JPH06116466A - Production of new fluoropolymer composition, and curable composition - Google Patents

Abstract

PURPOSE:To obtain a fluoropolymer compsn. useful for obtaining a curable compsn. which is stretchable and excellent in weatherability, stain resistance, and adhesion to a substrate by polymerizing a fluoroolefin-based polymerizable unsatd. monomer in a specific polyoxyalkylene. CONSTITUTION:A fluoroolefin-based polymerizable unsatd. monomer (e.g. tetrafluoroethylene) is polymerized, if necessary together with a copolymerizable unsatd. monomer (e.g. ethyl vinyl ether), in a polyoxyalkylene having functional groups into which hydrolyzable silyl groups can be introduced (e.g. allyl ether of polyoxypropylene diol).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing polymer having excellent weather resistance and a method for producing the same.

[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 recent years, in addition to this, for example, even if the above conditions are satisfied, such as a silicone resin, the problem of contamination occurrence due to migration of low molecular weight silicone oil or plasticizer contained therein, and the requirement for recoatability are required. Is also occurring. For example, taking sealing materials as an example, the oil-based caulking material, which does not have elasticity, has evolved to elastic urethane type and polysulfide type, and a silicone type with good weather resistance has been developed. There was a drawback that the sex was remarkable.

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, it cannot be said that these have sufficient weather resistance.

The one in which an acrylic resin is mixed for the purpose of improving the physical properties of the above-mentioned modified silicone is Japanese Patent Publication No. 63-65.
No. 086, JP-A No. 60-31556, JP-A No. 60-228516, and the like in which a vinyl polymer is mixed are proposed in Japanese Examined Patent Publication No. 4-56066. However, the weather resistance was not sufficient.

Further, a proposal for providing a polymer for pressure-sensitive adhesive by the same method is proposed in Japanese Patent Publication No. 15836/1992. However, even in this case, an acrylic resin is compounded and adhesiveness, particularly long-term The adhesion retention was not sufficient. On the other hand, fluororesin is widely used industrially as a resin having high weather resistance. For example, a tetrafluoroethylene polymer and a tetrafluoroethylene-olefin copolymer are known. Furthermore, fluoroolefin-vinyl ether copolymers and fluoroolefin-vinyl ester copolymers are known, and these are used as coating compositions and the like. The coating composition of the resin is excellent in weather resistance, and industrial benefits such as enhancing durability of buildings are being recognized.

[0006]

The present invention seeks to overcome the aforementioned drawbacks. That is, it is an object of the present invention to provide a novel polymer having excellent weather resistance and stain resistance while having stretchability, and to provide a curable composition using the novel polymer. .

[0007]

The present invention is the following invention. That is, in a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group, a polymerizable unsaturated group-containing monomer based on fluoroolefin and optionally a polymerizable unsaturated group-containing monomer based on fluoroolefin can be copolymerized. A process for producing a fluoropolymer composition characterized by polymerizing a polymerizable unsaturated group-containing monomer, and a fluoroolefin-based polymerizable monomer in a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group. After polymerizing a monomer containing a saturated group and optionally a monomer containing a polymerizable unsaturated group based on a fluoroolefin, the polymerizable unsaturated group-containing monomer is polymerized and then hydrolyzed to a functional group capable of introducing a hydrolyzable silyl group. Of a fluoropolymer composition characterized by introducing a hydrophilic silyl group It is the law.

The present invention also relates to a fluoroolefin-based polymerizable unsaturated group-containing monomer and optionally a fluoroolefin-based polymerizable unsaturated group-containing monomer in a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group. Curable composition containing a fluorine-containing polymer composition characterized by polymerizing a polymerizable unsaturated group-containing monomer copolymerizable with and a polymer having a functional group capable of introducing a hydrolyzable silyl group. After polymerizing a polymerizable unsaturated group-containing monomer based on a fluoroolefin and optionally a polymerizable unsaturated group-containing monomer based on a fluoroolefin in oxyalkylene, it is hydrolyzable It is characterized by introducing a hydrolyzable silyl group into a functional group capable of introducing a silyl group. That is a fluorine-containing polymer composition curable composition comprising a.

Examples of the polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group used in the present invention include those having a repeating unit whose main chain is substantially -RO-. Here, R has 1 to 10 carbon atoms.
Is a divalent hydrocarbon group and / or a halogen-containing hydrocarbon group.

Specifically,-(CH ₂ ) _n O- (n is an integer of 1 to 10)
, -CH (CH ₃ ) -CH ₂ -O-, -CH (C ₂ H ₅ ) -CH ₂ -O-, -CH (O-CH ₂ -C
_{H = CH 2) CHCH 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- and the like, and examples thereof include those repeating units alone or in a mixture of two or more kinds in a random or block form. It is not limited to these.

Preferred polyoxyalkylenes are polyoxyalkylene diols, polyoxyalkylene triols and polyoxyalkylene tetraols. Further, in the present invention, an olefin-terminated polyoxyalkylene compound such as an allyl-terminated polyoxyalkylene monool produced by using an initiator having an olefin group such as an allyl group can also be used.

As the functional group capable of introducing a hydrolyzable silyl group in the present invention, the polyoxyalkylene-terminated hydroxyl group is a preferred functional group. Preferred functional groups other than the hydroxyl group are an isocyanate group, an epoxy group and an amino group. , A mercapto group, an olefinically unsaturated group, and the like. The number of functional groups is preferably 2 to 4. The method of introducing these functional groups into polyoxyalkylene includes the following methods.

(A) Isocyanate Group A terminal hydroxyl group of polyoxyalkylene (mono) polyol is reacted with an excess of polyfunctional isocyanate. (B) Epoxy group After the terminal hydroxyl group of polyoxyalkylene (mono) polyol is alcoholated with an alkali metal, epichlorohydrin is reacted.

(C) Amino group The terminal hydroxyl group of the polyoxyalkylene (mono) polyol is directly aminated with ammonia. Or (A),
The terminal isocyanate group or epoxy group of the polyoxyalkylene obtained in (B) is reacted with an excess of polyfunctional amine.

(D) Mercapto group A cyclic sulfide is reacted with the end of the polyoxyalkylene (mono) polyol. Alternatively, the polyoxyalkylene terminal 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.

