JPH09279049A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which exhibits very excellent mechanical properties and bonding strength. SOLUTION: The composition contains an organic polymer having at least one hydrolyzable silicon group cross-linkable through hydrolysis and a silicon compound obtained by reacting an amine compound having hydrolyzable silicon group(s) with a fluorine compound having polyfluorohydrocarbon group(s) and ethylenically unsaturated group(s).

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 which exhibits remarkably excellent mechanical properties and has particularly excellent adhesive strength.

[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. For example, when this is used as an adhesive, there arises a problem that the shear adhesive strength is insufficient.

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 the 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. When the modified product is added, there are problems that the modulus of the cured product is large and the cured product becomes brittle and that the fracture state of the test substance after the water resistance test shows a tendency of interfacial peeling.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks, and the cured product thereof exhibits remarkably excellent mechanical properties and adhesive strength, and particularly the adhesive strength and interfacial peeling rate after a water resistance test are improved. An object of the present invention is to provide a curable composition characterized by being excellent in retention rate.

[0005]

The present invention is the following inventions. An organic polymer (A) having at least one hydrolyzable silicon group crosslinkable by hydrolysis in the molecule, and an amine compound (B) having a hydrolyzable silicon group, a polyfluorohydrocarbon group, and an ethylenic monomer. A curable composition comprising a silicon compound (D) obtained by reacting with a fluorine compound (C) having a saturated group.

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 fluorine compound (C) having a polyfluorohydrocarbon group and an ethylenically unsaturated group.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The organic polymer (A) having at least one hydrolyzable silicon group capable of being crosslinked by hydrolysis in the present invention is an organic polymer selected from polyether, polyester and polycarbonate. And organic polymers derived from 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 a hydrolyzable silicon group-containing polyether derived from polyether is particularly preferable.

The polyether is obtained by subjecting an initiator containing active hydrogen to a ring-opening polymerization reaction of an alkylene oxide 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.

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

As the catalyst, alkali metals such as sodium, potassium and cesium, alkali metal compounds such as 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 due to moisture, a curing catalyst or the like like a silanol group or an alkoxysilyl group. It is possible to promote high molecular weight by causing cross-linking of the organic polymer,
It is preferably represented by Formula 4.

[0014]

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

In the formula 4, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a monovalent 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 4 is usually introduced via an organic group. Therefore, the organic polymer (A) in the present invention preferably has a group represented by formula 5.

[0017]

Embedded image —R ⁰ —SiX _a R ¹ _3-a ... Formula 5

In formula 5, R ⁰ is a divalent organic group, R ¹ , X,
a is the same as above.

Here, R ⁰ in the formula 5 is a divalent organic group, preferably a hydrocarbon group having 8 or less carbon atoms. Formula 4, Formula 5
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 the formulas 4 and 5 is a hydroxyl group or a monovalent hydrolyzable group, and examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an amide group,
It is an amino group, an aminooxy group, a ketoximate group or 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 X is an alkoxy group having 4 or less carbon atoms, particularly a methoxy group, an ethoxy group or a propoxy group. 2 or 3 is preferable for a in Formula 4 and Formula 5.

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 organic silicon compound,
The compound of

[0024]

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.

The method for introducing the unsaturated group is as follows.
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 6 is reacted with the isocyanate group. .

[0028]

Embedded image W—R ² —SiX _a R ¹ _3-a ... Formula 6

In the formula 6, 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 6 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 7 alone or as a mixture of two or more kinds.

[0033]

Embedded image CR ³ ₂ = CR ⁴ R ⁵ ... Formula 7

In the formula 7, R ³ is a hydrogen atom, a halogen atom or a monovalent hydrocarbon group, preferably a hydrogen atom or a monovalent hydrocarbon group. R ⁴ and R ⁵ are hydrogen atom, halogen atom, monovalent hydrocarbon group, phenyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, glycidoxycarbonyl group, cyano group, alkenyl group, acyloxy group, amide group and A group selected from a pyridyl group.

Specific examples of the polymerizable monomer include styrene-based monomers such as styrene and α-methylstyrene, (meth) acrylic acid, their esters or (meth) acryl-based monomers such as (meth) acrylamide, acrylonitrile, 2 , 4-dicyanobutene-1 and other cyano group-containing monomers, vinyl acetate and other vinyl ester monomers, isoprene and butadiene and other diene 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 8 is used.

[0037]

Embedded image Y _3-b —SiR ⁶ _b R ⁷ ... Formula 8

In the formula 8, 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 group having a polymerizable unsaturated group, and b is an integer of 0 to 2.

