 and 2 or 3 functional groups are particularly preferable.

The hydrolyzable silicon group in the polyether polymer having at least one hydrolyzable silicon group in the molecule is represented by the following general formula (1). —SiX _q R _3-q (1) (wherein R is a monovalent organic group, X is a hydrolyzable silicon group, and q is 1, 2 or 3.)

In the formula, R is a monovalent organic group, preferably an alkyl group having 8 or less carbon atoms, a phenyl group or a fluoroalkyl group. Particularly preferred are methyl group, ethyl group, propyl group, propenyl group, butyl group, hexyl group, cyclohexyl group, phenyl group and the like.

X is a hydrolyzable group, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, an acid amide group and a hydride group.

Of these, the hydrolyzable group having a carbon atom preferably has 6 or less carbon atoms, and particularly preferably 4 or less carbon atoms. Preferred hydrolyzable groups are lower alkoxy groups having 4 or less carbon atoms, especially methoxy group, ethoxy group, propoxy group,
A propenyloxy group etc. can be illustrated. q is 1, 2 or 3, and particularly preferably 2 or 3.

The method of introducing the silyl group represented by the general formula (1) into the polyether compound is not particularly limited,
For example, it can be introduced by the following method.

(A) A method of reacting a hydrosilyl compound represented by the general formula (2) with an olefin group introduced at the terminal of a polyether compound such as polyoxypropylene having a hydroxyl group. HSiX _q R _3-q (2) (wherein R, X, and q are the same as above).

As a method for introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyether compound and bonded by an ether bond, an ester bond, a urethane bond, a carbonate bond or the like. There is a method.

(B) A method of reacting the terminal of a polyether compound having a functional group with a compound represented by the general formula (3). ^{_{R 3-q -SiX q -R 1}} NCO ··· (3) ( same .R ¹ in said R, X, q the formula 1 to 17 carbon atoms
A divalent hydrocarbon group. )

(C) A polyisocyanate compound such as tolylene diisocyanate is reacted with the end of the polyether compound having a functional group to form an isocyanate group end, and then the silicon compound represented by the general formula (4) is added to the isocyanate group. A method of reacting the W group.

R _3-q -SiX _q -R ¹ W (4) (wherein R, R ¹ , X and q are the same as above. W is a hydroxyl group, a carboxyl group, a mercapto group and an amino group (1 Group containing active hydrogen selected from primary or secondary).

(D) An olefin group is introduced at the terminal of a polyether compound having a functional group, and the olefin group and
A method of reacting a mercapto group of a silicon compound represented by the general formula (4), wherein W is a mercapto group.

The epoxy resin which can be added to the composition of the present invention includes general epoxy resins. As an epoxy resin, 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, hydrogenated bisphenol A type epoxy resin, bisphenol A propylene oxide adduct Glycidyl ether type epoxy resin, diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, etc., diglycidyl ester type epoxy resin, m-aminophenol type epoxy resin , Diaminodiphenylmethane-based epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N
-Diglycidylaniline, N, N-diglycidyl-o-
Commonly used epoxies such as toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized unsaturated polymers such as hydantoin type epoxy resins, and petroleum resins. Examples thereof include resins and vinyl polymers containing an epoxy group, but are not limited thereto.

Among these epoxy resins, those containing at least two epoxy groups in the molecule have high reactivity during curing, and the cured product easily forms a three-dimensional network. Preferred and more preferred are bisphenol A type epoxy resins, phthalic acid ester type diglycidyl esters, novolac type epoxy resins, and vinyl type polymers having at least two epoxy groups in the molecule.

The ratio of the polyether polymer of the present invention to the epoxy resin is determined in the range of 100/1 to 1/100 by weight, depending on the required physical properties, but the ratio of the polyether polymer containing a hydrolyzable silicon group is A ratio of 100/5 to 50/100 is particularly preferable in order to improve the strength properties.

In the present invention, it goes without saying that a curing catalyst for a polyether polymer having a hydrolyzable silicon group and a curing agent for curing an epoxy resin can be used. Examples of such curing catalyst include the following compounds.

Alkyl titanates, acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid, aliphatic diamines such as ethylenediamine and hexanediamine, and aliphatic polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine. , Amine compounds such as alicyclic amines such as piperidine and piperazine, aromatic amines such as metaphenylenediamine, ethanolamines, triethylamine, and various modified amines used as a curing agent for epoxy resins.

