JPH0782492A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition having elasticity after curing, excellent weather resistance, stain resistance and long-term bond strength retention, comprising a fluorine-containing organic elastic polymer having a curable site, a silane coupling agent and a curing catalyst. CONSTITUTION:This composition comprises (A) a fluorine-containing organic elastic polymer having a curable site, (B) a silane coupling agent (e.g. methyltrimethoxysilane) and (C) a curing catalyst for the component A and/or a catalyst for promoting the reaction of the component B. The component A, for example, is obtained by mixing a chlorotrifluoroethylene/ethyl vinyl ether/hydroxybutylvinyl vinyl ether copolymer with a polyoxypropylenetriol having a hydrolyzable silyl as a curable site introduced to the end. In the case wherein the curable site of the component A is a hydrolyzable silyl group or the component C is added as the curing catalyst for the component B, phosphoric acid, ethylenediamine, etc., can be used as the component C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to curable compositions.

[0002]

2. Description of the Related Art Conventionally, in the field of sealing materials and coating materials, it has been necessary to develop a resin which is excellent in stretchability and weather resistance and can be cured at room temperature. In addition to this, in recent years, for example, even if the above-mentioned conditions are satisfied, such as a silicone resin, the problem of occurrence of contamination due to migration of low-molecular weight silicone oil or plasticizer contained therein, and coating repeatability. Is also emerging. Taking sealing materials as an example, the oil-based caulking material, which has no elasticity, has evolved to urethane type and polysulfite type, which are elastic types, and a silicone type with good weather resistance has been developed. It had the drawback of being extremely contaminated.

Therefore, a modified silicone having a polyalkylene oxide as the skeleton and having a siloxane bond only at the cross-linking site has been developed. For example, JP-B-45-36319, JP-B-46-17553, and JP-B-46-30711. JP-A-61-18582, JP-A-60-67
47, JP-A-3-43449, JP-A-3-47.
825, JP-A-3-72527, JP-A-3
-79627, etc. However, even if these materials are used, the weather resistance is not sufficient, and when they are used as an adhesive or a sealant, they cannot be said to have sufficient adhesion to the substrate.

Further, a method of adding a silane coupling agent as an adhesiveness-imparting agent in order to improve the adhesion has been proposed in, for example, Japanese Patent Application Laid-Open No. 57-182350. The expected effect was not exhibited unless it was a silane coupling agent, and heat resistance and water resistance were not sufficient.

On the other hand, a fluorine-containing polymer having a polyoxyalkylene side chain as a flexible curable composition having excellent weather resistance is disclosed in JP-A-1-308433 and JP-A-2-2450.
05, JP 3-122152 A, JP 3
It is proposed in Japanese Patent Publication No. 126707.

Further, the present inventors have filed a patent application as a fluorine-containing polymer obtained by polymerizing a polymerizable monomer containing a fluoroolefin-based polymerized unit as an essential component in a polyoxyalkylene having a curable site. We have developed and applied for the one described in Japanese Patent No. 5-205872. These materials were also excellent in weather resistance and initial adhesiveness, but they were not satisfactory in terms of long-term adhesiveness retention.

Furthermore, the present inventors have developed a curable composition comprising a hydrolyzable silyl group-containing polyether and a fluorine-containing copolymer and applied for it as Japanese Patent Application No. 5-205875. Although it was excellent in weather resistance and also excellent in initial adhesiveness, it was not satisfactory in terms of maintaining long-term adhesiveness.

[0008] Further, the one-pack type is preferred because it can be used and stored as it is by mixing a curing catalyst in advance, and it is not necessary to repeat the work of accurate weighing and kneading each time it is used. Be preferred.

[0009]

The present invention seeks to overcome the aforementioned drawbacks. That is, it is an object of the present invention to provide a curable composition having stretchability, excellent weather resistance and stain resistance, and excellent long-term adhesive strength retention.

[0010]

Means for Solving the Problems As a result of intensive studies made by the present inventor to improve water-resistant adhesion, wet surface adhesion and the like as described above, a polymer and a silane having fluorine and having elasticity after curing. The present inventors have found that a composition comprising a coupling agent and a curing catalyst can solve the above problems, and completed the present invention.

That is, the present invention provides the following (A-1) to (A
Polymer (A) selected from (6) [where (A-3) and (A-4) are used in combination], (B) silane coupling agent, and curing catalyst of component (C) (A) And / or a catalyst that accelerates the reaction of the component (B).

(A-1) Fluorine-containing organic elastic polymer having a curable site, (A-2) Fluorine-containing organic elastic polymer having at least one polyoxyalkylene side chain and having a curable site, (A-3) Fluorine-containing organic polymer and (A-4) Fluorine-free organic elastic polymer having at least one curable moiety, (A-5) Fluorine-free organic polymer not containing. Fluorine-containing polymer obtained by polymerizing polymerizable monomer having polymerizable unsaturated group based on fluoroolefin in the presence of organic elastic polymer, and (A-6) polyoxyalkylene having curable site and fluorine .

The fluorine-containing organic elastic polymer having a curable site in the component (A-1) of the present invention is a polymer containing fluorine in the side chain or main chain of the polymer and exhibiting elasticity after curing. .

The polymer forming the skeleton of the fluorine-containing organic elastic polymer having the curable site of the component (A-1) is a polyoxyalkylene-based polymer, a dibasic acid such as adipic acid or maleic anhydride, and the like. Polyester-based polymer obtained by condensation with glycol or ring-opening polymerization of cyclic ester such as lactone, polyisobutylene or copolymer of isobutylene and isoprene, polychloroprene,
Polyisoprene or copolymer of isoprene and butadiene, styrene-acrylonitrile copolymer, styrene-
Acrylonitrile-butadiene copolymer, polybutadiene, polyisoprene, butadiene, or hydrogenated polyolefin polymer hydrogenated to a polymer having an unsaturated bond such as a copolymer containing isoprene, ethyl acrylate, butyl acrylate, etc. When a polyacrylic acid ester-based polymer, a polysulfide-based polymer, or the like obtained by polymerizing the acrylic acid ester-based monomer as described above is synthesized, a part or all of the monomers in these polymerizations are fluorinated monomers. And a polymer obtained by synthesizing the above-mentioned polymer, and then substituting part or all of hydrogen of the obtained polymer with fluorine.

Further, a grafted product of the above-described polymer chain and a fluorine-free polymer chain, or a mixture of a fluorine-containing elastic organic polymer and a fluorine-free polymer may be used. These fluorine-containing organic elastic polymers are preferably liquid at room temperature.

As the curable site, a hydrolyzable silyl group represented by the following formula (1), a hydroxyl group, an amino group, a mercapto group, an isocyanate group, a carboxyl group, an aldehyde group, an N-methylol group, and an unsaturated group. Examples thereof include groups such as groups, non-hydroxyl groups, and acid amide groups, with hydrolyzable silyl groups, epoxy groups, and hydroxyl groups being preferred in terms of workability and curability.

[0017]

[Chemical 2]

However, a is an integer of 0, 1, 2, or 3, b is an integer of 0, 1, or 2, m is an integer of 0 or more,
However, 1 ≦ a + mb. R ¹ and R ² are the same or different hydrocarbon groups having 1 to 10 carbon atoms or halogenated hydrocarbon groups, and X ¹ and X ² are the same or different hydrolyzable groups.

The method for synthesizing the fluorine-containing organic elastic polymer having at least one polyoxyalkylene side chain and having a curable site in the component (A-2) of the present invention includes the following methods.

(1) A polymerizable monomer having a polymerizable unsaturated group based on a fluoroolefin based on a polyoxyalkylene having one polymerizable unsaturated group and at least one curable site (hereinafter referred to as fluoroolefin). ), If necessary, it is synthesized by copolymerizing with a polymerizable monomer having a polymerizable unsaturated group based on fluoroolefin and a polymerizable monomer copolymerizable with the polymerizable monomer (hereinafter referred to as fluoroolefin copolymerizable monomer).

(2) Copolymerizing a polyoxyalkylene having one polymerizable unsaturated group and at least one group capable of introducing a curable site with a fluoroolefin and optionally a fluoroolefin copolymerizable monomer. After the fluorine-containing polymer is synthesized by the method, it is synthesized by introducing a curable site into the group capable of introducing the curable site.

Specific methods for producing the polyoxyalkylene described in (1) and (2) include, for example, a method of polymerizing the following cyclic ether using a compound having a polymerizable unsaturated group as an initiator. To be

Examples of such an initiator include a hydroxyl group,
Examples thereof include compounds having a functional group such as an amino group, a mercapto group, a carboxyl group or a non-hydroxyl group, and a polymerizable unsaturated group. Specific compounds include hydroxyl-containing compounds such as allyl alcohol, hydroxybutyl vinyl ether, 2-hydroxyl ethyl (meth) acrylate and 2-hydroxyethyl crotonic acid, and carboxyls such as (meth) acrylic acid, maleic anhydride and vinyl acetic acid. Group or its anhydride-containing vinyl group, amino group-containing vinyl group such as allylamine, and the like.

Examples of the method for introducing the curable moiety include a method in which the terminal hydroxyl group of the polyoxyalkylene obtained as described above or the polyoxyalkylene is copolymerized with a fluoroolefin and then introduced by the following method. To be

(A) Isocyanate group: The terminal hydroxyl group of the obtained polyoxyalkylene is reacted with an excess of polyfunctional isocyanate.

(B) Epoxy group: After the terminal hydroxyl group of polyoxyalkylene is alcoholated with an alkali metal,
React with epichlorohydrin. When the polyoxyalkylene is synthesized by cationic polymerization using epichlorohydrin as a cocatalyst, it is epoxidized with an alkali after the synthesis.

(C) Amino group: A terminal hydroxyl group of polyoxyalkylene is directly aminated with ammonia or a primary amine. After the addition of acrylonitrile, the nitrile group is modified to an amino group. Examples thereof include a method of directly reacting the polymerization terminal with ammonia or a primary amine. The polyoxyalkylene-terminated isocyanate group or epoxy group obtained in (a) or (b) is reacted with an excess of polyfunctional amine.

(D) mercapto group; the polyoxyalkylene-terminated isocyanate group obtained in (a) is reacted with a compound having a mercapto group such as mercaptoethanol and a group capable of reacting with an isocyanate group. Alternatively, the polyoxyalkylene terminal is chlorinated and then reacted with sodium disulfide or the like, and then reduced to introduce a terminal mercapto group. The polyoxyalkylene terminal is further reacted with a cyclic sulfide or the like to make the terminal a mercapto group.

(E) Aldehyde group: A polyoxyalkylene terminal hydroxyl group is converted into an aldehyde group by oxidation.

(F) Carboxyl group: a polyoxyalkylene terminal hydroxyl group is reacted with an excess of dicarboxylic acid or with an acid anhydride. The terminal hydroxyl group is directly oxidized or the terminal aldehyde group obtained in (e) is oxidized.

(G) Unsaturated group; a compound having a halogen atom and an unsaturated group after the terminal hydroxyl group is alcoholated with an alkali metal or a hydride thereof, a hydroxide, a low molecular alcohol such as methanol, ethanol, or isopropanol. (For example, allyl chloride, allyl bromide, 2-chloroethyl vinyl ether, 2-bromoethyl vinyl ether, acrylic acid chloride, 4-chloromethylstyrene, 4-bromomethylstyrene, etc.).