(E) Olefinically unsaturated group (a) A compound having a hydroxyl group-reactive group and a polymerizable group is reacted with the terminal hydroxyl group of the polyoxyalkylene (mono) polyol. As such a compound, for example, a terminal of a hydroxyl group-containing polymerizable monomer such as (meth) acrylic acid (chloride), allyl isocyanate, allyl alcohol or 2-hydroxyethyl vinyl ether is modified with a polyfunctional isocyanate or a large excess of phosgene. And maleic anhydride.

(A) The terminal hydroxyl group of the polyoxyalkylene (mono) polyol is denatured, and the unsaturated group-containing compound is further introduced at the terminal. For example, a compound containing a halogen and an unsaturated group such as allyl chloride, allyl bromide, p-chloromethylstyrene, p-bromomethylstyrene, and 2-chloroethyl vinyl ether is reacted with an alkali metal alkoxide of the terminal hydroxyl group of polyoxyalkylene. . Or an excess diisocyanate, or a large excess of phosgene, or a dicarboxylic acid (and / or its anhydride) is reacted with the terminal hydroxyl group of polyoxyalkylene to modify the terminal, and then allylamine, allyl alcohol, hydroxybutyl vinyl ether, Two
Reacting an active hydrogen-containing polymerizable monomer such as hydroxyethyl (meth) acrylate.

(C) Upon polymerization of polyoxyalkylene, an unsaturated group-containing monoepoxide compound such as allyl glycidyl ether, vinyl glycidyl ether and glycidyl methacrylate is copolymerized with a monoepoxide such as alkylene oxide. (D) A monoepoxide compound is reacted with a compound having a polymerizable unsaturated group and a hydroxyl group as an initiator.

The molecular weight of the polyoxyalkylene is not particularly limited, and various molecular weights can be used depending on the application. When a polymer having a molecular weight of 1000 or less is used, the obtained polymer, or one in which a curable site is introduced into the polymer, has relatively hard hardness but elasticity, and an elastic coating,
It can be used as a hot melt adhesive or the like. When a polymer having a molecular weight of 1,000 or more and 50,000 or less is used, the resulting polymer exhibits fluidity at room temperature, and a polymer having a pressure-sensitive adhesive or a curable moiety introduced therein can be used as a sealant or the like. When a polymer having a molecular weight of 50,000 or more is used, it can be used, for example, as a fluororubber excellent in fluidity, weather resistance and heat resistance.

The molecular weight distribution of polyoxyalkylene is not particularly limited, and the storage stability, viscosity,
It can be optionally used depending on workability and physical properties at the time of curing. Although the molecular weight distribution affects each of the above items, the molecular weight distribution is not affected in terms of providing the curable composition having excellent weather resistance of the present invention.

In the present invention, the fluoroolefin-based polymerizable unsaturated group-containing monomer includes tetrafluoroethylene, chlorotrifluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, pentafluoroethylene, and perfluoroethylene. 2 to 10 carbon atoms such as fluoropropyl vinyl ether,
Particularly, a fluoroolefin having about 2 to 6 carbon atoms is preferably adopted. Of these, perhalofluoroolefins in which hydrogen is completely replaced by halogen are most preferable.

By containing the polymerized units of the polymerizable unsaturated group-containing monomer based on these fluoroolefins in the polymer, surprisingly, the adhesiveness to the substrate more than that of the ordinary polyoxyalkylene polymer is exhibited. I understood it. It is considered that this is because the inclusion of polymerized units of these monomers improves the wettability with respect to the substrate.

In addition to the fluoroolefin-based polymerized units used in the present invention, the polymerized units of the polymerizable unsaturated-group-containing monomer that can be copolymerized with the fluoroolefin-based polymerized unsaturated-group-containing monomer may be a copolymerization component. Can be included as Examples of the copolymerizable unsaturated group-containing monomer mentioned here include compounds having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group and a methacryloyl group. Specific examples include olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acid esters, methacrylic acid esters, and crotonic acid esters.

As the polymerizable unsaturated group-containing monomer, one in which a part or all of hydrogen bonded to carbon is replaced by fluorine may be adopted. By containing these polymerized units in appropriate amounts, the temperature characteristics of the polymer can be controlled without impairing the weather resistance, and advantages such as cost reduction can be achieved.

Among the above-mentioned copolymerizable unsaturated group-containing monomers which can be added if necessary, vinyl ethers, vinyl esters, allyl ethers, allyl esters, α
The use of olefins and crotonic acid esters is preferable from the viewpoint of weather resistance because the probability of alternate copolymerization with fluoroolefins is high. Particularly preferred are vinyl ethers.

Specific compounds include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether,
Vinyl ethers such as isobutyl vinyl ether, chloroethyl vinyl ether and perfluoroalkyl vinyl ether, olefins such as ethylene, propylene, 1-butene, isobutylene and cyclohexene, allyl alcohol, methyl allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether , Allyl ethers such as 2-hydroxyethyl allyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate, vinyl caprylate, Veova 9 and Veova 10 (C Shell Chemical Co. ₉ and trade names vinyl esters of branched fatty acid consisting of C _10), fatty acid vinyl esters such as vinyl versatate, ethyl acrylate, methyl methacrylate, butyl Acrylic acid or methacrylic acid esters such as acrylate, butyl methacrylate, cyclohexyl methacrylate, and crotonic acid esters such as ethyl crotonic acid, butyl crotonic acid, cyclohexyl crotonic acid, 2-hydroxyethyl crotonic acid, and 2-hydroxylbutyl crotonic acid. Can be given.

The polymer of the present invention can be used as it is, for example, as a sealant or an adhesive, but it may also contain a polymerizable unsaturated group-containing monomer having a curable site,
It is preferable in order to improve the physical properties and adhesiveness of the novel fluoropolymer of the present invention. By curing the curable site with a curing agent or a curing catalyst, the physical properties of the novel fluoropolymer are improved, and even if the above-mentioned catalyst or curing agent is not used, the adhesive property of the polymer can be improved due to the polarity of the curable site. Can be significantly improved. Examples of such a curable site include a hydroxyl group, an amino group, an epoxy group, a mercapto group, an isocyanate group, a carboxyl group, an aldehyde group, an N-methylol group, an unsaturated group, a non-hydroxyl group, an acid amide group, and a hydrolyzable silyl group. And so on.