[0031]

## STR1 ## _{(n-C 4 H 9)} 2 Sn (OCOC 11 H 23 -
n) ₂ , (n-C ₄ H ₉ ) ₂ Sn (OCOCH = CHC
_{OO-C 4 H 9 -n)} 2, (n-C 4 H 9) 2 Sn (O
_{COCH = CHCOO-CH 3) 2} , (n-C 8 H 17)
₂ Sn (OCOC ₁₁ H ₂₃ -n) ₂ , (n-C ₈ H ₁₇ ) _{2
Sn (OCOCH = CHCOO-C 4} H 9 -n) 2,
_{(N-C 8 H 17)} 2 Sn (OCOCH = CHCOO-C
_{H 3) 2, (n-} C 8 H 17) 2 Sn (OCOCH = CH
_{COO-C 8 H 17 -iso)} 2, Sn (OCO-C 8 H
_17- n) ₂

Carboxylic acid type organotin compounds such as, and mixtures of the above listed carboxylic acid type organotin compounds with the above listed amines.

[0033]

Embedded image (n-C ₄ H ₉ ) ₂ Sn (SCH ₂ COO)
_{2, (n-C 4 H} 9) 2 Sn (SCH 2 COO-C 8 H
_{17 -iso) 2, (n-} C 8 H 17) 2 Sn (SCH 2 C
_{OO) 2, (n-C} 8 H 17) 2 Sn (SCH 2 CH 2 C
_{OO) 2, (n-C} 8 H 17) 2 Sn (SCH 2 COOC
_{H 2 CH 2 OCOCH 2 S)} 2, (n-C 8 H 17) 2 S
n (SCH ₂ COOC ₄ H ₈ OCOCH ₂ S) ₂ , (n
_{-C 8 H 17) 2 Sn (} SCH 2 COO-C 8 H 17 -is
_{o) 2, (n-C} 8 H 17) 2 Sn (SCH 2 COO-C
_{8 H 17 -n) 2, (} n-C 8 H 17) 2 Sn (SCH 2 C
_{OO-C 12 H 25 -n)} 2,

Mercaptide type organotin compounds such as (N-
_{C 4 H 9) 2 Sn =} S, (n-C 8 H 17) 2 Sn = sulfide type organic tin compounds such as S. _{(N-C 4 H 9)} 2 Sn
_{O, (n-C 8 H} 17) 2 SnO or the like organic tin oxide and their organic tin oxide and ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, Reaction products with ester compounds such as dioctyl phthalate. Organotin compounds such as tin chelate complexes such as dibutyltin diacetylacetonate.

Examples of the curing agent or curing catalyst for epoxy resin include generally used curing agents for epoxy resin. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4. Amines such as 6-tris (dimethylaminomethyl) phenol, tertiary amine salts, polyamide resins, imidazoles, dicyandiamides, boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride Acids, carboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic dianhydride, phenoxy resins, carboxylic acids, alcohols, etc. A polyalkylene oxide polymer having at least one in it (terminally aminated polyoxypropylene glycol, terminally carboxylated polyoxypropylene glycol, etc.), polybutadiene modified at the terminal with hydroxyl group, carboxyl group, amino group, etc., hydrogenated polybutadiene Examples thereof include liquid end functional group-containing polymers such as acrylonitrile-butadiene copolymer and acrylic polymers, but are not limited thereto. These curing agents may be used in an appropriate amount depending on the purpose within the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the epoxy compound.

Various known fillers, various fillers, plasticizers, and various additives may be added to the room temperature curable composition of the present invention, if necessary. As the filler, fumed silica, precipitated silica, filler such as silicic acid anhydride, silicic acid hydrate and carbon black, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, Fillers such as ferric oxide, zinc oxide, activated zinc oxide, hydrogenated castor oil and shirasu balloon, and fibrous fillers such as asbestos, glass fibers and filaments can be used.

As the plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate and butyl benzyl phthalate; Aliphatic carboxylic esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, butyl oleate; glycol esters such as pentaerythritol ester; trioctyl phosphate, phosphorus Phosphates such as tricresyl acid; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate; chlorinated paraffins and the like can be used alone or as a mixture of two or more kinds.

Examples of the additives include adhesion promoters, tackifiers, pigments, antioxidants, radical inhibitors, UV inhibitors, lubricants, pigments, air oxidation curable compounds, photopolymerizable compounds, photopolymerization initiators, A polymerizable monomer that can be polymerized with an initiator, a foaming agent, and the like can be used.

