JPH09255881A - Curing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curing composition containing a specific polymer, an amine compound and a (meth)acroyloxy compound, capable of being cured at room temperature by a moisture, excellent in mechanical strength and adhe sion strength to a fluororesin coated steel plate, etc., and useful as an elastic sealant, an adhesive, etc. SOLUTION: This curing composition contains (A) an organic polymer containing a hydrolyzable silicon group capable of forming a cross-linking by a hydrolysis in molecule thereof and (B) an amine compound having a hydrolyzable silicon group such as a compound of the formula: X<0> p Q<2> 3-p Si(Ch2 )3 (NHCH2 CH2 )q NHQ<3> [X<0> is OH or a hydrolyzable group; Q<2> is a 1-20C (substituted monovalent hydrocarbon group; Q<3> is H, a 1-6C alkyl or phenyl; (p) is 1-3; (q) is 0-3] and (C) a compound of the formula [CH2 =CQ<1> -COO-Q<0> ]mT ]Q<1> is H or methyl; Q<0> is a bonding, a 1-40C (branched) (substituted) divalent hydrocarbon group; T is a substituent selected from tetrahydrofurfunyl, phenoxy, OH and a cyclic acetal bond or a 1-40C organic group containing bonding part; (m) is 1-6].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 Organic polymers having one or more hydrolyzable silicon groups in the molecule are used for coating compositions, sealing compositions, etc. by taking advantage of the fact that cured products have rubber elasticity. However, the strength of the cured product, particularly the shear adhesive strength, is insufficient particularly for applications such as adhesives, and there is a practical problem.

In order to solve these drawbacks, an amino group-containing alkoxysilane or a modified product obtained by reacting an amino group-containing alkoxysilane with an epoxy group-containing alkoxysilane or a methacryl group-containing alkoxysilane in an organic polymer containing a hydrolyzable silicon group. Has been proposed (Japanese Patent Publication No. 62-35421). However, when an amino group-containing alkoxysilane is added, there is a problem that the primary amino group in the molecule impairs the water resistance of the cured product, and when the modified product is added, the modulus of the cured product changes greatly and the cured product becomes brittle. There was such a problem.

Further, there has been a problem that sufficient adhesion cannot be obtained for adherends such as polyvinyl chloride and fluorine steel plates, which have been conventionally difficult to adhere.

Further, a method of simultaneously using an amino group-containing alkoxysilane and a (meth) acrylic acid ester (JP-A-6-16921) or a method of using an adduct obtained by reacting both (JP-A-6- 88017), a method of improving the adhesiveness is known, but these methods also have a problem that sufficient adhesion cannot be obtained for adherends such as polyvinyl chloride and fluorine steel plate. .

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above-mentioned drawbacks and to provide a curable composition whose cured product has remarkably excellent mechanical properties and adhesive strength.

[0007]

The present invention is directed to an organic polymer (A) having at least one hydrolyzable silicon group crosslinkable by hydrolysis, an amine compound (B) having a hydrolyzable silicon group. ) And a (meth) acryloyloxy group-containing compound (C) represented by Formula 1 are contained in the curable composition.

[0008]

[CH ₂ = CQ ¹ -COO-Q ⁰ ] _m T Formula 1

In the formula 1, m is an integer of 1 to 6, Q ¹ is a hydrogen atom or a methyl group, Q ⁰ is a bond or has 1 to 4 carbon atoms.
A linear or branched divalent substituted or unsubstituted hydrocarbon group of 0, T is selected from a tetrahydrofurfuryl group, a phenoxy group, a hydroxyl group and a cyclic acetal bond 1
1 to 40 carbon atoms containing at least one substituent or bond
Is an organic group.

The organic polymer (A) having at least one hydrolyzable silicon group capable of being crosslinked by hydrolysis in the present invention is derived from an organic polymer selected from polyether, polyester and polycarbonate. Organic polymers are mentioned. Further, (meth) acrylic acid ester, vinyl alkyl ether, isobutylene, butadiene, chloroprene and other dienes, chlorotrifluoroethylene, tetrafluoroethylene, ethylene or propylene and other polymerizable monomers and hydrolyzable silicon group-containing polymerizable monomers Examples thereof include hydrolyzable silicon group-containing vinyl polymers obtained by copolymerization.

