JP3473049B2 - Curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates relates to room temperature curable composition excellent in weathering resistance.

[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 has excellent elasticity and weather resistance and can be cured at room temperature. The sealant from stretchable name have oily caulking material to take an example, urethane is an elastic system, developed into a poly scan Ruch I de system further weather resistance good silicone has been developed.

On the other hand, fluoroolefin-vinyl ether copolymers and fluoroolefin-vinyl ester copolymers are known as resins having high weather resistance and room temperature curability, and are used as coating compositions and the like. Has been done. The coating compositions according to the resin is excellent in weather resistance, is becoming usefulness on equal industry observed to enhance the durability of the building.

[0004]

Even if the above-mentioned conditions are satisfied, the silicone-based resin has a problem of contamination due to migration of the low-molecular-weight silicone oil and plasticizer contained therein , and the improvement of coating repeatability. Is being made.

[0005] Therefore backbone modified silicone or the like having a siloxane bond only cross-linked site by polyoxyethylene alkylene emissions also been developed, for example, Japanese Patent Publication 45-36319, JP-Sho 4
5 -17553, JP-B-46-30711, JP-Sho 61-18582, JP-Sho 60-67
47, JP-A-3-43449, JP-A-3-47.
825, JP-A-3-72527, JP-A-3
It has been proposed to -79627 Patent Gazette and the like. However, it cannot be said that these have sufficient weather resistance.

For the purpose of improving the physical properties of the modified silicone, a mixture of acrylic resins is disclosed in Japanese Examined Patent Publication No. 63-65.
No. 086, JP-A No. 60-31556, JP-A No. 60-228516 , and the like , a mixture of vinyl polymers is proposed in JP-B-4-56066, but these are also proposed. All of them were not sufficient in terms of weather resistance.

The present invention seeks to overcome the aforementioned drawbacks. That is, it is an object to provide a composition which gives a stretch and cured product excellent in both sides of the weather resistance and stain resistance.

[0008]

The present invention comprises a silyl group-containing polyoxyalkylene (A) having on average one or more reactive silyl groups in the molecule and a polymerized unit based on a fluoroolefin as an essential component. A curable composition containing a fluoropolymer (B), wherein the ratio of (A) / (B) is
100/1 to 1/100 (weight ratio), and
The fluoropolymer (B) is a fluoroolefin-based polymerization unit.
A curable composition characterized by being a polymer having a proportion of 20 mol% or more .

[0009] silyl group-containing poly Okishiaru having one or more <br/> reactive silyl group in the average molecule of the present invention
The xylene (A) is a polymer having an average of one or more reactive silyl groups in one molecule and a main chain consisting essentially of a polyoxyalkylene chain.

[0010] For example Japanese Patent Publication 45-36319, JP-Sho 4 5 -17553, JP-Sho 46-30711
JP-B, JP-B-61-18582, JP-A-60-
6747, JP-A-3-43449, JP-A-3-47825, JP-A-3-72527,
Ru polymer der proposed in JP-A 3-79627 Patent Gazette like. A method for producing such a polymer is shown in the above-mentioned document.

[0011] silyl group-containing poly Okishia used in the present invention
Rukilene (A) is described in, for example, the above-mentioned documents. The silyl group-containing polyoxyalkylene (A), the main chain ones can be mentioned up comprising repeating units consisting essentially of -R-O-. Here, R has 1 to 10 carbon atoms.
Is a divalent hydrocarbon group and / or a halogen-containing hydrocarbon group.

A specific example of -RO- is- (CH
_{2) n} O- _(n is an integer of from 1 to _{10), - CH (CH 3)} -
_{CH 2 -O-, -CH (C 2} H 5) -CH 2 -O -, - C
_{H (CH 2 - O-CH} 2 -CH = CH 2) - CH 2 O -, -
_{CH 2 -C (CH 3) 2} -CH 2 -O-, -CHCl-C
_{H 2 -O -, - CH 2} -C (CH 2 Cl) 2 -CH 2 -O-
Etc., and only one type of these repeating units
But or random form Moshiku with 2 or more kinds Included mixed in a block form can be mentioned up, not limited to these things.

[0013] Preferred polyoxyalkylene polyoxyalkylene diols, polyoxyalkylene triols and polyoxyalkylene tetraol can be mentioned <br/> up. Also, an olefin-terminated polyoxyalkylene such as an allyl-terminated polyoxyalkylene monool produced using an initiator having an olefin group such as an allyl group can be used.

As the reactive silyl group in the present invention,
For example, a hydrolyzable silyl group represented by the formula (1) is preferable.

[0015]

[Chemical 1]

(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, R ² is a homologous
May be heterologous also, or hydrocarbon group having 1 to 10 carbon atoms
Or a halogenated hydrocarbon group, and X is a hydrolyzable group. )

The process of the method for introducing the hydrolyzable silyl group of the following (a) ~ (c) are exemplified up. (A) Unsaturated bond obtained by the following methods (a) to (d)
Table with Poriokishia Le Killen and the following formula (2) which have a portion
A hydrosilane compound is Ru are reacted.

[0018]

[Chemical 2] (Here, a, b, m, X, R ¹ and R ² are the same as above.)

(A) Polyoxyalkylene poly (or
The terminal hydroxyl group of mono) ol has a group that can react with the hydroxyl group .
And reacting a compound having a polymerizable group. Such compounds, A acrylic acid For example, methacrylic acid, A <br/> acrylic acid chloride Li de, chloride methacrylate, triallyl Na over preparative, maleic anhydride, or allyl alcohol, 2-hydroxyethyl hydroxyl group-containing polymerizable end a polyfunctional isocyanate Na over preparative Moshiku monomeric, such as vinyl ether or the like was also modified with a large excess of phosgene or the like can be mentioned up.