(H) Hydrolyzable silyl group;
The functional group introduced in (g) or a silane coupling agent containing a group capable of reacting with the polyoxyalkylene terminal hydroxyl group synthesized by the above method and a hydrolyzable silyl group is reacted.

(3) After synthesizing a fluoropolymer having a group that can serve as a starting point in the polymerization of polyoxyalkylene, it is synthesized by addition-polymerizing the following cyclic ether monomer to the fluoropolymer. .

Examples of the group that can be a starting point in the polymerization of polyoxyalkylene include active hydrogen-containing groups such as hydroxyl group, epoxy group, carboxyl group, non-hydroxyl group, amino group, acid amide group and N-methylol group. Examples of the method of introducing these groups into the fluoropolymer include a method of copolymerizing a polymerizable monomer having the above group.

(4) Synthesis is carried out by further introducing a curable site into the polymer obtained in (3) above.

In the above (1) to (4), the polyoxyalkylene is a repeating unit whose main chain is essentially -R ⁰ -O-. However, R ⁰ is a divalent hydrocarbon group having 1 to 10 carbon atoms and / or a halogen-containing hydrocarbon group.

As a specific structure of -R ⁰ -O-,
_{(CH 2) n O -,} - CH 2 -CH (CH 3) -O-,
_{-CH 2 -CH (C 2 H 5} ) -O -, - CH 2 -CH
_{(O-CH 2 -CH = CH} 2) -O -, - CH 2 -C
_{(CH 3) 2 -CH 2 -O} -, - CHCl-CH 2 -O
_{-, - CH 2 -C (CH} 2 Cl) 2 -CH 2 -O-,
(N is an integer of 1 to 10), and the like.

Examples thereof include those containing these repeating units alone or as a mixture of two or more kinds in a random form or in a block form, but the present invention is not limited thereto.

These are monoepoxy compounds with ethylene oxide, propylene oxide and butylene oxide,
It is a polymer chain obtained by ring-opening polymerization of oxetane such as cyclic formal, oxetane, 3,3-dimethyloxetane and 3,3-dichloromethyloxetane, and cyclic ether such as tetrahydrofuran.

Examples of the polymerization method include anion polymerization using generally used alkali metals, coordination anion polymerization using an organic metal, cationic polymerization using a protic acid, a Lewis acid, an acid anhydride and the like.

The above-mentioned fluoroolefins include tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride,
A fluoroolefin having 2 to 10 carbon atoms, particularly about 2 to 6 carbon atoms, such as hexafluoropropylene or perfluoropropyl vinyl ether is preferably used. Of these, perhalofluoroolefins in which hydrogen is completely replaced by halogen are most preferable.

As the fluoroolefin copolymerizable monomer, there are compounds having a polymerizable site such as vinyl group, allyl group, acryloyl group, methacryloyl group and isopropenyl group. Specific examples include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acid esters, methacrylic acid esters, crotonic acid esters, isopropenyl ethers, isopropenyl esters and the like. It

Of these, compounds having a linear, branched or alicyclic alkyl group having about 1 to 15 carbon atoms are preferable. As such a monomer, a part or all of hydrogen bonded to carbon may be replaced with fluorine.

Specific compounds include vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether and perfluoroalkyl vinyl ether, olefins such as ethylene, propylene, 1-butene, isobutylene and cyclohexene, Allyl ethers such as allyl alcohol, methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, 2-hydroxyethyl allyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, capron. Vinyl acetate, vinyl caprylate, Veova 9 and Veova 10 (
(Trade name of vinyl ester of branched fatty acid consisting of C ₉ and C ₁₀ manufactured by Shell Chemical Co., Ltd.), fatty acid vinyl ester such as vinyl versatate, acryl such as ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate and cyclohexyl methacrylate. Examples thereof include acids or methacrylic acid esters, and crotonic acid esters such as ethyl crotonate crotonate, butyl crotonate, and cyclohexyl crotonate.

Among the above monomers, a monomer selected from vinyl ethers, vinyl esters, allyl ethers, allyl esters, isopropenyl ethers, isopropenyl esters and crotonic acid esters is particularly preferable. Most preferred are vinyl ethers, and the use thereof is preferable from the viewpoint of weather resistance, since the probability of alternate copolymerization with fluoroolefins is high.

It is also preferable that the fluoroolefin copolymerizable monomer has a curable site. Examples of the curable site include the curable site described above. By including these curable sites, the strength of the curable composition of the present invention is further improved. When the curable site of this monomer is a polar group, it improves the adhesion of the composition of the present invention to a substrate even when the curable site is not particularly involved in the curing reaction of the composition. And so on.

The component (A-2) is preferably liquid at room temperature.

A detailed description of these fluorine-containing organic elastic polymers is given in JP-A-1-308433 and JP-A-2-24.
It is described in JP-A-5005, JP-A-3-122152, JP-A-3-126707 and the like.

The fluorine-containing organic polymer (A-
3) is preferably a fluorine-containing polymer having the above-mentioned fluoroolefin-based polymerized units as an essential component.

Such a fluorine-containing organic polymer is particularly preferably a polymer having at least 20 mol% of polymerized units based on fluoroolefin. When the content of the polymerized units based on fluoroolefin is less than 20 mol%, sufficient weather resistance is not exhibited, and stains may become remarkable during long-term use, which is not preferable. In the fluoropolymer, the number of polymerized units based on fluoroolefin is 20 to
It is particularly preferable to have 80 mol%. More preferably 30 to 70 mol%, and even more preferably 40 to 70 mol%
Is.

The fluoropolymer (A-3) may have a polymer unit based on the above-mentioned fluoroolefin copolymerizable monomer in addition to the polymer unit based on the fluoroolefin.

In the fluoropolymer, the amount of polymerized units based on these fluoroolefin copolymerizable monomers is preferably 80 mol% or less. When it is more than 80 mol%, sufficient weather resistance is not exhibited, and stains may become remarkable during long-term use, which is not preferable. Especially 20-80 mol%
Is preferred. It is more preferably 30 to 70 mol%, further preferably 30 to 60 mol%.

In the present invention, an appropriate amount of polymerized units based on these fluoroolefin copolymerizable monomers is contained so that the fluorine-free organic elastic polymer (A- has at least one curable site without impairing weather resistance).
A cured product obtained by mixing the composition well with 4) and curing the composition can be a flexible cured product. Further, by exhibiting solvent solubility and preparing a solution of such a polymer, mixing with the component (A-4) becomes easy. Further, the fluoropolymer is (A-2)
Those containing a polyoxyalkylene chain as a component are also preferable.

The fluorine-containing polymer (A-3) has a molecular weight of 2,000,000 or less, and when it is used in the absence of a solvent such as a sealant or in the presence of a small amount of a solvent, it is especially 5000.
It is preferably about 0 or less. The lower limit of the molecular weight is not particularly limited, but is usually 1000 or more, preferably 2000 or more.

The above-mentioned method for polymerizing the fluoropolymer (A-3) may be any of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization. A predetermined amount of the monomer is mixed with a polymerization initiator or ionization. Polymerization is performed by causing a polymerization initiation source such as sexual radiation to act. Other various conditions can be the same as those usually used for solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

Examples of the fluorine-free organic elastic polymer in the component (A-4) of the present invention include polyoxyalkylenes having a main chain and vinyl polymers having an acrylic ester unit as a main component. , Flexibility after curing,
From the viewpoint of workability, polyoxyalkylene is preferable.

Examples of the curable portion include the same ones as described above.

Specifically, a polyoxyalkylene having a hydrolyzable silyl group, an epoxy group, a hydroxyl group, or a vinyl-based polymer containing an acrylic acid ester unit as a main component, a composite of these two kinds, or a polymer thereof. Among them, those obtained by polymerizing a vinyl monomer that does not contain fluorine can be cited. Particularly preferred is polyoxyalkylene having a hydrolyzable silyl group, an epoxy group or a hydroxyl group.

Regarding these polymers, for example, Japanese Patent Publication No.
5-36319, JP-B-46-17553, JP-B-46-30711, JP-B-61-18
582, JP-A-59-122541, JP-A-60-6747, JP-A-1-275648, JP-A-3-43449, and JP-A-3-4782.
No. 5, JP-A-3-72527, JP-A No. 3-7
9627, Japanese Examined Patent Publication No. 63-65086, and Japanese Examined Patent Publication No. 2-52935.

Further, the details of the composition of the components (A-3) and (A-4) are described in Japanese Patent Application No. 5-205872, Japanese Patent Application No. 5-205876, Japanese Patent Application No. 5-205878. Have been described.

As the organic elastic polymer having at least one curable site in the component (A-5) of the present invention, particularly the main chain is composed of the above-mentioned polyoxyalkylene and has the above-mentioned curable site at the molecular end. Compounds are preferred.

Specific polyoxyalkylenes include:
For example, polyoxyalkylene monool, polyoxyalkylene diol, polyoxyalkylene triol,
Examples thereof include those having a terminal hydroxyl group such as polyoxyalkylene tetraol and those having other functional groups introduced into the terminal hydroxyl group by the modification methods described in the above (a) to (h). The type and introduction rate of the functional group at this time may be freely changed depending on the number of terminal functional groups of the polyoxyalkylene used, required physical properties, etc., and is not particularly limited. As the functional group to be introduced, a hydrolyzable silyl group and an epoxy group are preferable from the viewpoint of workability and curability of the component (A-5).

The component (A-5) is obtained by polymerizing the above-mentioned fluoroolefin in the presence of such a polyoxyalkylene. However, in addition to the fluoroolefin, the above-mentioned fluoroolefin copolymerizable monomer is copolymerized. You can also let it.

Such a compound is disclosed in Japanese Patent Application No. 5-20587.
No. 2, Japanese Patent Application No. 5-205876, Japanese Patent Application No. 5-2058
No. 78, etc., for details. The present invention (A-
As the polyoxyalkylene having a curable moiety and fluorine as the component 6), for example, the main chain is substantially —R ⁰ —O.
A polymer having a chain (R ⁰ is as described above), and a part or all of R is an alkyl group having fluorine.

Specific examples of the polymer include 3,3,3-trifluoro-1,2-epoxypropane, the following fluorine-containing monoepoxy compounds, fluorine-containing oxetane polymers, and fluorine and these. Examples thereof include copolymers of alkylene oxides, oxetane, and cyclic ethers such as tetrahydrofuran, copolymers of vinyl monomers and hexafluoroacetone, copolymers of hexafluoroacetone and cyclic ethers, and the like.

H (CF ₂ ) ₆ CH ₂ -Q, H (CF ₂ )
_{8 CH 2 -Q, H (CF} 2) 4 CH 2 OCH 2 -Q, H
_{(CF 2) 6 CH 2 OCH} 2 -Q, CF 3 CF 2 CH 2
_{OCH 2 -Q, H (CF 2} ) 6 -Q,

[0067]

[Chemical 3]

However, in the above formula, Q represents the epoxy group of Chemical formula 4.

[0069]

[Chemical 4]

Examples of the curable site are the same as those mentioned above, but a hydrolyzable silyl group, an epoxy group and a hydroxyl group are preferred.

In the present invention, as the silane coupling agent which is the component (B), a generally used compound which can cause a condensation reaction with water can be used. For example, a compound represented by the following formula (2) may be mentioned.

R ³ _n SiX _4-n (2) In the formula, X is a hydrolyzable group, R ³ is hydrogen, and has 1 to 30 carbon atoms.
Is an organic group, and n is an integer of 0 to 3.