Particularly, an organic polymer derived from an organic polymer selected from polyether, polyester and polycarbonate is preferable, and among them, a hydrolyzable silicon group-containing polyether derived from polyether is particularly preferable.

The polyether is obtained by subjecting an initiator containing active hydrogen to an alkylene oxide ring-opening polymerization reaction in the presence of a catalyst. Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, epichlorohydrin, styrene oxide and allyl glycidyl ether. Also, oxetane, tetrahydrofuran, etc. can be used.

As the initiator, polyhydric alcohols, polycarboxylic acids, polyvalent active hydrogen compounds such as polyamines, terminal unsaturated group-containing monools, unsaturated phenols, unsaturated carboxylic acid-containing unsaturated groups, etc. Examples include active hydrogen compounds.

As the catalyst, alkali metal compounds such as alkali metals such as sodium, potassium and cesium and hydroxides of these alkali metals, complex metal cyanide complexes,
Metal porphyrin complexes can be used.

The hydrolyzable silicon group-containing polyether is
It is particularly preferred that it is derived from a hydroxyl group-containing polyether.

In the present invention, the hydrolyzable silicon group capable of being cross-linked by hydrolysis (hereinafter also simply referred to as a hydrolyzable silicon group) is a condensation reaction such as silanol group or alkoxysilyl group due to moisture or curing catalyst. It is possible to promote high molecular weight by causing cross-linking of the organic polymer,
It is preferably represented by Formula 3.

[0017]

Embedded image —SiX _a R ¹ _3-a ... Formula 3

In the formula 3, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3.

The hydrolyzable silicon group-containing polyether is
When derived from a hydroxyl group-containing polyether, the hydrolyzable silicon group represented by formula 3 is usually introduced via an organic group. Therefore, the organic polymer (A) in the present invention preferably has a group represented by formula 4.

[0020]

Embedded image —R ⁰ —SiX _a R ¹ _3-a ... Formula 4

In the formula 4, R ⁰ is a divalent organic group, R ¹ , X,
a is the same as above.

Here, R ⁰ in the formula 4 is a divalent organic group, preferably a hydrocarbon group having 8 or less carbon atoms. Formula 3, Formula 4
In the above, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and 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, butyl group, hexyl group, cyclohexyl group and phenyl group.

X in formulas 3 and 4 is a hydroxyl group or a hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group or It is a hydrido 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 X is an alkoxy group having 4 or less carbon atoms, particularly a methoxy group,
It is an ethoxy group or a propoxy group. 2 or 3 is preferable for a in Formula 3 and Formula 4.

Examples of the method for producing the organic polymer (A) in the present invention include, but are not limited to, the following (a) to (f). In addition, (a) to (d)
It is an example of a method for producing a hydrolyzable silicon group-containing polyether, and (e) to (f) are examples of a method for producing a hydrolyzable silicon group-containing vinyl polymer.

(A) A method of reacting an organosilicon compound having an isocyanate group and a hydrolyzable silicon group with a hydroxyl group-containing polyether.

As a concrete organosilicon compound,
The compound of

[0027]

Embedded image (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) Formula HSiX _a R ¹ _3-a (wherein R ¹ ,
X and a are the same as the above), and a method in which a silicon hydride compound represented by the above and a polyether having an unsaturated group introduced at the terminal are reacted.

Here, as a method for introducing an unsaturated group,
Method in which OH of hydroxyl group-containing polyether is changed to OM (M is an alkali metal) and then reacted with an unsaturated group-containing halogenated hydrocarbon such as allyl chloride, or a compound having an unsaturated group and a functional group capable of reacting with a hydroxyl group With a hydroxyl group-containing polyether to give an ester bond, a urethane bond,
There is a method of introducing an unsaturated group through a carbonate bond or the like. When polymerizing alkylene oxide in the production of a terminal hydroxyl group-containing polyether, a method of introducing an unsaturated group into a side chain by copolymerizing an unsaturated group-containing alkylene oxide such as allyl glycidyl ether, or a terminal as an initiator. There is also a method of introducing an unsaturated group at the terminal by using a hydroxyl group-containing polyether produced using an unsaturated group-containing monol.

(C) A method in which a polyisocyanate such as tolylene diisocyanate is reacted with an end of the hydroxyl group-containing polyether to form an isocyanate group end, and then the W group of the silicon compound represented by the formula 5 is reacted with the isocyanate group. .