(A) Polyoxyalkylene poly (or
To denature the terminal hydroxyl groups of mono) ol, Ru by reacting a compound of have a further unsaturation moiety at its terminus. For example,
After the terminal hydroxyl groups of a polyoxyalkylene with an alkali metal alkoxide, Arirukuro Li de, Ariruburo Mi de,
p- chloromethylstyrene, p- bromomethylstyrene, reacting a compound of have a halogen and an unsaturated bond moiety such as 2-chloroethyl vinyl ether. Or polyoxy excess diisocyanate to terminal hydroxyl groups of Ren, a large excess of phosgene, or after modified end by reacting dicarboxylic acids (and / or anhydride thereof), allylamine, allyl alcohol, hydroxybutyl vinyl ether, 2-hydroxyethyl luer Kurire <br/> bets, reacting an active hydrogen-containing polymerizable monomer such as 2-hydroxyethyl methacrylate.

[0021] (c) placed in the polymerization of polyoxyalkylene
Te, allyl glycidyl ether, vinyl glycidyl ether, unsaturated bond moiety, such as glycidyl methacrylate
A monoepoxide compound having a is copolymerized with a monoepoxide such as an alkylene oxide. (D) A monoepoxide compound is reacted with a compound having a polymerizable unsaturated bond portion and a hydroxyl group as an initiator.

[0022] (b) directly following formula (3) compounds represented by polyoxyalkylene terminal hydroxyl, or amino which had been introduced in advance following (e) - (h) in such was ani up method group, an epoxy group, isocyanate Na over preparative group, is reacted with a mercapto group.

[0023]

[Chemical 3]

(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. Groups, isocyanate groups, carboxyl groups, unsaturated bond moieties , acrylate groups
Royle group, and an organic group having one or more <br/> functional groups Metaku Ru is selected from Li acryloyl group. )

[0025] (e) reacting the isocyanate Na over preparative group polyoxyalkylene (or mono) terminal hydroxyl groups with excess polyfunctional isocyanate-ol. ( F ) Epoxy group The terminal hydroxyl group of polyoxyalkylene poly (or mono) ol is alcoholated with an alkali metal and then reacted with epichlorohydrin.

( G ) Amino group The terminal hydroxyl group of polyoxyalkylene poly (or mono) ol is directly aminated with ammonia. Or (e), terminal isocyanate Na over preparative group Moshiku of the resulting polyoxyalkylene in (vi) is reacted with an excess of polyfunctional amine to epoxy groups.

( H ) Mercapto group Polyoxyalkylene Poly (or mono) ol is reacted with a cyclic sulfide at the terminal. Or reacting a compound having a group reactive with a mercapto group and isocyanurate Na <br/> over preparative groups such as polyoxyalkylene terminal isocyanate Na over preparative group mercaptoethanol obtained in (e).
Or after chlorinating a polyoxyalkylene end, after reaction with sodium disulfide or the like, you - reducing.

[0028] (c) adding the following formula (4) a hydrolyzable silyl group-containing epoxy compound represented by the time of polymerization of the polyoxyalkylene, Ru by copolymerization reaction.

[0029]

[Chemical 4]

(Here, a, b, m, X, R ¹ and R ² are the same as above.)

The silyl group-containing poly Okishia in the present invention
Rukiren (A 2 ) has 1 in the molecule on average of reactive silyl groups.
Have more than one .

There are no particular restrictions on the molecular weight of the polyoxyalkylene , and various molecular weights can be used depending on the application. When using one with a molecular weight of 1000 or less,
A polymer obtained, or obtained by introducing cure site to the polymer is relatively hardness stiff but shows an elastic, wear in use as an elastic coating material, a hot melt adhesive or the like. Molecular weight 1
When using those 000 to 50,000, the polymer obtained is at normal temperature showed fluidity, as it can be utilized in pressure-sensitive adhesives, and sealants. Molecular weight 5000
When 0 or more is used, it can be used, for example, as a fluorine-containing rubber excellent in fluidity, weather resistance and heat resistance.

The molecular weight distribution (M _w / M _n ) of polyoxyalkylene is not particularly limited. A polyoxyalkylene having an arbitrary M _w / M _n can be used depending on storage stability, viscosity, workability, physical properties upon curing and the like. Although M _w / M _n affects each of the above items, M _w / M _n is not affected in giving the curable composition having excellent weather resistance of the present invention.

The fluoropolymer (B) in the present invention is a fluoropolymer having a polymerization unit based on a fluoroolefin as an essential component. As the fluoroolefin, tetrafluoroethylene, chlorotrifluoroethylene,
Trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, 2-6 carbon atoms such as pentafluoro propylene <br/> Ren, not particularly preferred are fluoroolefins of 2 to 4 carbon atoms. Of these, perhalopolyfluoroolefins in which hydrogen is completely replaced by halogen are most preferable.

[0035] Such fluorine-containing polymer (B) Ru polymer der having polymerized units based on a fluoroolefin than 20 mol%. If the polymerized units based on the fluoroolefin is less than 20 mol%, sufficient weather resistance may not be exhibited, and stains may become remarkable during long-term use.
It It is particularly preferable that the fluoropolymer (B) has 20 to 80 mol% of polymerized units based on fluoroolefin. More preferably, it is 30 to 70 mol%. More preferably, it is 40 to 70 mol%.

The fluoropolymer (B) in the present invention may have a polymer unit based on a comonomer copolymerizable with the fluoroolefin, in addition to the polymer unit based on the fluoroolefin.

[0037] As comonomers copolymerizable with fluoroolefin, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a compound having a polymerizable site such as isopropenyl group can be mentioned up.

Specifically, olefins, vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic acid esters, methacrylic acid esters, isopropenyl ethers, isopropenyl esters and crotonic acid esters, There be mentioned up. This Some even number of 1 to 15 about a straight, branched or compounds having alicyclic alkyl group is preferable. As such a comonomer, 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 , methylation allyl ether, ethyl allyl ether, butyl allyl ether, cyclohexyl ether, 2-allyl ethers of hydroxyethyl allyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl caproate , Vinyl caprylate, Veova 9 and Veova 10 (Shell Chemical Co., charcoal
Prime 9 and trade names of the vinyl ester of a branched fatty acid of 10), fatty acid vinyl esters such as vinyl versatate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylic acid or methacrylic acid ester such as cyclohexyl methacrylate s, crotonic acid ethyl, butyl crotonate, crotonic acid esters of cyclohexyl crotonate, allyl alcohol can be mentioned up.