Examples of X include a halogen atom, an alkoxy group, a hydroxyl group, an acyloxy group, a ketoximate group,
Amino group, amide group, aminooxy group, mercapto group,
Examples thereof include an alkenyloxy group.

Particularly, X is preferably an alkoxy group from the viewpoints of hydrolyzability and easy handling. Particularly preferably,
From the viewpoint of high reactivity, the hydrolyzable group is preferably a methoxy group or an ethoxy group, and it is preferable that two or more, and more preferably three or more of these groups are attached to one silicon atom.

Specifically, methyl silicate, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, phenyltrimethoxysilane, Functionality of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dibutyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, etc. Silane compounds having no group: silane compounds such as trimethoxysilane, dimethoxymethylsilane, triethoxysilane, vinyl Vinylsilanes such as methoxysilane and vinylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane and the like ( (Meth) acrylsilanes: γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ- Aminopropylmethyldimethoxysilane, N
-Β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ
-Amino group-containing silanes such as aminopropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane:
mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ
-Epoxysilanes such as glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycodoxypropyltriethoxysilane: β-carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2 -Methoxyethoxy)
Examples thereof include silanes and carboxysilanes such as N-β- (N-carboxylmethylaminoethyl) -γ-aminopropyltrimethoxysilane.

These silane coupling agents may be used alone or in combination of two or more kinds.

Further, R ³ is an organic group containing a functional group selected from an amino group, an epoxy group, a methacryl group, an acryl group and a mercapto group, and R ³ is a functional group. A reaction product of a silane coupling agent, which is a reaction product of a compound represented by the above formula (2), which is an organic group containing a group reactive with

Examples of such a reaction product are 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, and a reaction of an epoxysilane compound and a mercaptosilane compound. And a reaction product of a mercaptosilane compound with each other. These reaction products can be easily obtained by mixing the silane compound and stirring the mixture at room temperature to 180 ° C. for 1 to 8 hours.

The reaction products of the preferred silane coupling agents are methyltrimethoxysilane, methylorthosilicate, γ-glycidoxypropyltrimethoxysilane, γ.
Reaction product of glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane, N
Reaction product of-(β-aminoethyl) γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane and γ-glycidoxy There are reaction products with propyltrimethoxysilane.

A silane coupling agent having a group capable of reacting with the curable site in the components (A-1) to (A-6) of the present invention is also preferable. For example, if the curable site is a hydroxyl group,
Silane coupling agent having an isocyanate group, when the curable site is an epoxy group, an amino group, a mercapto group,
A silane coupling agent having an epoxy group, a carboxyl group, a hydroxyl group or the like, a silane coupling agent having an amino group, a mercapto group or the like, or a silane coupling agent having an H-Si bond, when the curable site is an unsaturated group, curing When the natural site is an isocyanate group, a combination of a silane coupling agent having an amino group, a mercapto group, a carboxyl group, a hydroxyl group and the like can be mentioned as a preferable combination.

(A-1), (A-2), {(A
-3) + (A-4)}, (A-5), and (A-6) components (as mentioned above, these components are generically referred to as (A) component)
The blending ratio of the component (B) with respect to the component (A) is 10
0.1 to 100 parts by weight of the component (B) with respect to 0 parts by weight,
It is preferably 0.1 to 20 parts by weight.

The composition of the present invention contains, as the component (C), a curing catalyst of the component (A) and / or a curing catalyst of the silane coupling agent of the component (B) for the purpose of promoting curing. As specific curing catalysts, for example, when the curable site of the component (A) is a hydrolyzable silyl group or when it is added as a curing catalyst for a silane coupling agent, the following may be mentioned. .

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. , Alicyclic amines such as piperidine and piperazine, aromatic amines such as metaphenylenediamine, ethanolamines, triethylamine, amine compounds such as various modified amines used as a curing agent for epoxy resins; (nC ₄ H ₉ ). ₂ Sn (OCOC ₁₁ H ₂₃ -n)
₂ , (nC ₄ H ₉ ) ₂ Sn (OCOCH = CHCOO-C ₄ H ₉ -n) ₂ , (nC ₄ H ₉ ) ₂ Sn
_{(OCOCH = CHCOO-CH 3)} 2, (nC 8 H 17) 2 Sn (OCOC 11 H 23 -n) 2,
(nC ₈ H ₁₇ ) ₂ Sn (OCOCH = CHCOO-C ₄ H ₉ -n) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (O
_{COCH = CHCOO-CH 3) 2} , (nC 8 H 17) 2 Sn (OCOCH = CHCOOC 8 H 17 -is
o) ₂ , carboxylic acid type organotin compounds such as Sn (OCOC ₈ H ₁₇ -n) ₂ , a mixture of the carboxylic acid type organotin compounds listed above and amines listed above; (nC ₄ H ₉ ). ₂ Sn (SCH ₂ COO) ₂ , (n
-C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ -iso) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ CO
_{O) 2, (nC 8 H} 17) 2 Sn (SCH 2 CH 2 COO) 2, (nC 8 H 17) 2 Sn (SCH 2
COOCH ₂ CH ₂ OCOCH ₂ S) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₄ H ₈ OCOH _{2
S) 2, (nC 8 H} 17) 2 Sn (SCH 2 COOC 8 H 17 -iso) 2, (nC 8 H 17) 2 S
n (SCH ₂ COOC ₈ H ₁₇ -n) ₂ , (nC ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ -n)
₂ , mercaptide type organotin compounds such as Chemical formula 5; (nC ₄ H ₉ ) ₂ Sn = S, (n
-C ₈ H ₁₇ ) ₂ Sn = S, sulfide type organotin compounds such as Chemical formula 6; (nC ₄ H ₉ ) ₂ SnO, (nC ₈ H
₁₇ ) ₂ SnO or other organic tin oxide, or (nC ₄ H ₉ ) ₂ SnO,
(nC ₈ H ₁₇ ) ₂ SnO and other organic tin oxides and reaction products with ethyl silicate, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate and other ester compounds; Organic tin compounds such as the organic tin compounds represented by Chemical formula 7 can be used.

[0084]

[Chemical 5]

[0085]

[Chemical 6]

[0086]

[Chemical 7]

However, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, Y is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and R,
Y may be the same or different.

When the curable site of the component (A) of the present invention is an epoxy group, a generally used epoxy curing agent is used, and the curable site of the component (A) is a hydroxyl group. In the case of curing with, a generally used urethane reaction catalyst is used. (A)
When the curable site of the component is an unsaturated group and is cured with, for example, a compound containing at least two H-Si bonds in the molecule, a generally used hydrosilation reaction catalyst such as a chloroplatinic acid catalyst is used. To be

When the composition of the present invention is used as a curable composition, a solvent (component (D)) may be added if necessary for the purpose of adjusting viscosity and improving storage stability of the composition. Such solvents include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, ketones, esters, ethers, alcohol esters, ketone alcohols, ether alcohols, ketone ethers, Examples thereof include ketone esters and ester ethers.

When an alkyl alcohol is used, it is preferable to store the composition of the present invention for a long period of time, and particularly to store it in the presence of a catalyst as a one-part curable composition because the storage stability is improved. As the alkyl alcohol, alcohols having 1 to 10 carbon atoms are preferable, and methyl alcohol, ethyl alcohol, isopropyl alcohol, isoamyl alcohol, hexyl alcohol, cellosolve and the like are used.

A dehydrating agent (component (D)) may be added, if necessary, for the purpose of improving the storage stability of the composition. Specific examples of the dehydrating agent include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, and hydrolyzable ester compounds such as the silane compound represented by the above formula (1). Among them, silane compounds having n of 2 to 4 in the formula (1) are preferable because of excellent dehydrating power. Particularly preferably, n is 3 or 4.

Specific compounds include methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate,
Examples thereof include ethyl silicate. These hydrolyzable ester compounds are synthesized even if added at the time of synthesizing the fluoropolymer having at least one side chain having two or more ether bonds of the component (A) of the present invention and having a curable site. May be added later.

If necessary, an epoxy compound ((D)
Ingredients) may be added. The strength of the composition is significantly improved by adding the epoxy compound to the system. You may use together with an epoxy resin hardening agent or an epoxy hardening agent as needed.

The epoxy compound which can be added to the composition of the present invention is not particularly limited as long as it is a compound having at least one epoxy group in the molecule, but specifically,
Common epoxy resins can be mentioned.

As the 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, novolak type epoxy resin, Hydrogenated bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct,
Diglycidyl ester-based epoxy resin such as diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, m-aminophenol-based epoxy resin, diaminodiphenylmethane-based epoxy resin , Urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N
-Diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, epoxidized unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, etc. Examples thereof include epoxy resins and epoxy group-containing vinyl polymers used, 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 composition of the present invention may be used in combination with a curing agent or curing catalyst for the above epoxy resin. Examples of such a curing agent include generally used curing agents for epoxy resins.

Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, Amines such as 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine salts,
Polyamide resins, imidazoles, dicyandiamides, boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, pyromellitic dianhydride, etc. A polyalkylene oxide polymer having at least one group capable of reacting with an epoxy group in the molecule on average such as carboxylic acid, phenoxy resin, carboxylic acids, alcohols (terminal aminated polyoxypropylene glycol, terminal carboxylated poly Oxypropylene glycol, etc.), polyether thiol having terminal mercapto group, polysulfite polymer, polybutadiene having terminal modified with hydroxyl group, carboxyl group, amino group, hydrogenated polybutadiene, acrylonitrile-butane Ene copolymers, although liquid terminal functional group-containing polymer such as acrylic polymer is exemplified by, but not limited to.

These curing agents are the above-mentioned epoxy compounds 10
It may be used in an appropriate amount depending on the purpose in the range of about 0.1 to 300 parts by weight relative to 0 parts by weight.

When the compound containing the epoxy group is added, it is also preferable to add a silane coupling agent having a group capable of reacting with the epoxy group.

If necessary, a photopolymerizable compound (component (D)) may be added. Examples of the photopolymerizable compound include polyfunctional acrylic monomers used for commonly used electron beam or ultraviolet curable resins.

In the present invention, the method for preparing a room temperature curable composition containing the component (A), the component (B), the component (C) and, if necessary, the component (D) as active ingredients is not particularly limited. A) to (D) components are blended as active ingredients and kneaded at room temperature or under heating with a mixer, roll or kneader, or a suitable solvent is used to dissolve the components. A usual method such as mixing by mixing can be adopted. Further, by appropriately combining these components, a one-pack type or a two-pack type compound can be prepared and used.

For example, when preparing a one-part formulation,
In addition to the method of blending components (A) to (D) at once and kneading while dehydrating, components other than component (C) are blended and kneading while dehydrating, and then component (C) is added. Method of mixing, when blending components other than the component (C) and dehydrating,
A method of adding a dehydrating agent as the component (D) and a catalyst for accelerating the dehydration reaction of the dehydrating agent, mixing components other than the components (B) and (C), and kneading while dehydrating, and then further adding (B) And a method of adding and mixing the component (C).

To the room temperature curable composition of the present invention, the active ingredients (A) to (C) and optionally (D) are added.
In addition to the components, various fillers, plasticizers, antioxidants, radical inhibitors, UV inhibitors, lubricants, pigments, physical property modifiers,
If necessary, an air-oxidation-curable compound, a photopolymerization initiator, a polymerizable monomer that can be polymerized by the initiator, and a foaming agent can be added.