[0031]

Embedded image W—R ² —SiX _a R ¹ _3-a ... Equation 5

In the formula 5, R ¹ , X and a are the same as defined above, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms,
W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group and an amino group (primary or secondary).

(D) A method of reacting the unsaturated group of the polyether having an unsaturated group introduced at the terminal with the mercapto group of the silicon compound represented by the formula 5 in which W is a mercapto group.

(E) A method of copolymerizing a polymerizable monomer having a hydrolyzable silicon group or an oligomer thereof with another polymerizable monomer or an oligomer thereof.

The polymerizable monomer is, for example, the compound represented by the formula 6 alone or as a mixture of two or more kinds.

[0036]

Embedded image CR ³ ₂ = CR ⁴ R ⁵ ... Formula 6

In the formula 6, R ³ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, and R ⁴ and R ⁵ are monovalent organic groups. R ³ is preferably a hydrogen atom or a monovalent hydrocarbon group, and R ⁴ and R ⁵ are a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a phenyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, A group selected from a glycidoxycarbonyl group, a cyano group, an alkenyl group, an acyloxy group, an amide group and a pyridyl group is preferable.

Specific examples of the polymerizable monomer include styrene-based monomers such as styrene and α-methylstyrene, (meth) acrylic acid, their esters or (meth) acrylic monomers such as (meth) acrylamide, acrylonitrile, 2 , 4-dicyanobutene-1 and other cyano group-containing monomers, vinyl acetate and other vinyl ester-based monomers, isoprene and butadiene and other diene-based monomers, isobutylene and other olefins and other unsaturated esters, halogenated olefins, vinyl ethers and the like. .

As the polymerizable monomer having a hydrolyzable silicon group, a compound represented by the formula 7 is used.

[0040]

[Image Omitted] Y _3-n -SiR ⁶ _n R ⁷ ... Formula 7

In the formula 7, R ⁶ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Y is a hydroxyl group, a halogen atom, an alkoxy group, an acyloxy group, an amido group, an amino group, It is a hydrolyzable group such as an aminoxy group and a ketoximate group, R ⁷ is an organic residue having a polymerizable unsaturated group, and n is an integer of 0 to 2.

Specific examples of the compound represented by the formula 7 include compounds represented by Chemical formula 11 and the like.

[0043]

CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₃ S
_{i (CH 3) (OCH 3} ) 2, CH 2 = C (CH 3) Si (CH 3) (OCH 3) 2.

(F) A method of polymerizing a polymerizable monomer in the presence of a chain transfer agent containing a hydrolyzable silicon group.

Specific examples of the chain transfer agent containing a hydrolyzable silicon group include the compounds of Chemical formula 12 and the like.

[0046]

Embedded image HS (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , HS (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ .

The molecular weight of the organic polymer (A) is preferably 1000 or more. It is more preferably 1,000 to 50,000, particularly preferably 5,000 to 30,000, and more preferably 8,000 to 30,000.

In the present invention, the amine compound (B) having a hydrolyzable silicon group is used. Amine compound (B)
Preferably has a hydrolyzable silicon group represented by Formula 3, and particularly preferably has an alkoxysilyl group. Examples of the alkoxysilyl group include a trialkoxysilyl group, a dialkoxysilyl group and a monoalkoxysilyl group.

The amine compound (B) is preferably a compound having one hydrolyzable silicon group in one molecule.
The amine compound (B) is preferably a compound having a primary amino group and / or a secondary amino group as an amino group, and particularly preferably a compound having a primary amino group. The amine compound (B) is preferably a compound having a molecular weight of less than 1000. The amine compound (B) is particularly preferably the compound represented by formula 2.

[0050]

Embedded image X ⁰ _p Q ² _3-p Si (CH ₂ ) ₃ (NHCH ₂ CH ₂ ) _q NHQ ³ ... Formula 2

In formula 2, X ⁰ is a hydroxyl group or a hydrolyzable group, Q ² is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Q ³ is a hydrogen atom, and 1 to 6 carbon atoms. An alkyl group or a phenyl group, p is an integer of 1 to 3, and q is an integer of 0 to 3.