Among the above comonomers, a monomer selected from vinyl ethers, vinyl esters, allyl ethers, allyl esters, isopropenyl ethers, isopropenyl esters and crotonic acid esters is particularly preferable. . Most preferably Ino is vinyl ethers, the use of this, a high probability of alternating copolymer and fluoroolefin, preferred in view of weather resistance.

In the fluoropolymer (B) , the polymerized units based on these comonomers are preferably 80 mol% or less. 8
If it is more than 0 mol%, sufficient weather resistance may not be exhibited, and stains may become remarkable during long-term use, which is not preferable. 20 to 80 mol% is particularly preferable. More preferably, it is 30 to 70 mol%. More preferably 30
Is about 60 mol%.

By containing an appropriate amount of polymerized units based on these comonomers in the fluoropolymer (B) ,
Polyoxyalkyl containing silyl group without impairing weather resistance
Provide good miscibility with the lens (A), the cured body obtained by curing the composition may name as a flexible cured product. Further, by exhibiting solvent solubility and preparing a solution of such a polymer, mixing with the silyl group-containing polyoxyalkylene (A) becomes easy. Also those fluoropolymer (B) is closed ether chain are also preferred. Examples of such fluoropolymers include JP-A-2-245005 and JP-A-3-122.
152, JP-A No. 3-126707, JP-it is described in etc. Hei 4-22 2 No. 051.

The fluorine-containing polymer (B) is also preferably a polymer having a reactive site capable of co-crosslinking with silyl group-containing polyoxyalkylene (A). As the reactive site capable of co-crosslinking, a reactive silyl group is particularly preferable.

The reactive silyl group is represented by the above formula (1)
A silyl group similar to the silyl group represented by is preferable. The fluorine-containing polymer having a reactive silyl group is described in, for example, JP-A-61 / 1986.
-141713, JP-A-62-558, JP-A-62-81409, and JP-A-62-14976.
No. 4, JP-A No. 2-245005, and the like.

As a method for introducing the reactive silyl group into the fluoropolymer (B), a known method as described in the above literature can be used. For example the polymerizable monomer how body allowed to copolymerize to have a a reactive silyl group and a fluoroolefin copolymerizable polymerizable unsaturated bond, such a reactive silyl group can be introduced group and fluoroolefin copolymerizable After copolymerizing a polymerizable monomer having a polymerizable unsaturated bond portion and a fluoroolefin, a method of introducing a reactive silyl group, a method of polymerizing using a chain transfer agent having a reactive silyl group, a reaction method in which polymerization using a radical initiator having a sexual silyl group can be mentioned <br/> up.

[0046] The reactive silicon that fluoropolymer (B) is capable of co-crosslinking silyl group-containing <br/> polyoxyalkylene (A)
Also have a reactive portion position other than group, in order to improve the physical properties of the curable composition of the present invention, the adhesive is preferred. The co-crosslinking in this case means the following.

(1) Silyl group-containing polyoxyalkylene
Co-crosslinking is carried out by a compound capable of reacting with both the silyl group of (A) and the reaction site of the fluoropolymer (B) . For example you co-crosslinking by a silane coupling agent having a group capable of reacting with the reactive sites fluoropolymer (B) it has. Specifically, the reaction of the fluoropolymer (B) has
If 応部-position hydroxyl groups, Y of the formula (3) is co-crosslinked with the silane coupling agent is isocyanate Na over preparative group.
Alternatively, when the reactive site is an epoxy group, Y is an amino group ,
Co-crosslinking with silane coupling agent such as mercapto group
To, Moshiku the silane coupling Y is an epoxy group
Reacting agent with silyl group-containing polyoxyalkylene (A)
Is, a method such as co-crosslinking are exemplified down by a further thereto a fluorine-containing polymer (B) an epoxy curing agent.

(2) Silyl group-containing polyoxyalkylene
When (A) has a reaction site other than a silyl group and the reaction site is a group capable of reacting with the reaction site of the fluoropolymer (B) , these reaction sites are co-crosslinked. For example, when silyl group-containing poly oxyalkylene emissions (A) has a hydroxyl group, it co-crosslinking with the fluorinated polymer having an acid anhydride group (B). Silyl group-containing polyoxyalkylene
When (A) has an unsaturated bond moiety, it co-crosslinking with the fluorine-containing polymer having a mercapto group (B). Well
And when the silyl group-containing polyoxyalkylene (A) has an epoxy group, acid anhydride group, an amino group, Karubamoi
Group, methods such as you co-crosslinking with the fluorine-containing polymer having a mercapto group (B) are exemplified up.

(3) Silyl group-containing polyoxyalkylene
When (A) has a reaction site other than a silyl group, it is co-crosslinked with a compound having in the molecule a group capable of reacting with each of the reaction site and the reaction site of the fluoropolymer (B) . For example, silyl group-containing polyoxyalkylene
(A), in the case where the fluorine-containing polymer (B) has a hydroxyl group in together, co-crosslinking them by more polyfunctional isocyanate Na over preparative compounds, silyl group-containing polyoxyalkylene
(A), the fluorine-containing polymer (B) is, if it has an epoxy group together, a method such as co-crosslinking with epoxy curing agents can be mentioned up.

By subjecting the composition of the present invention to co-crosslinking by these methods, it is possible to easily improve the elongation at break, the breaking strength and the like.
Can Ru. The catalyst for co-crosslinking may be added to the composition of the present invention to promote the co-crosslinking. Further, even if the above-mentioned co-crosslinking is not carried out, the polarity of the curable site of the fluoropolymer (B) can greatly improve the adhesiveness of the composition of the present invention during curing. Other hydroxyl group, an amino group such elevation clogs group Specific examples of the above example as cure site, a mercapto group, isocyanate group, carboxyl group, formyl group, N- methylol group, unsaturated binding
If partial, acid anhydride group, groups such as carbamoyl group can be mentioned up. As a method for introducing into the fluoropolymer of these functional groups (B), a method of copolymerizing during synthesis of the polymerizable monomer to the fluoropolymer that closed these functional groups (B), of , or addition of the polymerization initiator to have a functional group and / or a chain transfer agent during polymerization can be mentioned up.