In particular, when a polymerizable unsaturated group-containing monomer having a hydrolyzable silyl group is added during the polymerization, the resulting polymer is crosslinked by the addition of a curing catalyst and moisture even if no curing agent is used. It is preferable because it can improve strength properties and adhesiveness. Examples of such a monomer include compounds represented by the following formula (2).

[0029]

[Chemical 2]

(A is an organic group containing a polymerizable unsaturated group, a,
b, m, X, R ¹ and R ² are the same as above. )

Specific compounds represented by the formula (2) include, for example, dimethoxymethylvinylsilane, trimethoxyvinylsilane, diethoxymethylvinylsilane, dimethoxymethylallylsilane, dimethoxymethylsilylpropyl acrylate, trimethoxysilylpropyl methacrylate, Examples thereof include dimethoxymethylsilylpropyl vinyl ether and dimethoxymethylsilylpropyl allyl ether.

Further, hydroxyl group, epoxy group-containing polymerizable unsaturated group-containing monomer, (meth) acrylamide, (meth)
It is also preferable to add a polymerizable unsaturated group-containing monomer such as an acrylamide derivative or maleic anhydride at the time of polymerization, since sufficient adhesiveness is exhibited even when the obtained polymer is used as it is.

Specific compounds include hydroxyl groups such as 2-hydroxyethyl vinyl ether, 2-hydroxybutyl vinyl ether, allyl alcohol, 2-hydroxyethyl allyl ether, 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl crotonic acid. Polymerizable unsaturated group-containing monomers, epoxy group-containing polymerizable unsaturated group-containing monomers such as glycidyl allyl ether, glycidyl vinyl ether, glycidyl acrylate, glycidyl methacrylate, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide , Maleic anhydride and the like.

When the polymerizable unsaturated group-containing monomer copolymerizable with the above-mentioned fluoroolefin-based polymerizable unsaturated group-containing monomer is used, it is preferably 80 mol% or less based on the total amount of the monomers. If it exceeds 80 mol%, the polymer cannot obtain sufficient effects such as heat resistance, weather resistance and durable adhesion. It is more preferably 70 mol% or less, and particularly preferably 60 mol% or less.

In polymerizing the above-mentioned polymerizable unsaturated group-containing monomer, a chain transfer agent having a curable site and an initiator having a curable site may be used in order to improve the physical properties and adhesiveness of the obtained polymer. Is preferred. Specific examples of these compounds include the following.

Examples of the chain transfer agent include a hydroxyl group-containing chain transfer agent such as mercaptoethanol and thioglycerol, a mercapto-based chain transfer agent such as mercaptoacetic acid, and (H ₂ N--C).
_{6 H 4 -S) 2, (} HOOC-C 6 H 4 -S) 2, (H
A disulfide chain transfer agent such as OOC—CH ₂ —S) ₂ and a chain transfer agent represented by the following formulas (3) and (4).

[0037]

[Chemical 3]

[Chemical 4]

(Z is an organic group containing a group-polymerizable unsaturated group which is activated by free radicals, R ⁴ is a divalent hydrocarbon group containing no aliphatic unsaturated group having 1 to 20 carbon atoms, a, b,
m, X, R ¹ and R ² are the same as above. )

Specifically, compounds in which Z is a mercapto group, a chlorine group, a bromine group, or an amino group are preferable, and examples thereof include 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane. And other hydrolyzable silyl group-containing mercapto chain transfer agents, p-bromomethylphenyltrimethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropyltrimethoxysilane, 3-
Chloropropyltriethoxysilane, ((CH ₃ O) ₃
SiC ₃ H ₆ S-) ₂ and the like.

As the initiator, HO-C ₃ H ₆ -C (CH ₃ ) (CN) -N = NC (CH ₃ ) (CN) -C ₃ H ₆ -OH HO-CH ₂ -C (CH ₃ ) (CN) -N = NC (CH ₃ ) (CN) -CH ₂ -OH HOOC-C ₂ H ₄ -C (CH ₃ ) (CN) -N = NC (CH ₃ ) (CN) -C ₂ H _There are hydroxyl group- and carboxyl group-containing azo initiators such as _4- COOH and hydrolyzable silyl group-containing azo initiators such as the following formula (5). Specifically, they are represented by (6) and (7). The compound can be mentioned.

[0041]

[Chemical 5]

[Chemical 6]

[Chemical 7]

The polymerization method can be carried out in the same manner as in the case of polymerizing a usual fluoroolefin monomer. That is, as the initiator, in addition to the above-mentioned curable site-containing radical initiator, a method using an ordinary radical initiator, a method using ionizing radiation, or the like can be adopted. The solvent may be added as necessary, but when the reaction is carried out in polyoxyalkylene as in the present invention, a polymerization solvent which is indispensable when preparing a fluororesin solution or a fluororesin dispersion is not always necessary. That is not the case. Further, as the polymerization degree adjusting agent, a general chain transfer agent other than the above-mentioned curable site-containing chain transfer agent may be added. In the present invention, the monomers used for polymerization may be charged at once, or may be fed continuously or dividedly for controlling the internal temperature.

The fluoropolymer composition obtained by polymerizing a monomer in a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group can be used as it is as a curable composition. It is preferable to introduce a hydrolyzable silyl group after the polymerization. This curable composition may be used as a mixture with another curable composition, and if necessary, various additives may be added.

The hydrolyzable silyl group in the present invention is preferably a hydrolyzable silyl group represented by the following formula (1).

[0045]

[Chemical 8]

(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 is a hydrolyzable group. )

Examples of the method of introducing the hydrolyzable silyl group include the following methods (a) and (b). (A) An unsaturated group-containing polyoxyalkylene obtained by the above method is reacted with a hydrosilane compound represented by the following formula (8).

[0048]

[Chemical 9]

(Here, a, b, m, X, R ¹ and R ² are the same as above.) (B) A compound represented by the following formula (9) is directly added to the hydroxyl group at the polyoxyalkylene terminal or the following: It is introduced by reacting it with the amino group, epoxy group, isocyanate group, mercapto group, etc. introduced by the methods described in (A) to (D).

[0050]

[Chemical 10]

(Here, a, b, m, X, R ¹ and R ² are the same as above, R ³ is a divalent organic group having 1 to 10 carbon atoms, Y is an epoxy group, amino group, hydroxyl group, mercapto. An organic group having at least one functional group selected from a group, an isocyanate group, a carboxyl group, an unsaturated group, and a (meth) acryl group.)