Specific examples of the compound represented by the formula 8 include compounds represented by Chemical formula 11 and the like.

[0040]

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.

[0043]

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.

The fluorine compound (C) used in the present invention is preferably a compound represented by the formula 1.

[0046]

Embedded image [CH ₂ ═CQ ⁰ − (CH ₂ ) _n −Z−Q−] _m R ^f ... Formula 1

In the formula 1, n is an integer of 0 to 6, m is an integer of 1 to 3, Q ⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a bond, —O—, —COO—. , -OCO-,-
A group selected from CONH- and -NHCO-, Q is a bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^f is a monovalent polyfluoro group having 1 to 40 carbon atoms. It is a hydrocarbon group.

Among the compounds represented by the formula 1, the fluorine compound (C) is particularly preferably the compound represented by the formula 2.

[0049]

[CH ₂ ═CQ ¹ —COO-Q-] _m R ^f Formula 2

In formula 2, m is an integer of 1 to 3, Q ¹ is a hydrogen atom or a methyl group, Q is a bond or a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R ^f is Carbon number 1
-40 is a monovalent polyfluorohydrocarbon group.

The polyfluorohydrocarbon group in formula 1 or 2 means a group in which two or more hydrogen atoms of the hydrocarbon group are substituted with fluorine atoms. The polyfluorohydrocarbon group has 1 to 40 carbon atoms, particularly 1 to 22 carbon atoms, and further 1 to 1 carbon atoms.
8 is preferred.

With respect to the number of fluorine atoms in the polyfluorohydrocarbon group, the ratio of the number of substituted fluorine atoms to the number of hydrogen atoms of the unsubstituted hydrocarbon group is preferably 50% or more, more preferably 60% or more. 80% is more preferable, especially substantially 100%
Is preferred. Furthermore, some or all of the non-substituted hydrogen atoms may be replaced with chlorine atoms.

The structure of the polyfluorohydrocarbon group may be linear or branched. The polyfluorohydrocarbon group is carbon-
An etheric oxygen atom or a thioetheric sulfur atom may be inserted between the carbon bonds. The tip portion of the polyfluorohydrocarbon group is preferably a perfluorohydrocarbon portion.

Q may be substituted with a halogen atom or a hydroxyl group, but is preferably an unsubstituted alkylene group.

In Formula 2 or Formula 3, it is preferable that m is 1, that is, the polyfluorohydrocarbon group is monovalent. A specific example of the -Q-R ^f group when m is 1 is shown in Chemical formula 15. In Chemical formula 15, t represents an integer of 1 to 12.

[0056]

Embedded image F (CF ₂ ) _t CH ₂ —F (CF ₂ ) _t CH ₂ CH ₂ —F (CF ₂ ) _t CH ₂ CH ₂ CH ₂ —F (CF ₂ ) _t (CH ₂ ) ₆ — ( _{CF 3) 2 CF (CF 2} ) t CH 2 CH 2 - (CF 3) 2 C (CH 3) CH 2 - CF 3 CHFCF 2 CH 2 - H (CF 2) t CH 2 - F (CF 2) t _{CH = CHCH 2 - F (CF} 2) t CH 2 cHICH 2 - (CF 3) 2 CF (CF 2) t CH 2 cHICH 2 - F (CF 2) t CH 2 CH (OH) CH 2 - (CF 3 ) ₂ CF (CF ₂ ) _t CH ₂ CH (OH) CH
_{2 - F (CF 2) 3} OCF (CF 3) CH 2 - (CF 3) 2 CH- C t F 2t + 1 CH 2 CH 2 OCH 2 CH 2 - C t F 2t + 1 (CH 2) 6 OCH _{2 CH 2 - F (CF 2} ) t - (CF 3) 2 CF (CF 2) t - H (CF 2) t - (CF 3) 2 C = CF- CF 3 O [CF (CF ₃₎ CF ₂ O] _t CF (CF ₃ )
- C ₃ F ₇ O [CF (CF ₃₎ CF ₂ O] _t CF (CF
_{3) - CF 3 CHFO (CF} 2) 3 -

Specific examples of the fluorine compound (C) include the following, but the invention is not limited thereto. 2,
2,2-trifluoroethyl acrylate, 2,2
2,2 ′, 2 ′, 2′-hexafluoroisopropyl acrylate, (perfluorooctyl) ethyl acrylate, (perfluorononyl) ethyl acrylate.

The amine compound (B) used in the present invention preferably has a hydrolyzable silicon group represented by the formula 4, and particularly preferably 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 the formula 3.