The fluorine-containing polymer (B) preferably has a molecular weight of 2,000,000 or less, particularly about 50,000 or less. When used without a solvent such as for a sealant, those having a large molecular weight have extremely poor workability. When used without a solvent, it is preferable to employ one having a molecular weight of 15,000 or less, particularly 10,000 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 (B) may be any of solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization, and a predetermined amount of a monomer may be added to a polymerization initiator or ionizing radiation. Polymerization is carried out by acting a polymerization initiation source such as. Other various conditions can be the same as those usually used for solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like.

In the curable composition of the present invention, the mixing ratio of the silyl group-containing polyoxyalkylene (A) and the fluoropolymer (B) is (A) / (B) = 100/1 to 1/1
It is preferably 00. More preferably (A) /
(B) = 100/1 to 1/3 is preferable, and the curable composition of the present invention can be used for various purposes by using various constituents as necessary and various additives .

The additives that can be used will be described. In curing the curable composition of the present invention, a curing acceleration catalyst that accelerates the curing reaction of the reactive silyl group may be used.

[0055] Examples of the curing accelerating catalyst, such as alkyl titanates, organosilicon titanates, bismuth tris-2-ethylhexyl Sano benzoate, metal salts of such acids tin octylate and dibutyltin dilaurate, etc. dibutylamine-2-ethylhexyl Sano benzoate Amine salt,
And 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, fillers, solvents, light stabilizers, ultraviolet absorbers, heat stabilizers, leveling agents, plasticizers, physical property adjusting agents,
An air oxidation 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. These additives will be described below.

As the solvent, methanol, ethanol,
Isopropyl Piruaruko Lumpur, n- Bed Chiruaruko Lumpur, t-
Alcohols such as blanking Chiruaruko Lumpur, ketones such as methyl ethyl ketone, xylene, and aromatic solvents such as toluene can be mentioned up, alcohols are preferred for imparting storage stability to the present compositions. 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,
Various compounds such as sulfur compounds and phosphorus compounds can be appropriately used.

[0058] As the filler, fumed silica, precipitated silica, silicic anhydride, such reinforcing filler of precipitated silica and carbon black; calcium carbonate, heavy calcium carbonate, calcium carbonate surface treated, colloidal carbonate calcium, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, acid ferric, zinc oxide, <br/> Gotoki fillers active zinc white Contact and Shirasubaru emissions; glass fibers and filaments Fibrous fillers such as can be used.

[0059] When it is desired to obtain a high curing body strength is mainly fumed silica, precipitated silica, silicic anhydride, hydrous silicic acid, carbon black, surface-treated fine calcium carbonate, calcined clay, clay, and active zinc Preferable results are obtained by using a filler selected from flowers and the like in the range of 1 to 1000 parts by weight with respect to 100 parts by weight of the curable composition of the present invention. Further, when it is desired to obtain a cured product having low strength and large elongation, titanium oxide, calcium carbonate,
A preferable result is obtained by using a filler selected from magnesium carbonate, talc, ferric oxide, zinc oxide, and shirasu balloon in the range of 0.1 to 1000 parts by weight based on 100 parts by weight of the curable composition of the present invention. Is obtained . These fillers may be used only in one kind, may be mixed using two or more kinds.

When the composition is used as a sealant, an adhesive, etc., an additive having adhesiveness may be added. Such additives include, include the following
Ani-up it is.

1. Silane coupling agents such as the formula (3) or a compound represented by the following formula (5).

[0062]

[Chemical 5] (Wherein R ⁵ is met heterologous be R ^1, R ² the same kind
May be a hydrocarbon group or a halogenated hydrocarbon group having 1 to 10 carbon atoms, a, b, m, X , R 1, R 2 are as defined above. )

Specific compounds include tetramethoxysilane, tetraethoxysilane, tetraphenoxysilane, and other tetraalkoxysilanes, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyldimethoxymethylsilane. Three
- (N-2-aminoethyl) aminopropyl belt trimethoxysilane, 3- (N-2-aminoethyl) aminopropyl
Aminosilanes such as distearate methoxymethyl silane, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxypropyl dimethoxymethyl silane, beta-(3,4-
Epoxysilanes such as epoxycyclohexyl) ethyl trimethoxysilane, .gamma.-methacryloxypropyl trimethoxysilane, .gamma.-methacryloxypropyl methacryl acryloyloxy group-containing silane such as dimethoxymethyl silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinylsilane such as vinyl trichlorosilane can be mentioned up. 0.01 parts by weight or more of these compounds to 100 parts by weight of the composition of the present invention,
Excellent adhesion can be obtained by preferably adding about 0.1 to 20 parts by weight.

2. Epoxy compound As an epoxy compound that can be added to the composition of the present invention,
Generally epoxy resins can be mentioned up. 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 such as diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester Ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N-digly Jiruanirin, N, N-diglycidyl--o- toluidine, triglycidyl isocyanurate, polyoxypropylene Al <br/> Killen Geo Lumpur diglycidyl ether, glycidyl ethers of polyhydric alcohols such as glycerin, hydantoin type epoxy resins, such as petroleum resin such epoxidized unsaturated polymer, generally a vinyl polymer to have a epoxy resin or an epoxy group are used like the like can be mentioned, et al is not intended to be limited thereto.

Among these epoxy resins, those containing two or more epoxy groups in the molecule have high reactivity during curing, and the cured product easily forms a three-dimensional network. preferably, also is more preferably a bisphenol a type epoxy resins, phthalate glycidyl <br/> glycidyl esters, novolak epoxy resins, vinyl polymers which have a 2 or more epoxy groups in the molecule ani-up it is.