The novel fluoropolymer obtained as described above can be used as it is as a pressure-sensitive adhesive or an adhesive.
Alternatively, a curing catalyst or a curing agent may be added, or the mixture may be used by mixing with other curable composition. The additives will be described below.

As the curing catalyst, a curing accelerating catalyst which accelerates the curing reaction of the hydrolyzable silyl group may be used. Such curing catalysts include metal titanates, organosilicon titanates, bismuth tris-2-ethylhexoates, metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate: dibutylamine-2-ethyl. Amine salts such as hexoate and the like: as well as other acidic and basic catalysts may be used. Further, a mixture of the above catalysts and a mixture obtained by chemical modification such as heat treatment may be used.

Further, for example, when a hydroxyl group, an amino group, a mercapto group or the like is introduced as a curable site, a polyfunctional terminal having a functional group such as an isocyanate group, an epoxy group, a carboxyl group or a non-hydroxyl group is introduced into these as a curing agent. A curable composition may be prepared by adding a compound having the compound and, if necessary, a catalyst that accelerates the reaction of these functional groups. In addition to the above-mentioned three components, such a composition also includes a filler, a solvent, a light stabilizer, an ultraviolet absorber, a heat stabilizer, a leveling agent, an adhesiveness-imparting agent, a plasticizer, a physical property adjusting agent, and air oxidation. A curable compound, a photopolymerization initiator, a polymerizable monomer that is polymerized by the initiator, a photopolymerizable monomer, and the like may be added and blended.

Examples of the filler include reinforcing fillers such as fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide. , Fillers such as bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, hydrogenated castor oil and silas balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used.

When it is desired to obtain a hardened composition having high strength with these fillers, mainly fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay And a filler selected from activated zinc white, etc., the curable composition 10 of the present invention.
When it is used in the range of 1 to 1000 parts by weight with respect to 0 parts by weight, favorable results are obtained. Further, when it is desired to obtain a cured composition having low strength and large elongation, titanium oxide is mainly used,
The curable composition 10 of the present invention is a filler selected from calcium carbonate, ground calcium carbonate, surface-treated calcium carbonate, colloidal calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon.
If the amount is 0.1 to 1000 parts by weight based on 0 parts by weight, favorable results are obtained. Of course, these fillers may be used alone or in combination of two or more.

As the solvent, methanol, ethanol,
Examples thereof include alcohols such as isopropanol, n-butanol, and t-butanol, ketones such as methyl ethyl ketone, and aromatic solvents such as xylene and toluene. Generally used as a light stabilizer, an ultraviolet absorber, a heat stabilizer, a hindered amine type, a benzotriazole type, a benzophenone type, a benzoate type, a cyanoacrylate type, a phenol type, an acrylate type, a hindered phenol type, a sulfur type, Each compound such as phosphorus can be used as appropriate.

Examples of the adhesiveness-imparting agent include the following compounds. 1. Silane coupling agent For example, a compound represented by the above formula (9) or the following formula (10).

[0059]

[Chemical 11]

Here, R ⁵ is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 10 carbon atoms which is the same as or different from R ¹ and R ^2, and a, b, m, X, R ¹ and R ² are as described above. Examples of the same and specific compounds include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraphenoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ.
-Aminopropyldimethoxymethylsilane, 3- (2-
Aminoethylaminopropyl) trimethoxysilane, 3
Aminosilanes such as-(2-aminoethylaminopropyl) dimethoxymethylsilane, γ-glycidoxypropyltrimethoxysilane, γ-glycididopropyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Epoxy silanes such as
γ-methacryloxypropyltrimethoxysilane, γ-
Methacrylsilanes such as methacryloxypropyldimethoxymethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane,
Examples thereof include vinylsilanes such as vinyltrichlorosilane. These compounds are added to the composition of the present invention in an amount of 0.01
As described above, by adding about 0.1 to 20 parts by weight, excellent adhesiveness can be obtained.

2. Epoxy compound As an epoxy compound that can be added to the composition of the present invention,
Typical epoxy resins can be used. As the epoxy resin, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, hydrogenated Bisphenol A type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, etc. Diglycidyl ester-based epoxy resin, m-aminophenol-based epoxy resin, diaminodiphenylmethane-based epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-digly Epoxy of unsaturated polymers such as ziraniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycidyl ether of polyhydric alcohol such as glycerin, hydantoin type epoxy resin, petroleum resin, etc. Examples thereof include commonly used epoxy resins such as compounds, vinyl polymers containing an epoxy group, and the like, 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.

Further, 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, 2,4. Amines such as 6-tris (dimethylaminomethyl) phenol, tertiary amine salts, polyamide resins, imidazoles, dicyandiamides,
Boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynylsuccinic anhydride, carboxylic anhydrides such as pyromellitic dianhydride, phenoxy resins, carboxylic acids, Polyalkylene oxide polymers having at least one group capable of reacting with an epoxy group, such as alcohols, on average in the molecule (terminally aminated polyoxypropylene glycol, terminal carboxylated polyoxypropylene glycol, etc.) Group, carboxyl group, polybutadiene modified with hydroxyl group,
Examples include liquid vinyl polymers such as hydrogenated polybutadiene, acrylonitrile-butadiene copolymer, and acrylic polymers, but are not limited thereto. These curing agents may be used in an appropriate amount depending on the purpose within the range of about 0.1 to 300 parts by weight based on 100 parts by weight of the epoxy compound.