Particularly in the case where the compound is used as an elastic adhesive, it is preferable to add an adhesion imparting agent. Examples of such an adhesiveness-imparting agent include a compound containing a silicon atom to which a hydrolyzable group is bonded, which is known as a silane coupling agent. The hydrolyzable group is preferably an alkoxy group from the viewpoint of easy handling. Particularly preferably, a methoxy group or an ethoxy group is preferable because of high reactivity, and it is preferable that two or more, and more preferably three or more of these groups are attached to one silicon atom. These silane coupling agents may be used alone,
You may use together 2 or more types.

As the silane coupling agent, methyl silicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxy are used. Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane,
Diethyldiethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, silane compounds having no functional groups such as vinyltrimethoxysilane, Vinylsilanes such as vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane Silane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N -Β- (aminoethyl) -γ
-Aminopropylmethyldimethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-
Amino group-containing silanes such as β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane , Mercaptosilanes such as γ-mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycodoxypropyltri Epoxysilanes such as ethoxysilane; β-
Carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane,
N-β- (N-carboxylmethylaminoethyl) -γ
Examples include carboxysilanes such as aminopropyltrimethoxysilane.

A reaction product using two or more silane coupling agents may be used. Examples of such adducts include a reaction product of an amino group-containing silane compound and an epoxysilane compound, a reaction product of an amino group-containing silane compound and a (meth) acrylsilane compound, a reaction product of an epoxysilane compound and a mercaptosilane compound, and mercaptosilane. Examples include reaction products of compounds. These reactants can be easily obtained by mixing the silane compound and stirring at room temperature to 180 ° C. for 1 to 8 hours.

Preferred silane coupling agents are methyltrimethoxysilane, methylorthosilicate, γ-glycidoxypropyltrimethoxysilane, and a reaction product of γ-glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. , N- (β-aminoethyl) γ-aminopropyltrimethoxysilane and γ
-A reaction product with glycidoxypropyltrimethoxysilane, a reaction product with N- (β-aminoethyl) γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane, and the like. A silane coupling agent having an amino group and a mercapto group is particularly preferable because it can serve as a curing agent for an epoxy resin.

There is no particular limitation on the method for adjusting the hydrolyzable silicon group-containing polyether polymer and epoxy resin and these various additives. For example, the blended mixture may be mixed with a mixer, a roll, a kneader or the like at room temperature or A usual method such as kneading under heating or using a small amount of a suitable solvent to dissolve and mix the components may be employed.
Also, by combining these components appropriately, 1
It is also possible to prepare and use a liquid type or a two-component type compound.

[0044]

EXAMPLES The present invention will be described below with reference to examples. First, a synthetic example of the polymer used is shown.

Synthesis Example 1 Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene triol having an average molecular weight of 20,000. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxypropylene was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into methyldimethoxysilyl, to obtain a polymer A in which 82% of the terminals were silylated.

(Synthesis Example 2) Propylene oxide was polymerized using diethylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 17,000.
Of polyoxypropylene diol was obtained. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxypropylene was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into methyldimethoxysilyl, to obtain a polymer B in which 79% of the terminals were silylated.

(Synthesis Example 3) Except that the reaction amount of methyldimethoxysilane was lowered, the same reaction as in Synthesis Example 2 was carried out to obtain a polymer C in which 50% of the terminals were silylated.

Synthesis Example 4 Propylene oxide was polymerized using zinc hexacyanocobaltate catalyst with diethylene glycol as an initiator to give an average molecular weight of 10,000.
Of polyoxypropylene diol was obtained. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxypropylene was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into methyldimethoxysilyl, to obtain a polymer D in which 85% of the terminals were silylated.

(Synthesis Example 5) Propylene oxide was polymerized using diethylene glycol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol having an average molecular weight of 4000. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained polyoxypropylene having an allyl group at the end was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group to methyldimethoxysilyl, to obtain a polymer E having 78% of the terminals silylated.

(Synthesis Example 6) Propylene oxide was polymerized using poly (tetramethylene oxide) having a molecular weight of 2000 as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene diol having an average molecular weight of 4000. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxypropylene is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into methyldimethoxysilyl, and the terminal 83%
A polymer F having a silyl group was obtained.

Synthesis Example 7 Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 20,000.
To obtain polyoxypropylene pentaol. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained polyoxypropylene having an allyl group at the terminal was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group to methyldimethoxysilyl, to obtain a polymer G having 60% of the terminals silylated.