[0066] In addition to the composition of the present invention also a curing agent for the epoxy resin may be used in combination of a curing catalyst. Such general epoxy resin curing agent to be used in can be mentioned <br/> up as curing agent. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N- aminoethylpiperazine, m- xylylenediamine, m- phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone phon, isophorone diamine, 2 , 4,6-tris (dimethylaminomethyl) phenol, amines etc., tertiary amine salts, polyamide resins, imidazoles, dicyandiamide, boron trifluoride complex compounds, phthalic acid anhydride, Hekisahido b
Full barrel anhydride, Tetorahido Roff barrel anhydride, endomethylenetetrahydrophthalic tetrahydroborate Roff barrel anhydride, dodecenyl two Turkey C <br/> click anhydride, mosquitoes carboxylic acid anhydrides such as pin Romeritto anhydride
Products , phenoxy resins, carboxylic acids, alcohols, etc.
Polyoxyalkylene polymer having an average of at least one group capable of reacting with an epoxy group in the molecule (terminally aminated polyoxypropylene glycol, terminally carboxylated polyoxypropylene glycol, etc.), terminal hydroxyl group , carboxyl group, polybutadiene modified with an amino group or the like, hydrogenated polybutadiene, acrylonitrile - butadiene copolymer, although a liquid terminal functional group-containing polymer such as an acrylic polymer like et be, limited to these Absent. 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 with respect to 100 parts by weight of the epoxy resin .

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, aliphatic dibasic acid esters such as succinic acid di isodecyl, diethylene glycol dibenzoate, polyhydric Al co <br/> Ruesuteru such as pentaerythritol ester, butyl oleate, acetylricinoleate no <br/> Le fatty acid esters of methyl acid, tricresyl phosphate, trioctyl phosphate, phosphoric acid esters such as octyl diphenyl phosphate, epoxidized soybean oil, epoxy-based plasticizers such as epoxy stearic acid benzyl, chlorinated paraffins, etc. generally plasticizers are exemplified up. It is also preferable to use a polymer plasticizer in order to prevent contamination of the periphery due to migration of the plasticizer.

[0068] Specific examples of such a polymeric plasticizer, dibasic acid and polyester plasticizers such as polyesters of dihydric alcohols, polyoxyethylene alkylene emissions such as polyoxypropylene glycol or its derivative, poly −
α- methyl styrene, oligomers of polystyrene such as polystyrene, polybutadiene, butadiene - acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, although oligomers such as hydrogenated polybutene are exemplified <br/> up is limited to Not something. Among them, the molecular weight is 300 to 2 due to the effect as a plasticizer.
Preferably of about 0000, more preferably preferably good compatibility polyoxyethylene alkylene down polymer with the present invention compositions. Particularly preferably polyoxyethylene alkylene down a number average molecular weight has 1000 or more hydroxyl groups, or polyoxyethylene alkylene down does not have terminal hydroxyl groups.

[0069] Further a compound having one silanol group in a molecule as a physical property adjustment agent of the present invention compositions, or may be added a compound capable to generate by hydrolysis of the compound. Such compounds include silane compounds such as trimethylsilanol, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, trimethylchlorosilane, hexamethyldisilazane, dimethylvinylphenoxysilane, N, O-bis ( trimethylsilyl ) acetamide, and the like. There be mentioned up. These compounds should be added appropriately in the range of 0.01 to 1.5 times equivalent amount with respect to 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. You can

As the air-oxidation-curable compound, a drying oil typified by tung oil, linseed oil, etc., various alkyd resins obtained by modifying the compound, an acrylic polymer modified with the drying oil, and a silicone. Resin, poly- 1,2
- Bed Tajien, poly - 1,4 - Bed Tajien, carbon 5 ~
Diene-based polymers such as diene polymers and copolymers of 8 ,
Further, various modified products of the polymer or copolymer (maleic acid modified, boiled oil modified, etc.) can be mentioned. Among these, tung oil and liquid products 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.

[0071] In general, the compounds such as acetophenone used are exemplified up as the photopolymerization initiator. As the photopolymerizable monomer, typically an electron beam also used acrylic special monomer <br/> like are exemplified up which is used for the ultraviolet curable resin.

The curable composition of the present invention comprises a sealant,
Although it can be used as a waterproofing agent, a coating material, etc., it is particularly suitable for applications in which durability and weather resistance of the cured product are required.

[0073]

EXAMPLES The present invention will be described below with reference to examples.

(Synthesis Example 1) Polyoxypropylene triol was obtained by polymerizing propylene oxide using zinc hexacyanocobaltate catalyst with glycerin as an initiator. Allyl black
It was converted to hydroxyl groups of the end edge to the allyl group with the addition of Li de. Then, the obtained terminal allyl group-containing polyoxypropylene is reacted with methyldimethoxysilane in the presence of a platinum catalyst to convert the allyl group into a methyldimethoxysilyl group, and 80% of the terminals are silylated to give an average molecular weight of 20,000. A silyl group-containing polyoxypropylene was obtained.

[0075] (Synthesis Example 2-5) contents into a stainless steel stirrer with a pressure resistant reactor product 550 cm ^3, xylene 112 g, ethanol 112 g, potassium carbonate 1.6g and azobisisobutyronitrile 0.5
g was charged and a monomer having the composition shown in Table 1 was polymerized. Polymerization is carried out by charging monomers other than chlorotrifluoroethylene (CTFE) or tetrafluoroethylene (TFE), removing residual air by freeze degassing with liquid nitrogen, and then introducing CTFE or TFE, After gradually raising the temperature, 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 stop the polymerization. After cooling the reactor to room temperature, unreacted monomers were extracted and the reactor was opened. After filtering the polymer solution, ethanol was removed at 50 ° C. by an evaporator to obtain a xylene solution of a fluoropolymer. The molecular weight of the obtained fluoropolymer is shown in Table 1. However, in the table, E
VE represents ethyl vinyl ether, CHVE represents cyclohexyl vinyl ether, and HBVE represents 4 -hydroxybutyl vinyl ether.