The amine compound (B) is specifically 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldimethylmethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3
-Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyldimethylmethoxysilane, N-phenyl-3-aminopropyltrisilane Examples thereof include methoxysilane. The amine compound (B) may be used alone or in a mixture of two or more kinds.

The compound (B) is used in a weight ratio of (A) /
(B) = 100 / 0.1 to 100/40 is preferable, and 100 / 0.1 to 100/20 is particularly preferable.

In the present invention, the (meth) acryloyloxy group-containing compound (C) represented by the formula 1 is used. As the compound (C), only one type may be used, or two or more types may be used in combination.

[0055]

[CH ₂ = CQ ¹ -COO-Q ⁰ ] _m T Formula 1

In the formula 1, m is an integer of 1 to 6, Q ¹ is a hydrogen atom or a methyl group, Q ⁰ is a bond or has 1 to 4 carbon atoms.
A linear or branched divalent substituted or unsubstituted hydrocarbon group of 0, T is selected from a tetrahydrofurfuryl group, a phenoxy group, a hydroxyl group and a cyclic acetal bond 1
1 to 40 carbon atoms containing at least one substituent or bond
Is an organic group.

In the formula 1, m is preferably 1 to 2 when the elongation of the cured product of the composition is required. Q ¹ is preferably a hydrogen atom. T is preferably an organic group containing at least one substituent or bond selected from a tetrahydrofurfuryl group, a phenoxy group, and a cyclic acetal bond. In the present invention, the cyclic acetal bond means a structure represented by Chemical formula 15.

[0058]

Embedded image

In Chemical Formula 15, Z ^{1 to} Z ⁸ are a bond, a hydrogen atom, or a substituted or unsubstituted 1 to 1 to 20 carbon atom.
Represents a monovalent hydrocarbon group. Z ^{1 to} Z ⁸ may be the same or different.

A specific example of (B-2) will be given below. Examples of the tetrahydrofurfuryl group-containing (meth) acryloyloxy group-containing compound include Kayarad T manufactured by Nippon Kayaku Co., Ltd.
C-110S (Chemical formula 16) can be mentioned. In chemical formula 16, the average value of n is 1.

Examples of the phenoxy group-containing (meth) acryloyloxy group-containing compound include polyoxyalkylene glycol phenyl ether (meth) acrylate. Particularly, polyoxyethylene glycol phenyl ether (meth) acrylate is preferable, and examples include Kayarad R-564 (Chemical formula 17) manufactured by Nippon Kayaku. In Chemical formula 17, the average value of n is 2.3.

As the hydroxyl group-containing (meth) acryloyloxy group-containing compound, hydroxyalkyl (meth) acrylate and polyoxyalkylene glycol mono (meth)
Acrylate, polyhydric alcohol mono (meth) acrylate, etc. are mentioned. More specifically, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate such as BLEMMER AE-350 (Chemical Formula 18) manufactured by NOF CORPORATION, polypropylene glycol mono (meth) acrylate, poly Tetramethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate,
There is glycerol di (meth) acrylate.

Examples of the (meth) acryloyloxy group-containing compound containing a cyclic acetal bond include Kayarad R-644 (Chemical Formula 19) and Kayarad R-604 (Chemical Formula 20) manufactured by Nippon Kayaku. In chemical formula 19, the average value of n is 1.

Further, glycerol monophenyl ether mono (meth) acrylate (Kayarad R manufactured by Nippon Kayaku Co., Ltd.
-128H (Chemical Formula 21)) and the like, which may contain two or more kinds of substituents.

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

[Chemical 21]

The compound (C) is used in a weight ratio of (A) /
(C) = 100 / 0.1 to 100/40 is preferable, and 1
It is particularly preferably 00 / 0.1 to 100/20.

The molar amount of the amine compound (B) and the compound (C) used is preferably 100: 1 to 1: 100, and more preferably 5: 1 to 1: 5.

When elongation is required for the cured product of the composition, it is preferable to use the amine compound (B) and the compound (C) in a molar ratio of about 1: 1 to 1: 2. preferable. Further, the compound (C) preferably has 1 or 2 (meth) acryloyloxy groups. However, this does not apply if elongation of the cured product of the composition is not particularly required.

A filler, a plasticizer, a curing catalyst, and other additives may be added to the curable composition of the present invention, if necessary.