[0061]

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

In the formula 3, X ⁰ is a hydroxyl group or a monovalent hydrolyzable group, and Q ² is a substituted or unsubstituted 1 to 20 carbon atom.
Valent hydrocarbon group, 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, q is 0.
It is an integer of 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, N'-bis (3- Trimethoxysilylpropyl) ethylenediamine, N, N'-bis (3-methyldimethoxysilylpropyl) ethylenediamine, N, N'-bis (3-triethoxysilylpropyl) ethylenediamine, N-phenyl-3-aminopropyltrimethoxysilane , N-benzyl-3-aminopropyltrimethoxysilane and the like. The amine compound (B) may be used alone or in a mixture of two or more kinds.

In the present invention, a silicon compound (D) obtained by reacting an amine compound (B) having a hydrolyzable silicon group with a fluorine compound (C) having a polyfluorohydrocarbon group and an ethylenically unsaturated group ) Can be used.

When the silicon compound (D) is obtained, the amine compound (B) and the fluorine compound (C) are easily reacted by mixing them. It is particularly preferable to add the fluorine compound (C) dropwise while stirring the amine compound (B) at room temperature to 180 ° C under non-aqueous conditions. Two or more kinds of each of the amine compound (B) and the fluorine compound (C) may be used in the reaction.

At this time, the amounts of the amine compound (B) and the fluorine compound (C) used are preferably 100: 1 to 1: 100 in molar ratio, and particularly preferably 5: 1 to 1: 5. The ratio of the silicon compound (D) used to the organic polymer (A) is (A) / (B) = 100 / 0.1-100 in weight ratio.
The range of / 40 is preferable.

In the present invention, an amine compound (B) having a hydrolyzable silicon group, and a fluorine compound (C) having a polyfluorohydrocarbon group and an ethylenically unsaturated group
The composition can also be obtained by adding and mixing each of the above.

Amine compound (B) and fluorine compound (C)
When each is added, the amount of the fluorine compound (C) used is (A) / (C) = 100 / 0.1 to 100 by weight ratio.
/ 40 is preferable, and 100 / 0.1 to 100/20 is particularly preferable. The amount of the amine compound (B) and the amount of the fluorine compound (C) used is 100: 1 to 1: 1 in a molar ratio.
It is preferably 100, particularly preferably 5: 1 to 1: 5.

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

(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 anhydride, hydrous silicic acid and carbon black, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, Powdered filler such as zinc oxide, activated zinc flower, shirasu balloon, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, graphite, aluminum fine powder, flint powder, asbestos, glass fiber, glass filament, Fibrous filler such as carbon fiber, Kevlar fiber, 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, phthalic acid, ethylenediamine, hexanediamine, etc. Aliphatic polyamines such as aliphatic diamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine, heterocyclic amines such as piperidine and piperazine, aromatic amines such as m-phenylenediamine, alkanolamines and diamines. Amine compounds such as amine salts such as butylamine-2-ethylhexoate and various modified amines used as curing agents for epoxy resins.

Tin dioctylate, dibutyltin dilaurate, dioctyltin dilaurate and the carboxylic acid type organotin compounds of Chemical formula 17, and mixtures of these carboxylic acid type organotin compounds with the above amines.

The sulfur-containing organotin compound of Chemical formula 18

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, phthalic acid Reaction products with ester compounds such as dimethyl, diethyl phthalate and dioctyl phthalate.

The chelate tin compounds of Chemical formula 19 and the reaction products of these tin compounds with alkoxysilanes (where acac is an acetylacetonato ligand, e-aca)
c is an acetoacetic acid ester ligand).

The tin compound of Chemical formula 20:

[0081]

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.

[0082]

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.

[0083]

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). _{(nC 4 H 9) 2 (} C 8 H 17 O) Sn (e-acac).

[0084]

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 .

(Others) As the dehydrating agent, hydrolyzable organic silicon compounds such as alkyl orthoformates, vinyltrimethoxysilane, and tetraethylsilicate, hydrolyzable organic titanium compounds and the like 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. 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.

[0087]

【Example】

[Production Example 1] Polyoxypropylene triol was obtained by polymerizing propylene oxide with zinc hexacyanocobaltate catalyst using glycerin as an initiator. After converting the terminal hydroxyl group to an allyloxy group, methyldimethoxysilane is reacted in the presence of a platinum catalyst to convert the allyl group to a methyldimethoxysilylpropyl group.
000 polyethers P1 were obtained.