[0076]

[Table 1]

(Synthesis Example 6) (CH ₃ O) ₂ was added to the fluoropolymer obtained in Synthesis Example 5.
(CH ₃ ) —Si— (CH ₂ ) ₃ —NCO 4.75 g silane coupling agent and tin octylate 30 mg
Was added and the mixture was reacted at 90 ° C. for 6 hours to obtain a fluoropolymer having a reactive silyl group.

Examples 1 to 5 For each of the fluoropolymers obtained in Synthetic Examples 2 to 6, the silyl group-containing polyoxypropyene obtained in Synthetic Example 1 was prepared.
After mixing 300 g of Ren , the solvent was removed and a uniform curable composition was synthesized. Next, for 100 g of these compositions,
Antioxidant Nocrac ST (Ouchi Shinko Chemical Co., Ltd.) 0.2
5 g, benzotriazole type ultraviolet absorber 0.25 g ,
And, a mixed compound obtained by mixing tin octylate 3g and laurylamine 1g as a catalyst was added 1g, 20
A sheet having a thickness of about 2 mm was manufactured by curing at 60 ° C. and 60% RH for 14 days and curing.

[0079] Physical properties of the resulting sheet [50% modulus (k g / cm ^2), tensile strength (k g / cm ^2), elongation at break (%) were examined. It was also subjected to surface weathering test at Sunshine weather-O-Meter. The results are shown in Table 2 and Table 3.
Shown in. However, the evaluation of the surface weather resistance test is as follows. ⊚: No abnormality after 3000 hours, ×: Surface dissolution after 800 hours.

Comparative Example 1 With respect to 100 g of the silyl group-containing polyoxypropylene obtained in Synthesis Example 1, 0.25 g of antioxidant Nocrac ST (manufactured by Ouchi Shinko Chemical Co., Ltd.) and benzotriazole-based ultraviolet absorber 0 .25G, and stannous octoate 3 as catalyst
1 g of laurylamine and 1 g of a mixture obtained
g, and cured at 20 ° C. and 60% RH for 14 days to be cured to produce a sheet having a thickness of about 3 mm. The obtained sheet was evaluated in the same manner as in Examples 1-5. The results are shown in Table 3.

[0081]

[Table 2]

[0082]

[Table 3]

[0083] perform polymerization of propylene oxide using potassium hydroxide as a catalyst initiator (Synthesis Example 7) Propylene glycol was synthesized polyoxypropylene Geo Lumpur average molecular weight of 3,000. After the end of the polyoxypropylene Geo Lumpur was alcoholate by sodium metal, the end group 2/3
After reacting the fold equivalents of dichloromethane is reacted with Arirukuro Li de 1/3 equivalents, average molecular weight was obtained terminal allyl group-containing polyoxypropylene 8000. The thing hexane - dissolved in an aqueous and <br/> extracted polyoxyethylene pro pyrene emissions. Resulting presence of a platinum catalyst purification terminal allyl group-containing polyoxypropylene obtained by removing the hexane, reacted with methyldimethoxysilane, 75% of the terminal polyoxypropylene of average molecular weight 8000 to have a silyl group It was

Synthesis Example 8 Propylene glycol was polymerized with propylene glycol as an initiator and aluminum porphyrin as a catalyst, and _Mw / _Mn measured by gel permeation chromatography having an average molecular weight of 8000 was 1.10. to obtain a polyoxypropylene geo Lumpur. After the end of the polyoxypropylene Geo <br/> Lumpur was alcoholate by metallic sodium, is reacted with Arirukuro Li de, terminal allylated to give a terminal allyl group-containing polyoxypropylene. This was dissolved in a hexane-water system, the produced sodium chloride was removed to the aqueous phase, and the salt-removed terminal allyl group-containing polyoxypropylene was extracted in the hexane phase. The presence of the purified terminal allyl group-containing polyoxypropylene obtained by removing the hexane platinum catalyst, is reacted with methyldimethoxysilane, average molecular weight to have a silyl group to 75% of the terminal 8
000 polyoxypropylene was obtained.

(Examples 6 to 14 and Comparative Examples 2 to 10) Tables 5 and 5 show xylene solutions of the fluoropolymers 1 to 6 each having the composition (molar ratio) shown in Table 4 and each molecular unit and the molecular weight. After mixing the xylene solutions of Polymers 1 to 6 and Synthesis Examples 7 and 8 so that each composition (the unit in the table is g) ,
The solvent was removed to obtain a composition consisting of a silyl group-containing polyoxyalkylene and a fluorine-containing copolymer. Using these, a 2 mm thick sheet was prepared as in the following examples and subjected to a surface weather resistance test with a sunshine weatherometer.
There was no abnormality after 000 hours, but Comparative Examples 2 to
For No. 9, the surface was decomposed and melted within 500 to 1000 hours. Also, the one of Comparative Example 10 is 300
Before the lapse of 0 hours, cracks were generated on the surface. From the above, it can be seen that the composition of the present invention has excellent weather resistance. It was also found that the weather resistance is not impaired when the above-mentioned optional additives are added to the composition of the present invention. The details of each Example and Comparative Example will be described below.

[0086]

[Table 4]

CTFE; chlorotrifluoroethylene,
TFE; tetrafluoroethylene, HFP; hexafluoropropylene, PPVE; perfluoropropyl vinyl ether, EVE; ethyl vinyl ether, BVE;
Butyl vinyl ether, HBVE; 4-hydroxybutyl vinyl ether, PVac; vinyl pivalate, Va
c; vinyl acetate, V-9; VeoVa 9 (Shell Chemical Co. Charcoal
Trade name of vinyl ester of branched fatty acid with prime number 9 ), P
P; propylene, 1-BT; 1- butene, PFO; alpha-olefin having a carbon having a path Furuoro alkyl group 8-9 (representative _{structures; C 6 F 13 -CH = CH} 2), GV
E: glycidyl vinyl ether, AGE; allyl glycidyl ether, MAA; methacrylamide, MAAn;
maleic anhydride.