(Filler) As the filler, known fillers can be used. The amount of the filler used is 100% of the organic polymer (A).
0 to 1000 parts by weight, especially 50 to 250 parts by weight
Parts by weight are preferred. The following are specific examples of the filler. These fillers may be used alone,
Two or more kinds may be used in combination.

Calcium carbonate, fumed silica, precipitated silica, silicic acid anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, Powdered fillers such as zinc oxide, activated zinc white, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, asbestos, glass fiber, glass filament, Fibrous fillers such as carbon fiber, Kevlar fiber and polyethylene fiber.

(Plasticizer) As the plasticizer, known plasticizers can be used. The amount of the plasticizer used is the organic polymer (A) 10
0 to 100 parts by weight is preferable with respect to 0 parts by weight. The following are specific examples of the plasticizer.

Dioctyl phthalate, dibutyl phthalate,
Phthalates such as butylbenzyl phthalate. Aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate. Alcohol esters such as pentaerythritol ester. Phosphate esters such as trioctyl phosphate and tricresyl phosphate. Epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxystearate. Chlorinated paraffin. Polyester plasticizers such as polyesters of dibasic acids and dihydric alcohols, polyethers such as polyoxypropylene glycol and its derivatives, oligomers of polystyrene such as poly-α-methylstyrene and polystyrene, polybutadiene, butadiene- Polymer plasticizers such as acrylonitrile copolymer, oligomers such as polychloroprene, polyisoprene, polybutene, hydrogenated polybutene, and epoxidized polybutadiene.

(Curing catalyst) In curing the curable composition of the present invention, a curing catalyst that accelerates the curing reaction of the hydrolyzable silyl group may be used. The following compounds may be mentioned as specific examples. One or more of them are used. The curing catalyst is an organic polymer (A) 100.
It is preferable to use 0 to 10 parts by weight with respect to parts by weight.

Metal titanates, organosilicon titanates, metal salts such as bismuth tris (2-ethylhexoate), acidic compounds such as phosphoric acid, p-toluenesulfonic acid and phthalic acid, ethylenediamine, hexanediamine, etc. Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, heterocyclic amines such as piperidine and piperazine, aromatic amines such as m-phenylenediamine, alkanolamines and dibutylamine 2-amine compounds such as amine salts such as 2-ethylhexoate and various modified amines used as a curing agent for epoxy resins.

Tin dioctylate, dibutyltin dilaurate, dioctyltin dilaurate and the carboxylic acid type organotin compounds of Chemical formula 22 and mixtures of these carboxylic acid type organotin compounds with the above amines.

The sulfur-containing organotin compound of Chemical formula 23:

Organotin oxides such as (nC ₄ H ₉ ) ₂ SnO and (nC ₈ H ₁₇ ) ₂ SnO, and these organotin oxides and ethyl silicates, dimethyl maleate, diethyl maleate, dioctyl maleate and phthalic acid. Reaction products with ester compounds such as dimethyl, diethyl phthalate and dioctyl phthalate.

The chelate tin compounds of Chemical formula 24 and reaction products of these tin compounds with alkoxysilanes (where acac is an acetylacetonato ligand).

The tin compound of formula 25:

[0086]

Embedded image (nC ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOCH ₃ ) ₂ , (nC ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ -n) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (OCOCH _{= CHCOOCH 3) 2, (nC} 8 H 17) 2 Sn (OCOCH = CHCOOC 4 H 9 -n) 2, (nC 8 H 17) 2 Sn (OCOCH = CHCOOC 8 H 17 -iso) 2.

[0087]

Embedded image (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COO), (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO), (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO), (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOCH ₂ CH ₂ OCOCH ₂ S), (nC ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ -iso) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC _{8 H 17 -iso) 2, (} nC 8 H 17) 2 Sn (SCH 2 COOC 8 H 17 -n) 2, (nC 4 H 9) 2 SnS.

[0088]

Embedded image (nC ₄ H ₉ ) ₂ Sn (acac) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (acac) ₂ , (nC ₄ H ₉ ) ₂ (C ₈ H ₁₇ O) Sn (acac).