When a filler is used as an additive, wood flour, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut flour, rice flour, graphite, diatomaceous earth, white clay, fume silica, sedimentation Silica, anhydrous silicic acid, carbon black, calcium carbonate, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, surface treated calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz, aluminum, fine powder, flint powder, Sub-powder or the like can be used.
These fillers may be used alone or in combination of two or more.

As the antiaging agent, a commonly used antiaging agent, for example, citric acid, phosphoric acid or a sulfur antiaging agent can be used.

Examples of the sulfur anti-aging agent include mercaptans, mercaptan salts, sulfides including sulfide carboxylic acid esters and hindered phenol sulfides, polysulfides, dithiocarboxylic acid salts, thioureas, thiophosphides. , Sulfonium compounds, thioaldehydes, thioketones, mercaptars, mercaptols, monothio acids, polythio acids, thioamides, sulfoxides and the like.

Specific examples of such a sulfur type anti-aging agent include 2-mercaptobenzothiazole which is a mercaptan, zinc of 2-mercaptobenzothiazole which is a salt of mercaptan, and 4,4′- which is a sulfide.
Thio-bis (3-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-t-butylphenol), 2,2'-thio-bis (4-methyl-6-) t-butylphenol), bis (3-methyl-4)
-Hydroxy-5-t-butylbenzyl) sulfide,
Terephthaloyldi (2,6-di-methyl-4-t-butyl-3-hydroxybenzyl sulfide, phenothiazine, 2,2'-thio-bis (4-octylphenol)
Nickel, dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, distearyl β, β'-thiodibutyrate, lauryl-stearyl thiodipropionate, 2 , 2-thio [diethyl-
Bis-3 (3,5-di-t-butyl-4-hydroxyphenol) propionate], polybenzoic acid 2-benzothiazole disulfide, dithiocarboxylic acid salts zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, nickel dibutyl Dithiocarbamate, zinc di-n-butyldithiocarbamate, dibutylammonium dibutyldithiocarbamate, tink diethyl-phenyl-dithiocarbamate, zinc dimethylcarbamate, thiourea 1-butyl-3
Examples include -oxy-diethylene-2-thiourea, di-o-tolyl-thiourea, ethylenethiourea, and thiophosphates such as trilauryltrithiophosphate.

When used in the composition of the present invention, the sulfur type anti-aging agent as described above can significantly prevent decomposition and deterioration of the main chain due to heat, as compared with other anti-aging agents, and can reduce surface tack (stickiness). It can be prevented from occurring.

When an antioxidant, for example, a sulfur-based antioxidant is used, the amount used is (A) + (B) in the present invention.
0.1 to 5 parts is preferable for 100 parts of the component.

Examples of the radical inhibitor include 2,
2'-methylene-bis (4-methyl-6-t-butylphenol), tetrakis [methylene-3 (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane and other phenolic radical inhibitors, phenyl-β-naphthylamine, α-naphthylamine, N,
Examples thereof include amine radical inhibitors such as N′-tert-butyl-p-phenylenediamine, phenothiazine, N, N′-diphenyl-p-phenylenediamine.

As the ultraviolet absorber, for example, 2 (2 '
-Hydroxy-3 ', 5'-di-t-butylphenyl)
Examples thereof include benzotriazole and bis (2,2,6,6-tetramethyl-4-piperidine) sebacate.

In addition to these, hindered amine type, benzotriazole type, benzophenone type, benzoate type,
Each compound such as cyanoacrylate-based, acrylate-based, hindered phenol-based, phosphorus-based, etc. can be appropriately used.

It is also preferable to add a plasticizer to the composition of the present invention in order to improve workability.

As the plasticizer, generally used plasticizers, for example, phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, diallyl phthalate and butylbenzyl phthalate, dioctyl adipate,
Aliphatic dibasic acid esters such as isodecyl succinate, diethylene glycol dibenzoate, glycol esters such as pentaerythritol ester, butyl oleate, aliphatic esters such as methyl acetylsilinoleate, tricresyl phosphate, trioctyl phosphate, Phosphate esters such as octyldiphenyl phosphate, epoxidized soybean oil, epoxy-based plasticizers such as benzyl epoxystearate, and general plasticizers such as chlorinated paraffin, and other polymeric plasticizers can be used. It is also preferable to use it in order to prevent contamination of the periphery due to migration of the plasticizer.

Specific examples of such polymer plasticizers include polyester plasticizers such as polyesters of dibasic acid and dihydric alcohol, polyethers such as polyoxypropylene glycol and its derivatives, and poly-α. Examples thereof include oligomers of polystyrene such as methylstyrene and polystyrene, oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and hydrogenated polybutene, but are not limited thereto. Among these, those having a molecular weight of about 300 to 20,000 are preferable from the viewpoint of the effect as a plasticizer, and a polyalkylene oxide polymer having a good compatibility with the composition of the present invention is more preferable. Particularly preferred is a polyalkylene oxide having a hydroxyl group having a number average molecular weight of 1,000 or more, or a polyalkylene oxide having no hydroxyl group at the terminal.

Further, a compound having one silanol group in the molecule or a compound which can be produced by hydrolysis of the compound may be added as a physical property modifier for the composition of the present invention. Examples of such compounds include silane compounds such as trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylchlorosilane, hexamethyldisilazane, dimethylvinylphenoxysilane, and N, O-bistrimethylsilylacetamide. To be These compounds may be appropriately added within the range of 0.01 to 1.5 equivalents based on the total hydrolyzable groups bonded to the terminal hydrolyzable silyl group of the composition of the present invention so as to have desired physical properties. it can.

As the air-oxidation-curable compound, a drying oil represented by tung oil, linseed oil and the like, various alkyd resins obtained by modifying the compound, an acrylic polymer modified by the drying oil, a silicone resin , 1,2-polybutadiene, 1,4-polybutadiene, diene-based polymers such as C ₅ -C ₈ diene polymers and copolymers, and various modified products of these polymers and copolymers (maleization modification). , Boiled oil modified, etc.), among these, tung oil,
Among the diene polymers, liquid products (liquid diene polymers), hydrogenated castor oil and modified products thereof are particularly preferable. These air oxidation curable compounds may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include commonly used compounds such as acetophenone.

The curable composition of the present invention comprises a sealing material,
Although it can be used as a waterproofing agent, a coating material, etc., it is particularly suitable for applications that require long-term adhesive strength retention as well as durability and weather resistance of the cured product itself.

[0121]

EXAMPLES The present invention will be described with reference to examples. However,
Abbreviations in the text and tables are as follows.

(Polymerizable unsaturated group-containing monomer) CTFE; chlorotrifluoroethylene, TFE; tetrafluoroethylene, HFP; hexafluoropropylene, EVE; ethyl vinyl ether, BVE; butyl vinyl ether, CHVE; cyclohexyl vinyl ether, PVac; Vinyl pivalate, V-9; Veova 9
(Trade name of vinyl ester of branched fatty acid having 9 carbon atoms manufactured by Shell Chemical Co., Ltd.), VVac; vinyl valerate, Vac;
Vinyl acetate, PP; propylene, AGE; allyl glycidyl ether, GVE; glycidyl vinyl ether, H
BVE; hydroxybutyl vinyl ether, PPVE;
Perfluoropropyl vinyl ether, 1-BT; 1-
Butene, PFO; α-olefin having a perfluoro group having 8 to 9 carbon atoms (representative structure; C ₆ F ₁₃ —CH═CH
₂ ), MAA; methacrylamide, MAAn; maleic anhydride, DMP; 2,4,6-tris (dimethylaminomethyl) phenol, VEPSi; γ-dimethoxymethylsilylpropyl vinyl ether.

(Initiator) AIBN; Azobisisobutyronitrile, ADVN;
2,2'-azobis (2,4-dimethylvaleronitrile), AMDVN; 2,2'-azobis (4-methoxy-2,4-dimethoxyvaleronitrile), PBIB; t
-Butyl perisobutyrate.

(Catalyst) # 918; Silanol curing catalyst manufactured by Sankyo Machine Gosei Co., Ltd., DB
TDL; dibutyltin dilaurate.

(Additive) Additive 1; a compound having a composition of Mg _0.7 Al _0.3 O _1.15 ,
Additive 2; a compound having a composition of 2MgO · 6SiO ₂ · xH ₂ O.

(Silane coupling agent) (manufactured by Shin-Etsu Chemical Co., Ltd.) KBM603; N-β (aminoethyl) γ-aminopropyltrimethoxysilane, KBM602; N-β (aminoethyl) γ-aminopropyldimethoxymethylsilane, KBM903 Γ-aminopropyltrimethoxysilane, KBM403; γ-glycidoxypropyltrimethoxysilane, KBM803; γ-mercaptopropyltrimethoxysilane, KBM503; γ-methacryloxypropyltrimethoxysilane, KBM1003; vinyltrimethoxysilane.

In the table, the amounts of the above compounds used are indicated by g unless otherwise specified. Moreover, Tables 2-5, Tables 7-11,
In Table 17, AF: interface failure (a state where peeling occurs on the adherend of the adherend and the cured product), CF: cohesive failure (a state where the cured product itself is destroyed), TCF: thin layer cohesive failure (on the adherend) When a thin layer of the cured product remains and is peeled off).

(Synthesis Example 1) Propylene oxide was polymerized using 4-hydroxybutyl vinyl ether as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene monool having an average molecular weight of 4000. After the terminal of the obtained polyoxypropylene monool was alcoholated with sodium hydroxide, it was reacted with allyl chloride. This was dissolved in a hexane-water system, the by-product salt was removed in the aqueous layer, and hexane was removed from the hexane layer to obtain polyoxypropylenetriol having an allyl group at the terminal.

Further, when this product was reacted with methyldimethoxysilane in the presence of a platinum catalyst, ¹³ C-NMR was obtained.
As a result, it was found that the vinyl ether group remained, the allyl ether group disappeared, and the silyl group was introduced only into the allyl ether group. By the above method, the average molecular weight having a vinyl ether group and a silyl group at the terminal is 40
00 polyoxypropylene was obtained.

(Synthesis Example 2) Propylene oxide was polymerized using allyl alcohol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene monool having an average molecular weight of 4000.

(Synthesis Example 3) Propylene oxide was polymerized using 2-hydroxyethyl crotonic acid as an initiator and aluminum porphyrin as a catalyst, and measured by gel permeation chromatography (hereinafter referred to as GPC) having an average molecular weight of 8000. A polyoxypropylene monool having an M _w / M _n of 1.10 was obtained. This polyoxypropylene monool was reacted with γ-isocyanatopropyldimethoxymethylsilane to give a terminal having a crotonyl group and a silyl group and an average molecular weight of 8,000, M _w / M _n of 1.
10 polyoxypropylenes were obtained.

Synthesis Example 4 Polyoxytetramethylene monool having an average molecular weight of 4000 was obtained by polymerizing tetrahydrofuran using BF ₃ .Et ₂ O as a catalyst and allyl alcohol as an initiator and epichlorohydrin as a cocatalyst.

(Synthesis Example 5) Propylene oxide was polymerized using allyl alcohol as an initiator and a zinc hexacyanocobaltate catalyst to synthesize polyoxypropylene monool having an average molecular weight of 4000, and hydroxyl groups at the terminals were hydroxylated. Alcoholated with sodium (PPG-1).