[0088]

[Table 5]

[0089] For compositions shown in (Example 6) Table 5, dioctyl phthalate 50g as a plasticizer, 3- (N-2-aminoethyl) Aminopu <br/> Ropi belt trimethoxysilane 1 g, .gamma. glycidol 1 g of xypropyltrimethoxysilane, 1 g of Nocrac NS-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.), 1 g of benzotriazole type ultraviolet absorber, 1 g of hindered amine type anti-aging agent were added, and after thoroughly kneading with 3 paint rolls, dibutyl Su
It was added which was preheated stirred's oxide 1g and dioctyl phthalate 1g, thoroughly what the kneaded 2mm thick sheet further three paint rolls, 2
It was cured and cured at 0 ° C. and 60% RH for 14 days.

Example 7 For the composition shown in Table 5, 2 was carried out in the same manner as in Example 6.
A mm thick sheet was prepared by curing.

[0091] (Comparative Example 2) Example 6 Synthesis Example 7 was used, instead of the polymer 1, except that using 100g only polymer of Synthesis Example 7 examined in exactly the same manner as in Example 6 It was

[0092] (Comparative Example 3) Example 7 Synthesis Example 8 was used in place of polymer 1, except that using 100g only polymer of Synthesis Example 8 examined in exactly the same manner as in Example 7 It was

[0093] For compositions shown in Example 8 Table 5, 3- (N-2-aminoethyl) aminopropyl belt trimethoxysilane 2 g, 2, 2 '
- methylene - bis - (4-methyl -6-t-butylphenol) 1 g, methyltrimethoxysilane 2g, polyoxypropylene triol terminally aminated polio is primary amino of molecular weight 5000 alkoxy propylene 20
g, 2,4,6-tris (dimethylaminomethyl) phenol 6 g, and kneaded thoroughly with a three-paint roll (Liquid A). Separately, Epicoat 828 (bisphenol A manufactured by Yuka Shell Epoxy Co., Ltd. as an epoxy resin
Type epoxy resin) of 60 g, dibutyltin dilaurate 2g, previously sufficiently kneaded with a three roll paint mill heavy calcium carbonate 30g, and what the solution A was added and mixed thereto to 2mm thick sheet, 20 ℃, 60% It was cured and cured in RH for 14 days.

[0094] (Comparative Example 4) Example 8 Synthesis Example 7 was used, instead of the polymer 2, except that using 100g only polymer of Synthesis Example 7 examined in exactly the same manner as in Example 8 It was

Example 9 For the composition shown in Table 5, 50 g of polyoxypropylene diol having a number average molecular weight of 6000 and a molecular weight distribution (M _w / M _n ) by gel permeation chromatography of 1.10.
(N-2-aminoethyl) aminopropyl belt trimethoxysilane 2 g, gamma chromatography glycidoxypropyltrimethoxysilane 1g, Nocrac NS-6 (manufactured by Ouchi Shinko Chemical Co.) 1
g, TINUVIN 327 (manufactured by Ciba Geigy), 1 g of SANOL LS-770 (manufactured by Ciba Geigy), 2 g of methanol, # 918 ( organotin compound manufactured by Sankyo Machine Synthetic Co., Ltd.), and 3 paint rolls are added. After thoroughly kneading, make a 2mm thick sheet and make it 14 at 20 ℃ and 60% RH.
Cured and cured for days.

[0096] (Comparative Example 5) Example 9 Synthesis Example 8 was used in place of the polymer 3, examined other using 100g only polymer of Synthesis Example 8 the same procedure as in Example 9 It was

Example 10 Dioctyl phthalate 50 was added to the composition shown in Table 5.
g, trimethyl phenoxy silane 3g, tung oil 10 g, pentaerythritol Lumpur tetraacrylate 5g, styrenated phenol 1g, benzotriazole-based ultraviolet absorber 1g, hindered amine antioxidants 1g, water 0.1g
After thoroughly kneading with 3 paint rolls, octyl acid
3 g of tin and 0.5 g of laurylamine were added and further thoroughly mixed to form a 2 mm thick sheet, which was cured and hardened at 20 ° C. and 60% RH for 14 days.

[0098] (Comparative Example 6) Example 10 Synthesis Example 7 was used, instead of the polymer 6, the polymer only other using 100g Example 10 Synthesis Example 7
It examined by the method exactly the same as.

[0099] For compositions shown in (Example 11) Table 5, 3- (N-2-aminoethyl) aminopropyl distearate methoxymethyl silane 2 g, .gamma.
Glycidoxypropyltrimethoxysilane 1g, .gamma.-methacryloxypropyltrimethoxysilane 1g, Epikote 828 100 g, molecular weight 2000 polyoxypropylene diol termini aminated polio carboxymethyl propylene 10g which are primary aminated, triethylenetetramine 10g , Nocrac NS-6 (manufactured by Ouchi Shinko Chemical Co., Ltd.) 0.
5 g, benzotriazole-based ultraviolet absorber 0.25 g,
Add hindered amine anti-aging agent 0.25g and add 3
After thorough mixing in the paint roll, # 918 (Sankyo Organic Chemicals Co., Ltd. organotin compound) was added 2g, was thoroughly kneaded by three more roll paint mill, and the 2mm thick sheet, 20 ° C., It was cured and cured at 60% RH for 14 days.

[0100] (Comparative Example 7) Example 11 Synthesis Example 8 was used, instead of the polymer 5, the polymer only other using 100g Example 11 Synthesis Example 8
It examined by the method exactly the same as.

(Example 12) Dioctyl phthalate 50 was added to the composition shown in Table 5.
g, 3- (N- 2- aminoethyl) aminopropyl belt trimethoxysilane 1g, .gamma.-glycidoxypropyltrimethoxysilane 1g, .gamma.-methacryloxypropyltrimethoxysilane 1g, methanol 2g, NOCRAC NS-
6 (manufactured by Ouchi Shinko Chemical Co., Ltd.), 1 g of benzotriazole type ultraviolet absorber, 1 g of hindered amine type anti-aging agent,
It was added pentaerythritol tetraacrylate 2g, was thoroughly kneaded by a three-roll paint mill, dibutyl scan
A 2 mm thick sheet was prepared by adding 2 g of zudiacetylacetonate and kneading the mixture sufficiently with three paint rolls, and curing and curing at 20 ° C. and 60% RH for 14 days.