(Synthesis Example 8) Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 17,000.
To obtain polyoxypropylene pentaol. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained polyoxypropylene having an allyl group at the end was reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group to methyldimethoxysilyl to obtain a polymer H having 60% of the terminals silylated.

(Synthesis Example 9) Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 10,000.
To obtain polyoxypropylene pentaol. This was reacted with allyl chloride in the presence of alkali to convert the terminal hydroxyl group into an allyl group. Then, the obtained terminal allyl group-containing polyoxypropylene is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into methyldimethoxysilyl to obtain a polymer I in which 49% of the terminals are silylated. It was

Synthesis Example 10 Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 8,000.
To obtain polyoxypropylene pentaol. This was reacted with allyl chloride in the presence of alkali to convert 20% of the terminal hydroxyl groups into allyl groups. Then, the obtained polyoxypropylene containing an allyl group at the end, (CH ₃
O) ₂ CH ₃ Si (CH ₂ ) ₃ NCO was reacted to obtain a polymer J in which 98% or more of the residual hydroxyl groups in allylated polyoxypropylene were silylated.

[Examples 1 to 8, Comparative Examples 1 to 7] Synthesis Example 1
The polymers and epoxy compounds (Epicoat 828, manufactured by Konishi Co., Ltd., bisphenol A type epoxy resin) obtained in Nos. 10 to 10 were mixed in the compositions shown in Tables 1 to 3. The average molecular weights of the polyether polymers used are shown in Tables 1 to 3
It was shown to.

On the other hand, the viscosity (unit: poise) of the obtained composition was measured at 25 ° C. with a BH type viscometer (using a No. 6 rotor). The results are shown in Tables 1 to 3.

Further, with respect to 100 parts of these compositions,
2,4,6-Tris- (dimethylaminomethyl) phenol 3.3 parts, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 1 part, Irganox 10
10 0.5 parts, # 918 (organic tin compound manufactured by Sankyo Machine Gosei Co., Ltd.), and 0.3 part of water were added, and they were well kneaded using a planetary mixer.

These compositions obtained were tested according to JIS K68.
Based on 50, aluminum test pieces of 100 × 25 × 2 mm were stuck together to prepare a test sample.

This was kept at 20 ° C. for 1 week and then at 50 ° C.
Curing and curing for 1 week, shear tensile test (pull speed 50m
m / min). Further, the sample piece after curing and curing was allowed to stand in warm water of 50 ° C. for 2 weeks, and a shear tensile test after the water resistance test was conducted. The results are shown in Tables 1 to 3 (unit: kg / cm ² ).

Comparison of Examples 1 and 2 with Comparative Example 1, Example 3 with Comparative Example 2, Example 4 with Comparative Example 3, Example 5 with Comparative Example 4, Example 6 with Comparative Example 5, and Example 7. Example 6 and Example 8 and Comparative Example 7 are examples of compositions each using a polyether polymer having a similar average molecular weight. In each case, the compositions of Examples containing a terminally hydrolyzable silyl compound of a tetrafunctional polyether polymer had a lower viscosity and excellent workability as compared with the compositions of Comparative Examples. Further, it can be seen that the compositions of Examples are better than the compositions of Comparative Examples in both initial shear tensile strength and retention rate after water resistance.

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

[Table 3]

[0064]

EFFECT OF THE INVENTION The present invention can provide a room temperature curable composition which has a low viscosity, is excellent in workability, and is excellent in adhesiveness to a substrate and water resistance and useful as an elastic adhesive.

Claims (4)

[Claims] 1. A composition comprising a polyether polymer having at least one hydrolyzable silicon group in the molecule and an epoxy resin, wherein part or all of the polyether polymer is tetrafunctional or higher polyoxypropylene. A curable composition which is a polyether polymer (A) in which at least a part of the terminal hydroxyl groups of a polyol is substituted with a hydrolyzable silicon group. 2. The curable resin according to claim 1, wherein the polyether polymer (A) has an average molecular weight of 500 to 25,000 and 25% or more of the terminal hydroxyl groups are substituted with hydrolyzable silicon groups. Composition. 3. The room temperature curable composition according to claim 1, wherein the proportion of the polyether polymer (A) in the total polyether polymer is 5 wt% to 100 wt%. 4. The curable composition according to claim 1, wherein the hydrolyzable silicon group in the polyether polymer having at least one hydrolyzable silicon group in the molecule is represented by the following general formula (1). —SiX _q R _3-q (1) (wherein R is a monovalent organic group, X is a hydrolyzable silicon group, and q is 1, 2 or 3.)