It is also preferable to add a plasticizer to the composition of the present invention in order to improve workability. As the plasticizer, a commonly used plasticizer, for example, phthalates such as dioctyl phthalate, dibutyl phthalate, diallyl phthalate and butylbenzyl phthalate,
Dioctyl adipate, isodecyl succinate and other aliphatic dibasic acid esters, diethylene glycol dibenzoate, pentaerythritol ester and other glycol esters, butyl oleate, methyl acetylsilinoleate and other aliphatic esters, tricresyl phosphate, Examples include phosphoric acid esters such as trioctyl phosphate and octyl diphenyl phosphate, epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate, and general plasticizers such as chlorinated paraffin. It is also preferable to use a molecular plasticizer 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, but are not limited to, oligomers of polystyrene such as methylstyrene and polystyrene, oligomers such as polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, and hydrogenated polybutene. 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. Three

Further, a compound having one silanol group in the molecule, or a compound capable of producing the compound by hydrolysis may be added as a physical property adjusting agent 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, and a silicone Resins, 1,2-polybutadiene, 1,4-polybutadiene, diene polymers such as C _{5 to} C ₈ diene polymers and copolymers, and various modified products of these polymers and copolymers (maleization). Modified, boiled oil modified, etc.), but among these, tung oil, liquids of diene polymers (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 compounds. Examples of the photopolymerizable monomer include acrylic special monomers such as polyfunctional modified acrylates which are generally used for electron beam or ultraviolet ray curable resins.

When the above-mentioned additives are added, the adhesiveness, workability, storage stability, curability, etc. can be controlled to desired physical properties without impairing the high weather resistance obtained in the present invention. The weather resistance can be further improved in some cases. The novel fluoropolymer of the present invention can be used as it is in a pressure-sensitive adhesive sealing agent, a waterproofing agent, a coating agent, etc. or as a raw material mixed with other additives, and particularly, the durability and weather resistance of the cured product It is suitable for applications that require

[0070]

【Example】

Examples will be given below, but the present invention is not limited to the following examples.

Synthesis Example 1 Polyoxypropylene diol having an average molecular weight of 16000 was synthesized using a zinc hexacyanocobaltate catalyst as an ethylene glycol initiator. 800 g of this polyoxypropylene diol, 2 of sodium methoxide
20 g of 8% MeOH solution was charged into an autoclave, the system was purged with nitrogen, and the system was stirred at 100 ° C. for 2 hr, the system was depressurized, and methanol was removed at 100 ° C. for 2 hr. Subsequently, 8 g of allyl chloride was charged, and further 60 ° C. for 10 hours.
The reaction was carried out. After cooling this, n-hexane was added in an amount three times as much as the charged PPG to homogenize the system, and then a 3% hydrochloric acid aqueous solution was added to 1/2 weight of n-hexane, followed by stirring for 0.5 hr. Then, after standing for 3 hours, a transparent hexane layer and an aqueous layer were separated, so the hexane layer was separated and dehexaneized by an evaporator to obtain an average molecular weight of 16,000.
As a result, a polyoxypropylene diol having 95% of the ends of allyl etherified was obtained.

Synthesis Example 2 Propylene glycol was used as an initiator to polymerize propylene oxide using a potassium hydroxide catalyst to synthesize a bifunctional PPG having an average molecular weight of 3000. After the end of this PPG was alcoholated with sodium metal, it was reacted with 2/3 equivalent of dichloromethane of the end group, and then 1 /
By reacting with 3 equivalents of allyl chloride and removing the by-product salt and purifying by the same method as in Synthesis Example 1, a polyoxypropylene diol having an average molecular weight of 8000 and 95% of the terminals of which was allyl etherified was obtained. .

Synthesis Example 3 Polyoxypropylene diol having an average molecular weight of 8,000 and an Mw / Mn of 1.10 as measured by gel permeation chromatography, which was obtained by polymerizing propylene oxide using propylene glycol as an initiator and aluminum porphyrin as a catalyst. Got After the end of this polyoxypropylene diol is alcoholated with sodium metal, it is reacted with allyl chloride to allylate the end,
By the same method as in Synthesis Example 1, the by-product salt was removed and purified to obtain Mw / Mn having an average molecular weight of 8000 of 1.1.
A polyoxypropylene diol in which 95% of the 0 ends were allyl etherified was obtained.

Synthesis Example 4 Propylene glycol was used as an initiator to polymerize propylene oxide using a potassium hydroxide catalyst to synthesize a bifunctional PPG having an average molecular weight of 3000. After the terminal of this PPG is alcoholated with sodium metal, it is reacted with allyl chloride, and by-product salts are removed and purified in the same manner as in Synthesis Example 1 to give an average molecular weight of 3
A polyoxypropylene diol in which 95% of the 000 ends was allyl etherified was obtained.

Synthesis Example 5 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 16,000.

Synthesis Example 6 The polyoxypropylene triol obtained in Synthesis Example 5 was subjected to alcoholation of 0.4 equivalents of the terminal hydroxyl groups with sodium hydroxide, and then reacted with allyl chloride. This product was dissolved in a hexane-water system by removing and purifying a by-product salt by the same method as in Synthesis Example 1 to remove the by-product salt in the aqueous layer, and 40% of the end had an allyl group and a hydroxyl value of 6 Polyoxypropylene triol of 0.3 was obtained.

Synthesis Example 7 Propylene oxide was polymerized using pentaerythritol as an initiator and a zinc hexacyanocobaltate catalyst to obtain polyoxypropylene tetraol having an average molecular weight of 10,000. After the terminal of the obtained polyoxypropylene tetraol was alcoholated with sodium hydroxide, a mixed solution of allyl chloride and epichlorohydrin was reacted. This product was dissolved in a hexane-water system by removing and purifying a by-product salt in the same manner as in Synthesis Example 1 to remove the by-product salt in an aqueous layer, and 40% of the end
To give an allyl group and 60% to an epoxy group of polyoxypropylene tetraol.

Synthesis Example 8 After polyoxytetramethylene glycol having an average molecular weight of 4000 (PTG-4000 manufactured by Hodogaya Chemical Industry Co., Ltd.) was alcoholized at the end with sodium hydroxide,
Allyl chloride was added and reacted. By removing the by-product salt and purifying the product by the same method as in Synthesis Example 1, a polyoxytetramethylene glycol having an average molecular weight of 4000 and 95% of the terminals being allyl etherified was obtained.

Examples 1 and 2 Each polyoxypropylene, monomer, solvent, initiator and additive shown in Table 1 were charged in an autoclave and heated at 65 ° C. for 20 hours.
The mixture was stirred and polymerized. After the completion, the additives were removed by filtration, and the solvent was further devolatilized to obtain a polymer. The degree of unsaturation of the obtained polymer was 0.062 mmol · g ⁻¹ in both Examples 1 and 2. When methyldimethoxysilane was reacted with this polymer in the presence of a platinum catalyst to introduce a silyl group, the degree of unsaturation was 0.01.
It decreased to 25 mmol · g ⁻¹ and it was found that a silyl group was introduced.