[0102] (Comparative Example 8) Example 12 Synthesis Example 8 was used, instead of the polymer 4, polymer only other using 100g Example 12 Synthesis Example 8
It examined by the method exactly the same as.

[0103] (Synthesis Example 9) After the average molecular weight and the end of 4000 of polyoxytetramethylene Geo <br/> Lumpur (manufactured by PTG-4000 Hodogaya Chemical Co., Ltd.) and alcoholate of using sodium hydroxide, Arirukuro Li adding de to convert the terminal allyl group, to obtain a terminal allyl group-containing polyoxy tetramethylene methylate down. The thing hexane - dissolved in an aqueous, the resulting sodium chloride removed into the aqueous phase was extracted a terminal allyl group-containing polyoxy tetramethylene methylate down removing the salt hexane phase. The presence of purified terminal allyl group-containing polyoxy tetramethylene methylate down the platinum catalyst obtained by removing the hexane, reacted with methyldimethoxysilane, the average molecular weight of 4000 to have a silyl group to 80% of the terminal polyoxy tetramethylene to obtain a methylene down.

Example 13 70 g of the polymer obtained in Synthesis Example 9 and 30 g of the polymer 6 were used.
After mixing the xylene solution g containing, with respect to composition 100 g obtained by removing the xylene, NOCRAC NS-
6 (manufactured by Ouchi Shinko Chemical Co., Ltd.), TINUVIN 327 (manufactured by Ciba Geigy), 1 g of Sanol LS-770 (manufactured by Ciba Geigy), and 1 g of dibutyltin dilaurate were added, and defoaming was performed so that air bubbles were not mixed, and the temperature was 60 ° C. 60% R
After curing for 7 days in H, a 2 mm thick sheet was obtained.

Comparative Example 9 Example 13 was repeated except that 100 g of only the polymer of Synthesis Example 9 was used instead of Synthesis Example 9 and Polymer 6 used in Example 13.
It examined by the method exactly the same as.

(Synthesis Example 10) 100 g of butyl acrylate, 1.5 g of γ-methacryloxypropyldimethoxymethylsilane, 3.6 g of γ-mercaptopropyldimethoxymethylsilane and 2 g of azobisisobutyronitrile were stirred to obtain a mixed solution. did. 25 g of this mixed solution was charged into a flask and heated to 80 ° C. with stirring. Polymerization started after a few minutes,-out fever is caused
It was After the exotherm becomes gentle, and slowly added dropwise over the rest of the mixed solvent solution 3 hours, polymerization was allowed to proceed. The reaction was terminated when the exothermic heat disappeared after the dropwise addition, and a polymer was obtained. Its molecular weight was 6,500.

[0107] (Comparative Example 10) 2 mm by a method identical except that the polymer was used in Daiwa Ri in Synthesis Example 10 of the polymer 1 in Example 6 was used in Example 6
A thick sheet was created.

Example 14 100 g of the polymer obtained in Synthesis Example 1, 50 g of polytetrafluoroethylene fine powder, 60 weight of calcium carbonate
g, calcium carbonate 60g, polyoxypropylene diol 25 having a 2,000 molecular weight and allylated at the end
g, dioctyl phthalate 25g, Nocrac NS-6
(Ouchi Shinko Chemical Co., Ltd.) 1 g, benzotriazole type ultraviolet absorber 1 g, hindered amine type anti-aging agent 1 g were added and thoroughly kneaded with 3 paint rolls, then dibutyl
2 g of tin dilaurate and 1 g of laurylamine were added,
Further, knead the mixture sufficiently to make a 2 mm thick sheet, and
C. and 60% RH for 14 days for curing and curing. It was weathering test in Sunshine weather-o meter over with this thing, but had no abnormality after 3000 hours.

[0109]

As described above, the curable composition of the present invention greatly improves the weather resistance, which has been a problem in the past. Furthermore, by strong fluororesin skeleton are mixed, elongation properties are also improved.

─────────────────────────────────────────────────── ─── Continuation of the front page (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, Kawasaki-shi, Kanagawa 2 Asahi Glass Tamagawa Branch Room Co., Ltd. (72) Inventor Mikio Yokota 3-474 Tsukakoshi, Sachi-ku, Kawasaki City, Kanagawa 2 Asahi Glass Co., Ltd. Tamagawa Branch Room (56) Reference JP-A-1-188558 (JP, A) JP-A-1 -188556 (JP, A) JP-A-3-294361 (JP, A) JP-A-6-116466 (JP, A) JP-A-6-116465 (JP, A) (58) Fields investigated (Int.Cl) . ⁷ , DB name) C08L 71/02-71/03 C08L 27/12-27/20 C09K 3/10 CA (STN)

Claims (4)

(57) [Claims] 1. A fluorinated polymer (B) containing, as an essential component, a silyl group-containing polyoxyalkylene (A) having on average one or more reactive silyl groups in the molecule and a fluoroolefin-based polymerized unit. It is a curable composition containing
The ratio of (A) / (B) is 100/1 to 1/100
(Weight ratio), and the fluoropolymer (B) is full
It has 20 mol% or more of polymerized units based on oro-olefins
A curable composition which is a polymer . 2. The curable composition according to claim 1, wherein the fluoropolymer (B) is a polymer having a polymerized unit based on a comonomer which is copolymerizable with a fluoroolefin. 3. A fluorine-containing polymer (B) is a polymer having a reactive site capable of co-crosslinking silyl group-containing polyoxyalkylene (A), the curable composition according to claim 1 or 2. 4. The curable composition according to claim 3 , wherein the reactive site capable of co-crosslinking is a reactive silyl group.