Separately, using 4-hydroxybutyl vinyl ether as an initiator, propylene oxide was polymerized using a potassium hydroxide catalyst to synthesize polyoxypropylene monool having an average molecular weight of 2000. The terminal was alcoholated with sodium hydroxide, and excess bromochloromethane was reacted, and bromochloromethane was removed under reduced pressure to obtain chloromethylated terminal polyoxypropylene monool (PPG-2). .

By reacting equal amounts of PPG-1 and PPG-2 thus obtained, polyoxypropylene having an allyl ether group and a vinyl ether group at the ends and an average molecular weight of 6000 was obtained. Furthermore, when this was reacted with methyldimethoxysilane in the presence of a platinum catalyst, the vinyl ether group remained, the allyl ether group disappeared, and the silyl group was introduced only into the allyl ether group by ¹³ C-NMR. I understood it.
By the above method, polyoxypropylene having a vinyl ether group and a silyl group at the terminal and an average molecular weight of 6000 was obtained.

(Synthesis Example 6) The terminal hydroxyl group of the polyoxypropylene monool obtained in Synthesis Example 2 was alcoholated with sodium metal and then reacted with epichlorohydrin to give an average of allyl group and epoxy group at the terminal. Polyoxypropylene having a molecular weight of 2000 was obtained.

(Synthesis Examples 7 and 11) Monomers, polyethers, solvents, initiators and additives having the respective compositions shown in Table 1 were charged in an autoclave, heated to 70 ° C. and stirred for 10 hours to proceed with polymerization. Let Thereafter, the additives were removed and the solvent was removed to obtain each fluoropolymer.

(Synthesis Examples 8 to 10 and 12) CTFE, TFE, HFP, polyether, solvent of each composition shown in Table 1,
The additives were charged into an autoclave, the temperature was raised to 60 ° C. with stirring, and the mixture was gradually charged with a mixed liquid of the monomer other than the fluoroolefin and the initiator over 5 hours to proceed with polymerization. After the completion of this preparation, 5 more at 60 ° C
After continuing the reaction for a period of time, the additives were removed and the solvent was removed to obtain each fluoropolymer.

(Synthesis Example 13) The terminal hydroxyl group of the polymer obtained in Synthesis Example 8 was alcoholized with sodium metal and then reacted with allyl chloride, which was further dissolved in a hexane-water system to form an aqueous layer. The raw salt was dissolved, and a purified polymer having a modified terminal modified with an allyl group was obtained from the hexane layer. This was further reacted with methyldimethoxysilane in the presence of a platinum catalyst to obtain a polymer having a silyl group at the terminal.

(Synthesis Example 14) The polymer obtained in Synthesis Example 10 was reacted with γ-isocyanatopropyldimethoxymethylsilane to obtain a polymer having a silyl group at the terminal.

(Synthesis Example 15) Propylene glycol was used as an initiator to polymerize propylene oxide using a potassium hydroxide catalyst to give a bifunctional PPG having an average molecular weight of 3000.
Was synthesized. The end of this PPG was alcoholated with sodium metal, reacted with dichloromethane, further reacted with allyl chloride, dissolved in hexane-water system, the by-product salt was removed to the aqueous layer, and the hexane layer was taken out to obtain hexane. Was removed under reduced pressure to obtain a terminal allyl group-containing polyoxypropylene diol having an average molecular weight of 8000. Further, this was reacted with methyldimethoxysilane in the presence of a platinum catalyst to obtain polyoxypropylene having a silyl group at 70% of its terminals and an average molecular weight of 8000.

Synthesis Example 16 Synthesis Example 7 except that 8 g of GVE was added as a polymerizable monomer in Synthesis Example 7.
A fluorine-containing polymer was obtained by the same method as described above.

(Examples 1 to 7) Each polymer 10 shown in Table 2
For 0 g, 75 g of heavy calcium carbonate, 75 g of colloidal calcium carbonate, 20 g of titanium oxide, 50 g of dioctyl phthalate, 6 g of hydrogenated castor oil, silane coupling agent of each kind and amount shown in Table 2, and 1 g of styrenated phenol are substantially contained. After sufficiently kneading in the absence of water, 1 g of # 918 as a catalyst was added and further kneaded.
An H-type test body conforming to S-A-5758 was prepared for three types of adherends of glass (adherend 1), aluminum (adherend 2), and mortar (adherent 3), and after prescribed curing. Table 2 shows the tensile physical properties (adhesive strength, unit: kg / cm ² ) and the fractured state, and the tensile physical properties and the fractured state of the adherend after immersion in water.

(Comparative Examples 1 to 7) Polymers 10 shown in Table 3
The same test as in Examples 1 to 7 was performed except that 0 g, and each type and amount of the silane coupling agent were used. The results are shown in Table 3. The test of Comparative Examples 3 to 5 was impossible because the peeling occurred at the interface during immersion of the test body in water.

A system comprising a polyoxyalkylene having a silylated end and a silane coupling agent does not exhibit excellent adhesiveness unless the silane coupling agent is a specific aminosilane compound, and even in these cases, the water resistant adhesiveness is poor. . Further, the polymer of the component (A) of the present invention alone has some performance in terms of initial adhesiveness and water-resistant adhesiveness, but is particularly inferior in water-resistant adhesiveness. It can be seen that even if the ring agent is added, very excellent initial adhesiveness and water resistant adhesiveness are exhibited.

Reference Example 1 (Synthesis of Reaction Product of Silane Coupling Agent) 25 g of KBM603 and 30 g of KBM503 were preliminarily stirred and reacted at 120 ° C. for 3 hours in a nitrogen atmosphere, and an infrared spectrum of the obtained product was obtained. From this, it was found that the peaks derived from the acryloyl group and the amino group were reduced.

Reference Example 2 (Synthesis of Reaction Product of Silane Coupling Agent) 25 g of KBM602 and 30 g of KBM403 were preliminarily stirred and reacted at 130 ° C. for 3 hours in a nitrogen atmosphere, and an infrared spectrum of the obtained product was obtained. From this, it was found that the peaks derived from the epoxy group and the amino group were reduced.

(Examples 8 to 11 and Comparative Examples 8 to 10) The types of synthetic examples used in Examples 8 to 11 and Comparative Examples 8 to 10, the type and amount of the added silane coupling agent,
The test results are shown in Table 4. The details of each example and comparative example will be described below.

Example 8 Polymer 100 of Synthesis Example 13
g, heavy calcium carbonate 50 g, colloidal calcium carbonate 5
0 g, titanium oxide 20 g, hydrogenated castor oil 6 g, trimethylolpropane triacrylate 3 g, the compound obtained in Reference Example 1 1.5 g, methanol 2 g, styrenated phenol 1 g, benzotriazole ultraviolet absorber 1 g,
The same tests as in Examples 1 to 7 were carried out using 1 g of the hindered amine anti-aging agent sufficiently kneaded with 3 paint rolls, then adding 2 g of # 918 and further kneading. Further, a glass plate was used as an adherend, and a durability test based on JIS-A-5758 was conducted.

Comparative Example 8 A test was conducted in the same manner as in Example 8 except that the compound obtained in Reference Example 1 was not added.

(Example 9) 100 g of the polymer of Synthesis Example 9,
Heavy calcium carbonate 75g, colloidal calcium carbonate 75
g, 20 g of titanium oxide, 1.5 g of the reaction product obtained in Reference Example 2, 50 g of polyoxypropylene diol having a molecular weight of 2000 and allyl etherified at the terminal, 2 g of methanol, Nocrac NS-6 (Ouchi Shinko Kagaku) (Made by the company)
After thoroughly kneading 1 g, Tinuvin 327 (manufactured by Ciba Geigy) 1 g, and Sanol LS-770 (manufactured by Ciba Geigy) with 3 paint rolls, 2 g of dibutyltin bisacetylacetonate was added and further kneaded. Then, the same test as in Example 8 was performed.

Comparative Example 9 A test was conducted in the same manner as in Example 9 except that the compound obtained in Reference Example 2 was not added.

Example 10 Polymer 100 of Synthesis Example 14
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5 g, titanium oxide 20 g, KBM603 1 g, dioctyl phthalate 50 g, styrenated phenol 1 g, benzotriazole ultraviolet absorber 1 g, hindered amine anti-aging agent 1 g, and xylene 3 g were sufficiently kneaded with 3 paint rolls, and then dibutyl tin. The same test as in Example 8 was conducted by using 2 g of bisacetylacetonate added and kneading sufficiently.

Example 11 KBM used in Example 10
Example 10 except that KBM803 was used instead of 603
The test was conducted in exactly the same manner as in.

(Comparative Example 10) A test was conducted in the same manner as in Example 10 except that KBM603 was not added.

When only the component (A) of the present invention is cured as in Comparative Examples 8 to 10, both water-resistant adhesive property and durable adhesive property are moderate, but as in Examples 8 to 11, the present invention is used. It can be seen that the composition (1) is extremely excellent in both water-resistant adhesive property and durable adhesive property, and the silane coupling agent is not limited to the specific amino group-containing silane coupling agent.

(Examples 12 to 19) Table 5 shows the types of synthesis examples used in Examples 12 to 19, the type and amount of the added silane coupling agent, and the test results.
The details of each example and comparative example will be described below.

Example 12 100 g of the polymer obtained in Synthesis Example 12, 50 g of heavy calcium carbonate, 50 g of colloidal calcium carbonate, 10 g of titanium oxide and 1 of KBM603 were used.
g, 2 g of KBM602, 10 of triethylenetetramine
g, 30 g of polyoxypropylene diol having an average molecular weight of 2,000 with primary amination at the end, 1 g of styrenated phenol, benzotriazole-based UV absorber 1
g, 1 g of the hindered amine anti-aging agent were sufficiently kneaded with three paint rolls, 2 g of dibutyltin dilaurate was added, and the mixture was sufficiently kneaded, and the same test as in Example 8 was performed.

Example 13 Polymer 100 of Synthesis Example 11
g, heavy calcium carbonate 50 g, colloidal calcium carbonate 5
3 g of 0 g, 10 g of titanium oxide, 2 g of KBM602, 1 g of styrenated phenol, 1 g of benzotriazole type ultraviolet absorber, and 1 g of hindered amine type anti-aging agent were sufficiently kneaded with a paint roll, and then 2 g of # 918 was added to further sufficiently mix them. The same test as in Example 8 was performed using the kneaded product.

Example 14 Polymer 100 of Synthesis Example 11
g, heavy calcium carbonate 50 g, colloidal calcium carbonate 5
0 g, 10 g of titanium oxide, 2 g of KBM602, Epicoat 828 (bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd.
Type epoxy resin) 20 g, hexahydrophthalic acid diglycidyl ester 20 g, triethylenetetramine 10
g, 30 g of dioctyl phthalate, 1 g of styrenated phenol, 1 g of benzotriazole type ultraviolet absorber, 1 g of hindered amine type anti-aging agent were thoroughly kneaded with 3 paint rolls, then 2 g of # 918 was added and further kneaded. Then, the same test as in Example 8 was performed.