Examples 3 and 4 The polyoxypropylene, the monomers, the solvent, the initiator and the additives shown in Table 1 were charged into an autoclave, and the temperature was 65 ° C. for 20 hours.
The mixture was stirred and polymerized. After the completion, the additives were removed by filtration, and the solvent was further devolatilized to obtain a polymer. The degree of unsaturation of the obtained polymer was 0.1 mmol · g ⁻¹ in Examples 3 and 4. Methyldimethoxysilane was reacted with this polymer in the presence of a platinum catalyst to introduce a silyl group, and the degree of unsaturation was 0.025 m.
It was found that the concentration dropped to mol · g ⁻¹ and that a silyl group was introduced.

Examples 5 and 6 The polyoxypropylene, chlorotrifluoroethylene, solvent and additives shown in Table 1 were charged in an autoclave,
Warm to 65 ° C. While stirring, a mixture of a monomer other than chlorotrifluoroethylene and an initiator was gradually added over 5 hours. 5 more after addition
The mixture was stirred for hr and polymerized. After the completion, the additives were removed and the solvent was further removed by volatilization to obtain a polymer. The hydroxyl value of the obtained polymer was 4.4 in Example 5 and 9.4 in Example 6. Further, each polymer thus obtained was reacted with γ-isocyanatopropyldimethoxymethylsilane in an amount equal to the hydroxyl value in the presence of tin octylate at 70 ° C. for 5 hours. The isocyanate value of the obtained polymer was quantified by a back titration method using an excess amine, and it was found that 98% of γ-isocyanatopropyldimethoxymethylsilane was reacted.

Examples 7 and 8 Each polyoxypropylene, monomer, solvent, initiator and additive shown in Table 1 were charged in an autoclave and heated at 65 ° C. for 20 hours.
The mixture was stirred and polymerized. After the completion, the additives were removed by filtration, and the solvent was further devolatilized to obtain a polymer. The amount of the epoxy groups contained in the resulting polymer Example 7 0.18 mmol · g ^-1 at was 0.40 mmol · g ^-1 in Example 8. Further, the obtained polymer was reacted with γ-aminopropyldimethoxymethylsilane in an amount of 1.05 equivalent to the epoxy group amount at 70 ° C. for 8 hours. The amount of amino groups in the obtained polymer was quantified by acid titration to find that it was 9% of γ-aminopropyldimethoxymethylsilane.
It was found that 0% had reacted.

Examples 9-16 100 g of the polymer obtained in Examples 1-8, 75 g of ground calcium carbonate, 75 g of colloidal calcium carbonate, 15 g of titanium oxide, 50 g of dioctyl phthalate, 50 g of Nocrac NS
-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.), Tinuvin 327 (manufactured by Ciba Geigy) and Sanol LS770 (manufactured by Ciba Geigy)
1g of each is thoroughly kneaded with 3 paint rolls,
Here, as a curing catalyst, 2 g of dibutyltin bisacetylacetonate was used in Examples 1 to 4, a mixture of 3 g of tin octylate and 1 g of laurylamine was mixed in Examples 5 and 6, and # in Examples 7 and 8. 2 g of 918 (manufactured by Sansha Kisei Gosei Co., Ltd.) was added and further kneaded. Table 1 also shows the results of a tensile test conducted by preparing an H-shaped test piece according to JIS-A-5758 using the obtained composition, and carrying out predetermined curing.

As can be seen from the table, the tensile strength of each of the examples is higher than that of the comparative example (described in Table 2 and described later).
Excellent adhesion, elongation, epoxy group, hydroxyl group,
It can be seen that the adhesive strength is dramatically improved by copolymerizing a polymerizable monomer having a curable site such as a hydrolyzable silyl group. A 2 mm thick sheet was prepared using the above composition and subjected to a surface weather resistance test with a sunshine weatherometer.
There was no abnormality after the lapse of hr.

Comparative Examples 1 to 3 Each of the polymers obtained in Synthesis Examples 1 to 3 used in Examples 1 to 4 was reacted with methyldimethoxysilane using a chloroplatinic acid catalyst to give a terminal allyl group. 90% was silylated. Substituting the three types of terminally silylated polyoxypropylene obtained instead of the polymers used in Examples 9-12,
The examination was conducted in the same manner as in Examples 9 to 12. Table 2 shows the tensile test results of the H-shaped test piece. 2 mm
Thick sheets were prepared and surface weather resistance tests were performed using a sunshine weatherometer.
The surface was decomposed and melted before reaching hr.

Comparative Example 4 A polymer obtained by introducing γ-isocyanatopropyldimethoxymethylsilane into the hydroxyl group of the polymer obtained in Synthesis Example 6 in the same manner as in Examples 5 and 6 was synthesized. Using this polymer, examination was conducted in the same manner as in Examples 5 and 6. H
Table 2 shows the tensile test results of the mold test pieces. 2m again
An m-thick sheet was created and a surface weather resistance test was performed using a sunshine weatherometer.
The surface was decomposed and melted before reaching 0 hr.

Comparative Example 5 Examples 7 and 8 were added to the epoxy group of the polymer obtained in Synthesis Example 7.
A product in which γ-aminopropyldimethoxymethylsilane was introduced was synthesized by the same method as described in (1) above. Using this polymer,
The examination was conducted in the same manner as in Examples 7 and 8. Table 2 shows the tensile test results of the H-shaped test piece. In addition, a 2 mm thick sheet was prepared and a surface weather resistance test was conducted using a sunshine weatherometer.
The surface was decomposed and melted before reaching r.

Comparative Example 6 100 g of the polymer obtained in Synthesis Example 6 was charged into an autoclave, degassed under reduced pressure, the system was replaced with nitrogen, the temperature was raised to 90 ° C., and the mixture was heated and stirred. There, n-butyl acrylate 48.5g, 2-ethylhexyl acrylate 48.
A mixed solution of 5 g, 2 g of γ-methacryloxypropyldimethoxymethylsilane and 5 g of AIBN was added dropwise at 90 ° C. over 2 hours while stirring in the autoclave. 30 minutes after the end of dropping, add 0.25 g of AIBN to each
The mixture was added and stirred for 30 minutes to obtain a pale yellow transparent polymer. Γ-Isocyanatopropyldimethoxymethylsilane was reacted with the obtained polymer in the same manner as in Examples 5 and 6. Using this polymer, a 2 mm thick sheet was prepared in the same manner as in Examples 13 and 14, and a surface weather resistance test was conducted using a sunshine weatherometer. However, cracks were generated on the entire surface before 3000 hours had elapsed. Was.