[Production Example 2] A 500 mL flask equipped with a stirrer, a temperature controller, a thermometer and a condenser was charged with N-.
(2-Aminoethyl) -3-aminopropyltrimethoxysilane (hereinafter referred to as compound B1) (111 g, 0.
5 mol), and 2,2,2-trifluoroethyl acrylate (hereinafter referred to as compound C1) under non-aqueous conditions (7
(7 g, 0.5 mol) was added dropwise at room temperature, and the mixture was further reacted for 1 hour to obtain compound P2.

[Production Example 3] Amine compound B1 (111 g, 0.5 mol) was added to the same flask as in Production Example 2, and the average carbon number of the perfluoroalkyl moiety was 9 under non-aqueous conditions (per). Fluoroalkyl) ethyl acrylate (hereinafter referred to as compound C2) (284 g, 0.5 mol) was added dropwise at room temperature, and the mixture was further reacted for 2 hours to give compound P3.
I got

[Production Example 4] Amine compound B1 (111 g, 0.5 mol) was added to the same flask as in Production Example 2, and octyl acrylate (hereinafter referred to as compound C3) (50 g, 0) under non-aqueous conditions. 0.5 mol) at room temperature,
The reaction was continued for 2 hours to obtain compound P4.

Examples 1 to 4 and Comparative Examples 1 to 2 100 parts by weight of polyether P1 (hereinafter referred to as "parts") 150 parts of calcium carbonate, 50 parts of a plasticizer, 3 parts of a thixotropic agent, Of the compounds P2 to P4, the parts shown in the table, 5 parts of vinyltrimethoxysilane and 2 parts of bisacetylacetonate tin catalyst were added and mixed well, followed by curing and curing under humidity, in accordance with JIS A5758. Then, the tensile adhesion between the aluminum plate and 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. The results are shown in Table 1 as Examples 1 to 4 and Comparative Examples 1 and 2.

[0092]

[Table 1]

[Examples 5 to 8 and Comparative Examples 3 to 4] The same procedure as in Example 1 was carried out except that instead of the compound P2, the parts shown in the table of the compound B1 and the parts shown in the table of the compounds C1 to C3 were used. . Table 2 shows the results.

[0094]

[Table 2]

[0095]

The curable composition of the present invention exhibits remarkably excellent mechanical properties and adhesive strength, and is particularly excellent in adhesive strength and interfacial peeling retention after a water resistance test. It has the effect of giving things.

Claims (8)

[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 polyfluorohydrocarbon. A curable composition comprising a silicon compound (D) obtained by reacting a fluorine compound (C) having a group with an ethylenically unsaturated group. 2. 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 fluorine compound (C) having a polyfluorohydrocarbon group and an ethylenically unsaturated group. 3. The curable composition according to claim 1, wherein the fluorine compound (C) is a compound represented by formula 1. [CH ₂ ═CQ ⁰ − (CH ₂ ) _n −Z−Q−] _m R ^f ... Formula 1 In Formula 1, n is an integer of 0 to 6, m is an integer of 1 to 3, Q ⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z is a bond, a group selected from —O—, —COO—, —OCO—, —CONH— and —NHCO—, and Q is a bond or a carbon. A substituted or unsubstituted divalent hydrocarbon group of the number 1 to 10,
R ^f is a monovalent polyfluorohydrocarbon group having 1 to 40 carbon atoms. 4. The curable composition according to claim 3, wherein the fluorine compound (C) is a compound represented by formula 2. [CH ₂ ═CQ ¹ —COO-Q-] _m R ^f ... Formula 2 In Formula 2, m is an integer of 1 to 3, Q ¹ is a hydrogen atom or a methyl group, and Q is a bond or A substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ^f is 1 to 1 to 40 carbon atoms
It is a trivalent polyfluorohydrocarbon group. (5) The amine compound (B) is a compound having one hydrolyzable silicon group in one molecule.
Curable composition in any one of. 6. 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. 7. The curable composition according to claim 1, wherein the amine compound (B) is a compound represented by formula 3. Embedded image X ⁰ _p Q ² _3-p Si (CH ₂ ) ₃ (NHCH ₂ CH ₂ ) _q NHQ ³ ... Formula 3 In Formula 3, X ⁰ is a hydroxyl group or a monovalent hydrolyzable group, and Q is ²
Is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, 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, q is 0 to 3 Is an integer. 8. The curable composition according to claim 1, wherein the hydrolyzable silicon group is a group represented by formula 4. Embedded image -SiX _a R ¹ _3-a in Equation 4 Equation 4, R ¹ is 1 substituted or unsubstituted 1 to 20 carbon atoms
A valent hydrocarbon group, X is a hydroxyl group or a monovalent hydrolyzable group, and a is an integer of 1 to 3.