Example 15 Polymer 100 of Synthesis Example 13
g, heavy calcium carbonate 100 g, colloidal calcium carbonate 50 g, titanium oxide 20 g, KBM603 2 g, KB
2 g of M1003, 2,2'-methylene-bis- (4-
Methyl-6-t-butylphenol) 1 g, 4,4'-
Thio-bis (2-methyl-6-t-butylphenol)
Molecular weight distribution (M _w by GPC of 1 g, molecular weight 6000)
/ _Mn ) of 1.10 polyoxypropylene diol 50 g, Tinuvin 327 0.5 g, Sanol LS-7
0.5 g of 70, 2 g of pentaerythritol tetraacrylate were thoroughly kneaded with 3 paint rolls, 2 g of BTDL and 0.5 g of laurylamine were added, and further kneaded with 3 paint rolls. The same test as in Example 8 was performed.

Example 16 Polymer 100 of Synthesis Example 13
g, ground calcium carbonate 25g, colloidal calcium carbonate 2
5 g, titanium oxide 5 g, KBM603 2 g, KBM1
2g of 003, 1 g of 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-t-butylphenol) 1
g, Tinuvin 327 0.5 g, Sanol LS-770
0.5 g of polyoxypropylene diol having a molecular weight of 2000 and the end thereof being primary aminated 20 g, DMP
Was thoroughly kneaded with 3 paint rolls (Liquid A). Separately, 60 g of Epikote 828, 2 g of BTDL, and 30 g of heavy calcium carbonate were sufficiently kneaded with three paint rolls, and the mixture of the previously kneaded solution A was used in the same manner as in Example 8. Was tested.

Example 17 Polymer 100 of Synthesis Example 14
g, ground calcium carbonate 25g, colloidal calcium carbonate 2
5 g, titanium oxide 5 g, dioctyl phthalate 50 g,
1 g of KBM603, 2,2'-methylene-bis- (4
-Methyl-6-t-butylphenol) 1 g, 4,4 '
-Thio-bis (2-methyl-6-t-butylphenol) 1 g, tinuvin 327 0.5 g, SANOL LS-
0.5 g of 770, 20 g of a polysulfite resin having a molecular weight of 3000, and 5 g of DMP were sufficiently kneaded with three paint rolls (solution A). Separately, 60 g of Epicoat 828, 1 g of # SB-65 (a silanol curing catalyst manufactured by Sansha Kisei Gosei Co., Ltd.), 1 g of lauric acid, and 30 g of ground calcium carbonate were sufficiently kneaded with a paint roll and kneaded in advance. The same test as in Example 8 was performed using the mixture of the prepared solution A.

Example 18 Polymer 100 of Synthesis Example 13
g, heavy calcium carbonate 60g, titanium oxide 5g, KB
2 g of M602, 1 g of 2,2′-methylene-bis- (4-methyl-6-t-butylphenol), 4,4′-thio-bis (2-methyl-6-t-butylphenol) 1
g, Tinuvin 327 0.5 g, Sanol LS-770
0.5g, Epicoat 828 70g, DMP 8
g, molecular weight distribution by GPC with an average molecular weight of 5000 (M
The same test as in Example 8 was carried out by using 20 g of polyoxypropylene triol having _w / M _n ) of 1.10 whose terminal was primary aminated and 2 g of # 918 were sufficiently kneaded with three paint rolls. I went.

Example 19 Polymer 100 of Synthesis Example 16
g, heavy calcium carbonate 60 g, colloidal calcium carbonate 6
0 g, titanium oxide 20 g, KBM603 1 g, KBM
803 1 g, 2,2′-methylene-bis- (4-methyl-6-t-butylphenol) 1 g, 4,4′-thio-bis (2-methyl-6-t-butylphenol) 1
g, Tinuvin 327 1 g, Sanol LS-770 1
g, 3 g of tin octylate, and 1 g of laurylamine were sufficiently kneaded with three paint rolls, and the same test as in Example 8 was performed.

From Examples 12 to 19, the composition of the present invention exhibits excellent water-resistant adhesive property and durable adhesive property by adding various silane coupling agents, and if necessary, an epoxy resin, an epoxy resin curing agent, etc. may be added. By adding
It can be seen that even more excellent adhesion is exhibited.

(Synthesis Example 17) Propylene oxide was polymerized using glycerin as an initiator and a zinc hexacyanocobaltate catalyst to obtain a polyoxypropylene triol having an average molecular weight of 20,000. The end of the obtained polyoxypropylene triol was alcoholized with sodium hydroxide and then reacted with allyl chloride. This was dissolved in a hexane-water system, the by-product salt was removed in the aqueous layer, and hexane was removed from the hexane layer to obtain polyoxypropylenetriol having an allyl group at the terminal. Further, this was reacted with methyldimethoxysilane in the presence of a platinum catalyst to obtain polyoxypropylenetriol having a silyl group at 60% of its terminals and an average molecular weight of 20,000.

Synthesis Example 18 Propylene glycol was used as an initiator to polymerize propylene oxide using a potassium hydroxide catalyst to give a bifunctional PPG having an average molecular weight of 3000.
Was synthesized. The end of this PPG was alcoholated with sodium metal, reacted with dichloromethane, further reacted with allyl chloride, and then dissolved in hexane-water system to remove the by-product salt in the aqueous layer and remove hexane from the hexane layer. By doing so, a terminal allyl group-containing polyoxypropylene diol having an average molecular weight of 8000 was obtained. Further, this was reacted with methyldimethoxysilane in the presence of a platinum catalyst to obtain polyoxypropylene diol having a silyl group at 70% of its terminals and an average molecular weight of 8000.

(Synthesis Example 19) Polymerization of propylene oxide was carried out using propylene glycol as an initiator and aluminum porphyrin as a catalyst to give an average molecular weight of 8,000.
Of polyoxypropylene diol having M _w / M _n of 1.10 measured by GPC was obtained. After the terminal of this polyoxypropylene diol is alcoholated with sodium metal, it is reacted with allyl chloride to allylicize the terminal and dissolved in hexane-water system to remove the by-product salt in the aqueous layer and remove hexane from the hexane layer. By doing so, the terminal was modified to an allyl group. Further, this was reacted with methyldimethoxysilane in the presence of a platinum catalyst to give a silyl group at the terminal 70% of which an average molecular weight of 8000 and M _w.
A polyoxypropylene diol having an _Mn of 1.10 was obtained.

(Synthesis Example 20) Propylene glycol was polymerized with propylene glycol as an initiator and potassium hydroxide as a catalyst to obtain polyoxypropylene diol having an average molecular weight of 2000. After this polyoxypropylene diol is alcoholized with sodium metal, it is reacted with allyl chloride, dissolved in hexane-water system, the by-product salt is removed in the aqueous layer, and hexane is removed from the hexane layer, so that the terminal is allyl. A polyoxypropylene diol having an average molecular weight of 2000 was obtained.

(Synthesis Example 21) Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain an average molecular weight of 170.
00 polyoxypropylene tetraol was obtained. After the end of the obtained polyoxypropylene tetraol was alcoholated with sodium hydroxide,
% After reacting with an equivalent amount of allyl chloride, the end group is reacted with an equivalent amount of epichlorohydrin, further the resulting product is dissolved in hexane-water system, the by-product salt is removed in the aqueous layer,
By removing hexane from the hexane layer, polyoxypropylene tetraol having an average molecular weight of 17,000, 30% at the terminal of which is an allyl group and 70% at the end of which is an epoxy group was obtained.

(Synthesis Examples 22 to 24, 29) Monomers, polyethers, solvents, initiators and additives having the respective compositions shown in Table 6 were charged in an autoclave, heated to 70 ° C. and stirred for 10 hours for polymerization. Was advanced. Thereafter, the additives were removed and the solvent was removed to obtain each fluoropolymer.

(Synthesis Examples 25 and 26) CTFE, polyethers, solvents and additives having the respective compositions shown in Table 6 were charged in an autoclave, and the temperature was raised to 60 ° C. with stirring.
Polymerization proceeded while gradually charging a mixed liquid of a monomer other than E and an initiator over 5 hours. After the completion of the charging, the reaction was further continued at 60 ° C. for 5 hours, the additives were removed, and the solvent was removed to obtain each fluoropolymer.

(Synthesis Example 27) CTF of each composition shown in Table 6
E, a polyether, a solvent and an additive were charged into an autoclave, the temperature was raised to 60 ° C. with stirring, and a mixed solution of a monomer other than CTFE and an initiator was gradually charged into the autoclave over 5 hours to proceed with polymerization. . After the completion of the charging, the reaction was further continued at 60 ° C. for 5 hours, the additives were removed, and the solvent was removed to obtain each fluoropolymer. The unsaturated degree of the obtained polymer was measured and found to be 0.25 mmol · g ⁻¹ . When this was reacted with methyldimethoxysilane in the presence of a chloroplatinic acid catalyst, the degree of unsaturation was 0.02.
It was confirmed that the silyl group had been introduced by the decrease to mmol · g ⁻¹ .

(Synthesis Example 28) Monomers, polyethers, solvents, initiators, and additives having the respective compositions shown in Table 6 were charged in an autoclave, heated to 70 ° C., and stirred for 10 hours to proceed polymerization. . Thereafter, the additives were removed and the solvent was removed to obtain each fluoropolymer. The unsaturated degree of the obtained polymer was measured and found to be 0.33 mmol · g ⁻¹ . When this was reacted with methyldimethoxysilane in the presence of a chloroplatinic acid catalyst, the degree of unsaturation was 0.06 mm.
It was confirmed that the silyl group had been introduced by decreasing the ^value to ol · g ⁻¹ .

(Examples 20 to 26) For 100 g of each polymer shown in Table 7, 75 g of heavy calcium carbonate, 75 g of colloidal calcium carbonate, 50 g of titanium oxide, 30 g of dioctyl phthalate, 6 g of hydrogenated castor oil, 1 g of styrenated phenol. The types and amounts of the silane coupling agents shown in Table 7 were kneaded while being sufficiently dehydrated so as to be substantially free of water, and 1 g of # 918 as a catalyst was added thereto and further kneaded. The same test as in ~ 7 was performed.

(Comparative Examples 11 to 17) The same tests as in Examples 1 to 7 were conducted except that 100 g of each polymer shown in Table 8 and each kind and amount of the silane coupling agent were used. The results are also shown in Table 8. Note that in Comparative Examples 13 to 15, the test was impossible because the peeling occurred at the interface during immersion of the test body in water.

As can be seen from the above examples and comparative examples, a system comprising a polyoxyalkylene having a silylated end and a silane coupling agent exhibits excellent adhesiveness unless the silane coupling agent is a specific aminosilane compound. No, and even if these are used, the water-resistant adhesion is poor. Further, when the polymer of the component (A) of the present invention is used alone, the initial adhesiveness,
Water-resistant adhesiveness has a certain level of performance, but particularly inferior in water-resistant adhesiveness, on the other hand, for the composition of the present invention, even if any silane coupling agent is added, very good initial adhesiveness and water-resistant adhesiveness It can be seen that

(Examples 27 to 30, Comparative Examples 18 to 21)
Table 9 shows the types of synthesis examples used in Examples 27 to 30 and Comparative Examples 18 to 21, the type and amount of the added silane coupling agent, and the test results. The details of each example and comparative example will be described below.

Example 27 Polymer 100 of Synthesis Example 22
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5g, titanium oxide 20g, dioctyl phthalate 50
g, hydrogenated castor oil 6 g, KBM603 1 g styrenated phenol 1 g, benzotriazole ultraviolet absorber 1
g and 1 g of a hindered amine anti-aging agent were sufficiently kneaded with three paint rolls, 2 g of # 918 was added, and the kneaded mixture was further sufficiently kneaded to carry out the same test as in Example 8.

Comparative Example 18 The same test as in Example 27 was carried out except that 100 g of the polymer obtained in Synthesis Example 17 was used instead of 100 g of the polymer obtained in Synthesis Example 22 used in Example 27. It was

(Comparative Example 19) KBM used in Example 27
The same test as in Example 27 was carried out except that 603 was not used.

Example 28 Polymer 100 of Synthesis Example 22
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5g, titanium oxide 20g, dioctyl phthalate 50
g, hydrogenated castor oil 6 g, trimethylolpropane triacrylate 3 g, KBM603 1 g styrenated phenol 1 g, benzotriazole-based UV absorber 1 g, hindered amine-based antioxidant 1 g, after thoroughly kneading with 3 paint rolls, # The same test as in Example 27 was carried out by using 2 g of 918 and further thoroughly kneading.

Example 29 A test was conducted in the same manner as in Example 27 except that 100 g of the polymer of Synthesis Example 23 was used instead of the polymer of Synthesis Example 22 used in Example 27.

(Comparative Example 20) KBM used in Example 29
The same test as in Example 29 was carried out except that 603 was not used.

Example 30 A test was conducted in the same manner as in Example 27 except that 100 g of the polymer of Synthesis Example 24 was used instead of the polymer of Synthesis Example 22 used in Example 27.

Comparative Example 21 KBM used in Example 30
The same test as in Example 30 was carried out except that 603 was not used.

Example 31 KBM used in Example 29
A test was conducted in the same manner as in Example 29 except that 1 g of KBM803 was used instead of 603.

As in Comparative Example 18, in the composition comprising a polyether having a hydrolyzable silyl group and a silane coupling agent, water-resistant adhesion was not exhibited unless a specific amino group-containing silane coupling agent was used. Even in this case, the water-resistant adhesion was not sufficient, and in the case of durable adhesion, the adhesive surface partly peeled off, and the test was impossible.

On the other hand, when only the component (A) of the present invention as in Comparative Examples 19 to 21 is cured, the water resistant adhesive property and the durable adhesive property are moderate, but Examples 27 to 31 are used.
As described above, it can be seen that the composition of the present invention is extremely excellent in both water-resistant adhesive property and durable adhesive property, and that the silane coupling agent is not limited to the specific amino group-containing silane coupling agent.

(Examples 32 to 39, Comparative Examples 22 to 23)
Tables 10 and 11 show the types of synthesis examples used in Examples 32 to 39 and Comparative Examples 22 to 23, the type and amount of the added silane coupling agent, and the test results. The details of each example and comparative example will be described below.

Example 32 Polymer 100 of Synthesis Example 27
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5 g, 20 g of titanium oxide, 1.5 g of the reaction product obtained in Reference Example 1, 50 g of polyoxypropylene diol having a molecular weight of 2000 and the end being allyl etherified, 2 g of methanol, 1 g of Nocrac NS-6, and tinuvin 3
1 g of 27, 1 g of Sanol LS-770, and 2 g of methanol were sufficiently kneaded with 3 paint rolls, and then 2 g of dibutyltin bisacetylacetonate was added and further sufficiently kneaded. Was tested.

Comparative Example 22 The same test as in Example 32 was carried out except that the reaction product obtained in Reference Example 1 used in Example 32 was not used.

Example 33 Polymer 100 of Synthesis Example 28
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5 g, titanium oxide 20 g, the reaction product obtained in Reference Example 2 1.5 g, polyoxypropylene diol having a molecular weight distribution (M _w / M _n ) by GPC of molecular weight 6000 of 1.10, 50 g, and styrenated phenol 1 g. After thoroughly kneading 1 g of the benzotriazole-based ultraviolet absorber and 1 g of the hindered amine-based antioxidant with three paint rolls,
The same test as in Example 27 was carried out using 2 g of dibutyltin bisacetylacetonate added and kneaded sufficiently.

Comparative Example 23 The same test as in Example 33 was carried out except that the reaction product obtained in Reference Example 1 used in Example 33 was not used.

Example 34 Polymer 100 of Synthesis Example 22
g, heavy calcium carbonate 50 g, colloidal calcium carbonate 5
0 g, titanium oxide 10 g, KBM602 2 g, Epicoat 828 50 g, triethylenetetramine 10 g,
Dioctyl phthalate 30g, styrenated phenol 1
g, benzotriazole-based UV absorber 1 g, and hindered amine-based anti-aging agent 1 g were sufficiently kneaded with 3 paint rolls, and then # 918 (2 g) was added and kneaded sufficiently, using the same mixture as in Example 27. The test was conducted.

Example 35 Polymer 100 of Synthesis Example 22
g, heavy calcium carbonate 50 g, colloidal calcium carbonate 5
0 g, titanium oxide 20 g, KBM602 2 g, Epicoat 828 70 g, triethylenetetramine 10 g,
After fully kneading 30 g of polyoxypropylene diol having a molecular weight of 2000 with primary amination at the terminal, 1 g of styrenated phenol, 1 g of benzotriazole ultraviolet absorber, and 1 g of hindered amine anti-aging agent with three paint rolls, The same test as in Example 27 was carried out by using 2 g of 918 and further thoroughly kneading.

Example 36 Polymer 100 of Synthesis Example 29
g, ground calcium carbonate 75g, colloidal calcium carbonate 7
5 g, titanium oxide 20 g, KBM603 2 g, KBM
2 g of 1003, 1 g of 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 4,4'-thio-bis (2-methyl-6-t-butylphenol) 1
g, Tinuvin 327 0.5 g, Sanol LS-770
Was thoroughly kneaded with 3 paint rolls. The same test as in Example 27 was conducted using a mixture of 2 g of BTDL.

Example 37 Polymer 100 of Synthesis Example 29
g, ground calcium carbonate 30g, colloidal calcium carbonate 3
0 g, titanium oxide 10 g, KBM1003 2 g, Epicoat 828 60 g, 2,2′-methylene-bis-
(4-methyl-6-t-butylphenol) 1 g, 4,
4'-thio-bis (2-methyl-6-t-butylphenol) 1 g, Tinuvin 327 0.5 g, Sanol LS
0.5 g of -770 was thoroughly kneaded with three paint rolls. Here, 2 g of KBM603 and a molecular weight of 20
The same test as in Example 27 was carried out by adding 20 g of the polyoxypropylene diol of 00 having an aminated end, 20 g of DMP, 2 g of BTDL, and further mixing them.

Example 38 Polymer 100 of Synthesis Example 22
g, heavy calcium carbonate 50g, titanium oxide 5g, KB
1 g of M603, 3 g of KBM1003, 1 g of 2,2′-methylene-bis- (4-methyl-6-t-butylphenol), 4,4′-thio-bis (2-methyl-6-t)
-Butylphenol) 1 g, tinuvin 327 1 g, SANOL LS-770 1 g, and DMP 5 g were sufficiently kneaded with three paint rolls (solution A). Separately, 50 g of hexahydrophthalic acid diglycidyl ester, # SB-
65 g, lauric acid 1 g, ground calcium carbonate 25
g was sufficiently kneaded with three paint rolls, and a mixture of the previously kneaded liquid A was used to perform the same test as in Example 27.

Example 39 Polymer 100 of Synthesis Example 22
g, heavy calcium carbonate 50g, titanium oxide 5g, KB
2 g of M603, 2 g of KBM1003, 1 g of 2,2′-methylene-bis- (4-methyl-6-t-butylphenol), 4,4′-thio-bis (2-methyl-6-t)
-Butylphenol) 1 g, Tinuvin 327 0.5
g, Sanol LS-770 0.5 g, average molecular weight 40
00 g of liquid polysulfide resin, 6 g of DMP
Was thoroughly kneaded with 3 paint rolls (A
liquid). Separately, 50g of Epicoat 828 and 2 of BTDL
g and 30 g of ground calcium carbonate were sufficiently kneaded with three paint rolls, and the mixture of the previously kneaded solution A was used to perform the same test as in Example 27.

(Synthesis Example 30) Xylene, synthetic magnesium silicate (Kyowa Kagaku, KW-2000), and AIBN were charged in a pressure resistant reactor made of stainless steel and equipped with a stirrer.
The monomer shown in 2 was polymerized. Polymerization was carried out by charging monomers other than CTFE and then removing the dissolved air with liquid nitrogen.
Next, CTFE was introduced, the temperature was gradually raised, the temperature was maintained at 65 ° C., the polymerization reaction was continued for 10 hours under stirring, and then the reaction vessel was cooled with water to terminate the polymerization. After cooling the reactor to room temperature, unreacted monomers were extracted and the reactor was opened. The polymer solution was filtered and then concentrated under vacuum to obtain a fluoropolymer having a solid content concentration of 60%.

(Synthesis Examples 31 and 32) Similar to Synthesis Example 30, among the compounds shown in Synthesis Examples 31 and 32 of Table 12, C
After the monomers except TFE were charged, the dissolved air was removed by liquid nitrogen, then CTFE was introduced and polymerization was carried out to obtain a fluoropolymer having a solid content concentration of 60%.

(Synthesis Example 33) Polyoxypropylene triol having a molecular weight of 20,000 was obtained by polymerizing propylene oxide in the presence of a double metal cyanide complex catalyst using glycerin as an initiator. Sodium methylate (28% was added to the obtained polyoxypropylene triol.
Methanol solution) to the hydroxyl value of the polyol.
After adding 1 equivalent and demethanoling, 1.1 equivalent was added with respect to the sodium which added allyl chloride, it was made to react, and the allyl group was introduce | transduced into the terminal. The salt formed in the system was removed by filtration, and the purified polymer was reacted with methyldimethoxysilane in the presence of a platinum chloride catalyst to introduce a silyl group at the terminal. The rate of introduction of terminal silyl groups in the obtained polymer was 75%.

(Synthesis Example 34) A polyoxypropylene glycol having a molecular weight of 10,000 was obtained by polymerizing propylene oxide in the presence of a potassium hydroxide catalyst using ethylene glycol as an initiator. Sodium methylate (28% methanol solution) was added to the obtained polyoxypropylene glycol in an amount of 1.1 equivalents based on the hydroxyl value of the polyol, and methanol was removed. One equivalent was added and reacted to introduce an allyl group at the terminal. The salt formed in the system was removed by filtration, and the purified polymer was reacted with methyldimethoxysilane in the presence of a platinum chloride catalyst to introduce a silyl group at the terminal. The rate of introduction of terminal silyl groups in the obtained polymer was 80%.

(Synthesis Example 35) Propylene glycol was polymerized with propylene glycol as an initiator and aluminum polyfin as a catalyst to obtain polyoxypropylene glycol having a molecular weight of 10,000. When the obtained polyoxypropylene glycol was measured by gel permeation chromatography, M _w / M _n was 1.10. Sodium methylate (28% methanol solution) was added to the obtained polyoxypropylene glycol in an amount of 1.1 equivalents based on the hydroxyl value of the polyol, and methanol was removed.
One equivalent was added and reacted to introduce an allyl group at the terminal. The salt formed in the system was removed by filtration, and the purified polymer was reacted with methyldimethoxysilane in the presence of a platinum chloride catalyst to introduce a silyl group at the terminal. The rate of introduction of terminal silyl groups in the obtained polymer was 80%.

(Synthesis Example 36) Propylene oxide was prepared using polyoxytetramethylene glycol (PTG-4000, Hodogaya Chemical Co., Ltd.) having an average molecular weight of 4000 and having a hydroxyl group at the terminal as an initiator in the presence of a complex metal cyanide complex catalyst. Was polymerized to obtain a polyoxyalkylene glycol having a molecular weight of 6000. Sodium methylate (28% methanol solution) was added to the obtained polyoxyalkylene glycol in an amount of 1.1 equivalents based on the hydroxyl value of the polyol, and methanol was removed. One equivalent was added and reacted to introduce an allyl group at the terminal. The salt produced in the system was removed by filtration, and the purified polymer was present in the presence of a platinum chloride catalyst.
Methyldimethoxysilane was reacted to introduce a silyl group at the terminal. The rate of introduction of terminal silyl groups in the obtained polymer was 75%.

(Synthesis Example 37) Butyl acrylate, γ-
Methacryloxypropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane, AIBN
Was stirred to give a mixed solution. This mixture was charged into a flask and heated to 80 ° C. with stirring. Polymerization begins after a few minutes and an exotherm occurs. After the exotherm was moderated, the remaining mixed solution was gradually added dropwise over 3 hours to obtain a polymer. Its molecular weight was 6,500.

Reference Example 3 Synthesis of Reaction Product of Silane Coupling Agent N-β- (aminoethyl) was added to a N ₂ -substituted eggplant flask.
-Γ-aminopropyltriethoxysilane (A-112
0, manufactured by Nippon Unicar Co., Ltd.) 22.2 g and KBM40
23.6 g of 3 was added and the reaction was carried out at 130 ° C. for 3 hours with stirring under N ₂ gas flow. The reaction product was a pale red liquid, and it was confirmed from the infrared spectrum that characteristic absorption derived from epoxy groups and amino groups was reduced.

Reference Example 4 (Synthesis of Reaction Product of Silane Coupling Agent) 22.2 g of A-1120 was placed in a N ₂ -substituted eggplant flask.
And, 24.8g of KBM503 is thrown in, 120 degreeC
The mixture was stirred for 3.5 hours under N ₂ flow to obtain a reaction product. The reaction product was a pale red liquid, and it was confirmed from the infrared spectrum that characteristic absorption derived from acryloyl group and amino group was reduced.

(Examples 40 to 42) 50 g of the fluoropolymer obtained in Synthesis Examples 30 to 32, 70 g of the polymer obtained in Synthesis Example 33, 3 g of a catalyst and 1 g of a silane coupling agent were mixed well. Then, a composition was obtained. The composition obtained,
Based on JIS-K-6854, a T-type peel test specimen was prepared and evaluated. As the adherend, JIS-H-4000
Aluminum plate A-1050P (100 × 25 × 2m
m of the above composition with a spatula to about 0.5 m
The coating was applied to a thickness of m and laminated together, and a hand roller of 5 kg was used to perform pressure bonding 5 times without reciprocating in the length direction. These samples were cured and cured at 23 ° C. for 2 days and further at 50 ° C. for 3 days, and subjected to a tensile test. The results obtained are shown in Table 1.
3 shows. However, the tensile speed is
50 mm / min, 200 mm for T-type peel test
/ Min. However, the unit of tensile shear strength is kg / cm ² , and the unit of T-type peel strength is kg / 25 mm.

(Comparative Examples 24 to 26) 50 g of the fluoropolymers obtained in Synthesis Examples 30 to 32 and 70 g of the polymer obtained in Synthesis Example 33 were added with 3 g of a curing catalyst alone to prepare cured products. did. Using this cured product, a T-type peel test was conducted in the same manner as above. The results are shown in Table 13.

(Comparative Example 27) A cured product was prepared in the same manner as in Example 40 except that the polymer of Synthesis Example 30 was used in Example 40. Using this cured product, a T-type peel test was conducted in the same manner as above. The results are shown in Table 13.

From Table 13, it can be seen that the adhesion of the cured product is improved by adding the silane coupling agent to the composition comprising the fluoropolymer and the polyether.
Further, the strength is improved by incorporating the fluoropolymer.

(Synthesis Examples 40 to 45) In the same manner as in Synthesis Example 40, among the compounds (molar ratio) shown in Synthesis Examples 40 to 45 in Table 14, monomers except CTFE were charged and then dissolved in liquid nitrogen. Was removed, CTFE was then introduced, and polymerization was carried out to obtain a fluoropolymer having a solid content concentration of 60%. Moreover, the molecular weight of each fluoropolymer was measured by GPC. The results are shown in Table 14.

(Examples 43 to 47) 50 g of the fluoropolymers obtained in Synthesis Examples 40 to 44, 70 g of the polymers obtained in Synthesis Examples 34 to 37, 3 to 5 g of a catalyst, and a silane coupling agent. A composition was obtained by thoroughly mixing 1 g and 0 to 20 g of an epoxy resin. About the obtained composition, Example 4
The same test as 0 to 42 was performed.

Also from each of the above compositions a thickness of 2
mm hardened material sheet is prepared, a No. 3 type dumbbell is punched out in accordance with JIS-K-6301, and a tearing speed is 50.
The breaking strength (unit: kg / cm ² ) and the elongation at break (unit:%) were measured at 0 mm / min. The respective results obtained are shown in Table 15.

(Comparative Examples 28 to 32) Synthesis Examples 40 and 42,
50 g of the fluoropolymer obtained in 44, Synthesis Example 34 to
A cured product was prepared by adding only 3 to 5 g of the curing catalyst and 0 to 20 g of the epoxy resin to 70 g of the polymer obtained in 37. Using this cured product, a T-type peel test was conducted in the same manner as above. The results are shown in Table 16.

(Comparative Example 33) A cured product was prepared in the same manner as in Example 43 except that the polymer of Synthesis Example 40 was used in Example 43. Using this cured product, a T-type peel test was conducted in the same manner as above. The results are shown in Table 16.

From Tables 15 and 16, it can be seen that the adhesiveness is improved by incorporating the silane coupling agent. Furthermore, addition of an epoxy resin is useful because a composition having high strength can be obtained.

(Examples 48 to 49, Comparative Examples 34 to 36)
0 to 50 g of the fluoropolymers of Synthesis Examples 41 and 43, 70 to 100 g of the polymer of Synthesis Example 33, 3 g of a curing catalyst, and 0 to 1 g of a silane coupling agent were mixed well to obtain a composition. An ISO type test body was prepared from the obtained composition according to JIS A5758, and the adhesiveness of the composition was tested. However,
As a pretreatment, an adherend was immersed in water at 20 ° C. for 7 days, and then an ISO type test body was prepared without performing a drying treatment.

The results are shown in Table 17. However, the adherend 4: mortar, the adherend 5: anodized aluminum, and the adherend 6: pretreated mortar plate (water content relative to the dried mortar plate was 40.2%).

The tensile adhesive strength (kg / cm ² ) is JIS-
ISO type test body is prepared according to A-5758, and 23 ° C.
-After being cured at 60% humidity for 14 days, it was further cured at 30 ° C and then subjected to a tensile test at a speed of 50 mm / min.

From Table 17, it is seen that the cured product containing the silane coupling agent has excellent adhesive strength, and the adhesiveness to the wet surface is particularly improved by the effect of fluorine.

[0225]

[Table 1]

[0226]

[Table 2]

[0227]

[Table 3]

[0228]

[Table 4]

[0229]

[Table 5]

[0230]

[Table 6]

[0231]

[Table 7]

[0232]

[Table 8]

[0233]

[Table 9]

[0234]

[Table 10]

[0235]

[Table 11]

[0236]

[Table 12]

[0237]

[Table 13]

[0238]

[Table 14]

[0239]

[Table 15]

[0240]

[Table 16]

[0241]

[Table 17]

[0242]

EFFECT OF THE INVENTION The curable composition of the present invention is a highly practical curable composition having good elasticity, excellent weather resistance and good adhesiveness.

Adhesion is improved by incorporating a silane coupling agent into a resin composed of a fluoropolymer and a polyether containing a hydrolyzable silyl group.

Further, the fluorine-containing polymer is contained in the composition, and it has excellent water resistance at the adhesive portion and excellent adhesion to the wet surface of the adherend. To be done.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Etsuko Sakai 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Central Research Laboratory, Asahi Glass Co., Ltd.

Claims (12)

[Claims] 1. A fluorine-containing organic elastic polymer having a curable site, (A-1), a silane coupling agent (B), and
(C) Component (A-1) curing catalyst and / or (B)
A curable composition comprising a catalyst that accelerates the reaction of the components. 2. A fluorine-containing organic elastic polymer having (A-2) at least one polyoxyalkylene side chain and having a curable site, (B) a silane coupling agent, and
(C) Component (A-2) curing catalyst and / or (B)
A curable composition comprising a catalyst that accelerates the reaction of the components. 3. A fluorine-containing organic polymer (A-3), (A-
4) Fluorine-free organic elastic polymer having at least one curable site, (B) silane coupling agent, and (C) component (A-4) curing catalyst and / or (B) component reaction A curable composition comprising: (A-5) Obtained by polymerizing a polymerizable monomer having a polymerizable unsaturated group based on a fluoroolefin in the presence of a fluorine-free organic elastic polymer having at least one curable site. A curable composition comprising the above-mentioned fluoropolymer, (B) a silane coupling agent, and a curing catalyst for the component (A-5) and / or a catalyst for promoting the reaction of the component (B). 5. The curable composition according to claim 3, wherein the fluorine-free organic elastic polymer is polyoxyalkylene. 6. (A-6) a polyoxyalkylene having a curable site and fluorine, (B) a silane coupling agent, and (C) a curing catalyst for the component (A-6) and / or
Alternatively, a curable composition containing a catalyst that accelerates the reaction of the component (B). 7. The curable composition according to claim 1, wherein the curable moiety is a hydrolyzable silyl group represented by the following formula (1). [Chemical 1] However, a is an integer of 0, 1, 2, or 3, b is 0,
An integer of 1 or 2, m is an integer of 0 or more, provided that 1 ≦ a
+ Mb. R ¹ and R ² are the same or different hydrocarbon groups having 1 to 10 carbon atoms or halogenated hydrocarbon groups,
X ¹ and X ² are the same or different hydrolyzable groups. 8. The curable moiety is an epoxy group.
Curable composition of 1 chosen from -6. 9. The curable portion is a hydroxyl group, and the curable portion is a hydroxyl group.
1. A curable composition selected from 10. The curable composition according to claim 1, wherein the silane coupling agent is represented by the following formula (2). R ³ _n SiX _4-n (2) In the formula, X represents a hydrolyzable group, R ³ represents an organic group having 1 to 30 carbon atoms, and n represents an integer of 0 to 3. 11. A compound represented by the following formula (2), wherein R ³ is an organic group containing a functional group selected from an amino group, an epoxy group, a methacryl group, an acryl group and a mercapto group. The curable composition according to claim 1, wherein R ³ is a reaction product of a compound represented by the following formula (2), which is an organic group containing a group reactive with the functional group. R ³ _n SiX _4-n (2) In the formula, X represents a hydrolyzable group, R ³ represents an organic group having 1 to 30 carbon atoms, and n represents an integer of 0 to 3. 12. The curable composition according to claim 1, further comprising at least one selected from (D) a dehydrating agent, a solvent, an epoxy resin, an epoxy curing agent and a photopolymerizable monomer. Curable composition containing a compound.