Example 19 Each polyoxypropylene having the composition shown in Table 3, a monomer, a solvent, an initiator and an additive were charged in an autoclave and heated to 65 ° C.
The mixture was stirred and polymerized for 20 hours. After the completion, the additives were removed by filtration, and the solvent was further devolatilized to obtain a polymer. The degree of unsaturation of the obtained polymer was 0.20 mmol · g ⁻¹ . When methyldimethoxysilane was allowed to react with this polymer in the presence of a platinum catalyst to introduce a silyl group, the degree of unsaturation decreased to 0.0125 mmol · g ⁻¹ , indicating that the silyl group was introduced.

Example 20 Each polyoxypropylene, monomer, solvent and additive shown in Table 3 were charged in an autoclave and stirred at 65 ° C. for 20 hours.
Polymerized. After the completion, the additives were removed and the solvent was further removed by volatilization to obtain a polymer. The hydroxyl value of the obtained polymer is 9.4.
Met. Further, each polymer thus obtained was reacted with γ-isocyanatopropyldimethoxymethylsilane in an amount equal to the hydroxyl value in the presence of tin octylate at 70 ° C. for 5 hours. The isocyanate value of the obtained polymer was quantified by a back titration method using an excess amine, and it was found that 98% of γ-isocyanatopropyldimethoxymethylsilane was reacted.

Example 21 Each polyoxytetramethylene glycol having the composition shown in Table 3, a monomer, a solvent, an initiator and an additive were charged in an autoclave, and stirred at 65 ° C. for 20 hours for polymerization. After the completion, the additives were removed by filtration, and the solvent was further devolatilized to obtain a polymer.
The degree of unsaturation of the obtained polymer was 0.20 mmol · g ⁻¹ . When methyldimethoxysilane was reacted with this polymer in the presence of a platinum catalyst to introduce a silyl group, the degree of unsaturation was 0.01.
It decreased to 25 mmol · g ⁻¹ and it was found that a silyl group was introduced.

Example 22 To 100 g of the polymer of Example 21, 1 g of Nocrac NS-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.), 1 g of tinuvin 327 (manufactured by Ciba Geigy), 1 g of SANOL LS-770 (manufactured by Ciba Geigy), dibutyltin After degassing after mixing 1 g of dilaurate, form into a sheet with a thickness of 2 mm, 50 ° C, 60% R
Aged for 2 weeks. A weather resistance test with a sunshine weatherometer was conducted on this sheet.
There was no abnormality even after the lapse of hr.

Comparative Example 7 Dimethoxymethylsilane was introduced to the end of the polymer of Synthesis Example 8 used in Example 21 by using a platinum catalyst to obtain 90 at the end.
What was silylated was synthesize | combined. Example 22 except that this polymer was used in place of the polymer obtained in Example 21
A 2 mm thick sheet was prepared by the same method as above, and a weather resistance test was conducted using a sunshine weatherometer.
It had decomposed and melted before reaching 00 hr.

Examples 23 to 26 In each of the following methods, the additives which can be added to the polymer of the present invention described in each Example were added to prepare 2 mm thick sheets, and the weather resistance was examined with a sunshine weatherometer. However, there was no abnormality after 3000 hours, and it was found that the addition of the above-mentioned additive to the polymer of the present invention does not impair the excellent weather resistance, which is a feature of the polymer of the present invention.

Example 23 100 g of the polymer obtained in Example 19, 75 g of ground calcium carbonate, 75 g of colloidal calcium carbonate, titanium oxide 2
0 g, dioctyl phthalate 50 g, 3- (2-aminoethylaminopropyl) trimethoxysilane 1 g, γ-
Glycidoxypropyltrimethoxysilane 1 g, Nocrac NS-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.) 1 g, Tinuvin 32
7 (manufactured by Ciba Geigy), Sanol LS-770
(Manufactured by Ciba Geigy) 1 g and # 918 (organic tin compound manufactured by Sankyo Machine Gosei Co., Ltd.) 2 g were added, and sufficiently kneaded with 3 paint rolls, and then made into a 2 mm thick sheet at 20 ° C.
It was cured and cured at 60% RH for 14 days.

Example 24 100 g of the polymer obtained in Example 20, 75 g of heavy calcium carbonate, 75 g of colloidal calcium carbonate, and titanium oxide 2
0 g, dioctyl phthalate 50 g, trimethylphenoxysilane 3 g, tung oil 10 g, pentaerythritol tetraacrylate 5 g, styrenated phenol 1 g, benzotriazole ultraviolet absorber 1 g, hindered amine anti-aging agent 1 g, water 0.1 g 3 bottles The mixture was thoroughly kneaded with a paint roll, 3 g of tin octylate and 1 g of laurylamine were further added, and the sufficiently kneaded product was made into a 2 mm thick sheet, which was cured and cured at 20 ° C. and 60% RH for 14 days.

Example 25 100 g of the polymer obtained in Example 8, 30 g of ground calcium carbonate, 20 g of colloidal calcium carbonate, and titanium oxide 10
g, dioctyl phthalate 50 g, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane 2 g, γ
-Glycidoxypropyltrimethoxysilane 1 g, γ-
1 g of methacryloxypropyltrimethoxysilane, 50 g of Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), 20 g of polyoxypropylene triol having a molecular weight of 5000 and primary aminated ends of polyoxypropylene triol, and triethylene tetramine 10
g, 1 g of styrenated phenol, 0.3 g of benzotriazole type ultraviolet absorber, 0.3 g of hindered amine type anti-aging agent, sufficiently kneaded with 3 paint rolls, then add 2 g of # 918 and further 3 paint rolls. Kneaded thoroughly in a 2 mm thick sheet,
It was cured and hardened at 0% RH for 14 days.