[0089]

Embedded image (nC ₄ H ₉ ) ₂ (CH ₃ COO) SnOSn (OCOCH ₃ ) (nC ₄ H ₉ ) ₂ , (nC ₄ H ₉ ) ₂ (CH ₃ O) SnOSn (OCH ₃ ) (nC ₄ H ₉ ) ₂ .

The curable composition of the present invention is cured at room temperature in the presence of moisture and can be used especially for elastic sealants and adhesives. The curable composition has excellent adhesive strength, and particularly has excellent adhesiveness to a fluorine steel plate. Therefore, it is suitable as an adhesive or a sealing agent for a building material coated with a fluorine-based coating material such as an outer wall material, a sash, or a fluorine-based coating agent.

[0091]

The present invention will be described below with reference to Examples (Examples 1 to 12) and Comparative Examples (Examples 13 to 16).

[Preparation of Polyether P1] A molecular weight of 1700 obtained by polymerizing propylene oxide with glycerin as an initiator and a zinc hexacyanocobaltate catalyst.
After converting the terminal hydroxyl group of polyoxypropylene triol of 0 to an allyloxy group, it was purified. Methyldimethoxysilane was reacted in the presence of a platinum catalyst to convert the allyl group into a methyldimethoxysilylpropyl group to obtain polyether P1.

Examples 1 to 16 Polyether P1 100
15 parts by weight (hereinafter referred to as “parts”) of calcium carbonate
0 parts, 50 parts of plasticizer, 3 parts of thixotropic agent, the number of parts of the compound (C) shown in the table, and the compound (B),
The number of parts shown in the table for N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (compound (C), the combination of the number of parts and the number of parts of compound (B) are shown by the example numbers shown in Tables 1 and 2). ), Vinyltrimethoxysilane 5 parts, S
After adding 2 parts of bisacetylacetonato tin as an n-based curing catalyst and mixing well, it was cured and cured under moisture to give JIS A
According to 5758, the tensile adhesion of the aluminum plate to the aluminum plate was evaluated. Further, this was immersed in ion-exchanged water at 20 ° C. for 7 days, and then the same test was performed to evaluate the water-resistant adhesion.

Similarly, the tensile adhesion between the fluorine steel plate and the fluorine steel plate was evaluated. The results are shown in Tables 3-5.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

[0100]

EFFECTS OF THE INVENTION The curable composition of the present invention has an effect of exhibiting remarkably high mechanical strength and providing a curable composition having particularly excellent adhesive strength.

Claims (5)

[Claims] 1. An organic polymer (A) having at least one hydrolyzable silicon group crosslinkable by hydrolysis, an amine compound (B) having a hydrolyzable silicon group, and
A curable composition comprising a (meth) acryloyloxy group-containing compound (C) represented by Formula 1. [CH ₂ ═CQ ¹ —COO-Q ⁰ ] _m T ... Formula 1 In Formula 1, m is an integer of 1 to 6, Q ¹ is a hydrogen atom or a methyl group, and Q ⁰ is a bond or A linear or branched divalent substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms,
T is an organic group having 1 to 40 carbon atoms containing at least one substituent selected from a tetrahydrofurfuryl group, a phenoxy group, a hydroxyl group and a cyclic acetal bond or a bond. 2. The curable composition according to claim 1, wherein the amine compound (B) is a compound having one hydrolyzable silicon group in one molecule. 3. The curable composition according to claim 1, wherein the amine compound (B) is a compound having a primary amino group and / or a secondary amino group. 4. The curable composition according to claim 1, wherein the amine compound (B) is a compound represented by formula 2. Embedded image X ⁰ _p Q ² _3-p Si (CH ₂ ) ₃ (NHCH ₂ CH ₂ ) _q NHQ ³ ... Formula 2 In Formula 2, X ⁰ is a hydroxyl group or a hydrolyzable group, and Q ² is carbon. A substituted or unsubstituted monovalent hydrocarbon group of the number 1 to 20, Q
³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, p is an integer of 1 to 3, and q is an integer of 0 to 3. 5. The curable composition according to claim 1, wherein the hydrolyzable silicon group is a group represented by formula 3. Embedded image —SiX _a R ¹ _3-a ... Formula 3 In Formula 3, R ¹ is a substituted or unsubstituted 1 having 1 to 20 carbon atoms.
Valent hydrocarbon group, X is a hydroxyl group or a hydrolyzable group, and a is an integer of 1 to 3.