Example 26 100 g of the polymer obtained in Example 1, 40 g of ground calcium carbonate, 40 g of colloidal calcium carbonate, 20 titanium oxide.
g, 3- (2-aminoethylaminopropyl) trimethoxysilane 2g, 2,2'-methylene-bis (4-methyl-6-t-butyl) phenol 1g, methyltrimethoxysilane 2g, molecular weight 2000 polyoxy 20 g of aminated polyol in which the terminal of propylene diol was primary aminated, and 6 g of 2,4,6-tris (dimethylaminomethyl) phenol were added and sufficiently kneaded with three paint rolls. To this, 60 Epicoat 828
g, 2 g of dibutyltin dilaurate, and 30 g of heavy calcium carbonate, which had been sufficiently kneaded in advance with three paint rolls, were mixed and further kneaded. This one is 2mm
It was made into a thick sheet, and cured and hardened at 20 ° C. and 60% RH for 14 days.

Example 27 100 g of the polymer obtained in Example 20, 50 g of heavy calcium carbonate, 50 g of colloidal calcium carbonate, titanium oxide 2
0g, 1g each of phenol-based antioxidant, benzotriazole-based UV absorber and hindered amine-based antioxidant
20 g of an isocyanate prepolymer obtained by modifying the end of polyoxypropylene triol having a molecular weight of 3000 with an excess of hexamethylene diisocyanate and 2 g of tin octylate were sufficiently kneaded with three paint rolls.
A 2 mm thick sheet was prepared and cured for 1 week. Using this sheet, a weather resistance test was conducted with a sunshine weatherometer, but no abnormality was found even after 3000 hours had elapsed.

Tables 1 to 3 are shown below. The abbreviations in the table are as follows. CTFE; chlorotrifluoroethylene, TFE; tetrafluoroethylene, EVE; ethyl vinyl ether,
PP; propylene 1-BT; 1-butene, PFO; α-olefin having a C 8-9 perfluoro group (representative structure; C6F13-CH = CH2), GVE;
Glycidyl vinyl ether, AIBN; azobisisobutyronitrile, PBIB; t-butyl perisobutyrate, HFP; hexafluoropropylene, PPVE; perfluoropropyl vinyl ether, BVE; butyl vinyl ether, AA; allyl alcohol, PVac; vinyl pivalate , Vac; vinyl acetate, V-9; Veova 9 (trade name of vinyl ester of C9 branched fatty acid manufactured by Shell Chemical Co., Ltd.), MMA; methyl methacrylate, GVE; glycidyl vinyl ether, AGE; allyl glycidyl ether, VEPSi; γ- Dimethoxymethylsilylpropyl vinyl ether, additive 1; compound of composition Mg _0.7 Al _0.3 O _1.15 , additive 2; compound of composition 2MgO · 6SiO ₂ · xH ₂ O, additive 3; K
₂ CO ₃ The amounts used are shown in g. Also, CF indicates cohesive failure.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

As described above, the present invention is a method for easily synthesizing a fluoropolymer composition. The curable composition containing the fluoropolymer composition of the present invention is one in which the weather resistance, which has been a problem in the past, is greatly improved, and in addition, a strong fluororesin skeleton is mixed, so that the elongation is improved. It has been revealed that the characteristics are also improved. Further, it was found that when the polymer contains a polymerized unit of a polymerizable unsaturated group-containing monomer based on a fluoroolefin, a surprising adhesion of the base material is exhibited.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI technical display location C08L 71/02 LQE 9167-4J (72) Inventor Etsuko Sakai 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Institute (72) Inventor Shigeyuki Ozawa 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Nobuyuki Miyazaki 3-474, Tsukagoshi 2, Kawasaki-shi, Kanagawa Asahi Glass Co. Company Tamagawa Branch Office (72) Inventor Mikio Yokota 3-474 Tsukakoshi 2-chome, Saiwai-ku, Kawasaki City, Kanagawa Prefecture Asahi Glass Co., Ltd. Tamagawa Branch Office

Claims (8)

[Claims] 1. In a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group, a polymerizable unsaturated group-containing monomer based on fluoroolefin and optionally a polymerizable unsaturated group-based monomer based on fluoroolefin are used together. A process for producing a novel fluoropolymer composition, which comprises polymerizing a polymerizable unsaturated group-containing monomer. 2. In a polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group, a polymerizable unsaturated group-containing monomer based on fluoroolefin and optionally a polymerizable unsaturated group-containing monomer based on fluoroolefin are used together. Production of a novel fluoropolymer composition characterized by introducing a hydrolyzable silyl group into a functional group capable of introducing a hydrolyzable soryl group after polymerizing a polymerizable unsaturated group-containing monomer Method. 3. A polymerizable unsaturated group-containing monomer copolymerizable with a fluoroolefin-based polymerizable unsaturated group-containing monomer is vinyl ethers, vinyl esters, allyl ethers, allyl esters, olefins and crotonic acid. The method according to claim 1 or 2, comprising at least one polymerizable unsaturated group-containing monomer selected from esters. 4. A polymerizable unsaturated group-containing monomer having a curable site, wherein at least one of the polymerizable unsaturated group-containing monomers copolymerizable with the fluoroolefin-based polymerizable unsaturated group-containing monomer is a polymerizable unsaturated group-containing monomer having a curable site. Item 1 or claim 2
Manufacturing method. 5. The method according to claim 4, wherein the curable site 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 ,
R ² is the same or different hydrocarbon group having 1 to 10 carbon atoms or halogenated hydrocarbon group, and X is a hydrolyzable group. ) 6. The method according to claim 4, wherein the curable site is an organic group selected from an epoxy group and a hydroxyl group. 7. A polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group, wherein the polymerizable unsaturated group-containing monomer based on a fluoroolefin and optionally a polymerizable unsaturated group-containing monomer based on a fluoroolefin are used together. A curable composition comprising a fluorine-containing polymer composition characterized by polymerizing a polymerizable unsaturated group-containing monomer. 8. A polyoxyalkylene having a functional group capable of introducing a hydrolyzable silyl group, wherein the polymerizable unsaturated group-containing monomer based on a fluoroolefin and optionally a polymerizable unsaturated group-containing monomer based on a fluoroolefin are used together. After the polymerizable polymerizable unsaturated group-containing monomer is polymerized, a fluorine-containing polymer composition characterized by introducing a hydrolyzable silyl group into a functional group capable of introducing a hydrolyzable silyl group is contained. A curable composition comprising: