JPH08217836A - Production of fluorine-containing polymer - Google Patents

Abstract

PURPOSE: To obtain a fluorine-containing polymer having elasticity, excellent weatherability and resistance to staining and useful for a sealing material, etc., by polymerizing a polymerizable monomer comprising fluoroolefin as a principal component in the presence of an organic elastic polymer without having a long-chain polyoxyalkylene as a main chain. CONSTITUTION: This fluorine-containing polymer is obtained by polymerizing a polymerizable monomer having fluoroolefin as a principal component in the presence of an organic elastic polymer such as a polymer selected from a polysulfide-based polymer, an olefinic polymer, an acrylic polymer, a polysiloxane-based polymer and a polyester-based polymer copolymerizable with a polymerizable monomer containing fluoroolefin such as tetrafluoroethylene without having a long-chain polyoxyalkylene such as polyoxypropylene as a main chain, having one or more active point such as an unsaturated group, a chain transfer point or a radical initiation point in a molecule.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable composition.

[0002]

2. Description of the Related Art Conventionally, in the field of sealing materials and coating materials, it has been necessary to develop materials having excellent stretchability and weather resistance. Examples of resins used in the conventional market include urethane-based or modified silicone-based polymers having polyoxyalkylene as a main chain, polysulfide-based polymers, acrylic-based polymers, polyisobutylene-based polymers, silicone-based polymers, and the like. It is used by selecting the right material in the right place. However, none of the polymers other than the silicone-based polymer are satisfactory in terms of weather resistance, and even if the silicone-based polymer is satisfactory in weather resistance, the low molecular weight silicone contained in the polymer does not However, problems such as the occurrence of contamination around the periphery and low coating repeatability are occurring.

On the other hand, there has been proposed a method for improving weather resistance by combining a polyoxyalkylene with a fluororesin having excellent weather resistance, which is disclosed in JP-A-6-199970 and JP-A-6-1999.
Japanese Patent Laid-Open No. 10071, Japanese Patent Laid-Open No. 6-116465,
It is described in JP-A-6-116466.

[0004]

The present invention seeks to overcome the aforementioned drawbacks. That is, it is intended to provide a polymer having elasticity and excellent weather resistance and stain resistance.

[0005]

The present inventors have found that a curable composition obtained by compositing a polyoxyalkylene polymer and a fluorine-containing resin has excellent weather resistance, and filed a prior application. However, further studies, polymers other than polyoxyalkylene-based polymers, to examine the composite with fluorine-containing resin, various polymers, weather resistance or stain resistance is significantly improved. The inventors have found the present invention and have reached the present invention.

The present invention is the following inventions.

A process for producing a fluorine-containing polymer, which comprises polymerizing a polymerizable monomer containing a fluoroolefin as a main component in the presence of an organic elastic polymer having no long chain polyoxyalkylene as a main chain. And a curable composition containing the fluoropolymer produced by the production method.

The organic elastic polymer in the present invention is a polymer which does not have a long chain polyoxyalkylene as the main chain, and exhibits elasticity due to the polymer having a high molecular weight or gelation (crosslinking). It is a polymer that does.

The long-chain polyoxyalkylene is a polymer chain obtained by polymerizing alkylene oxide, and includes polyoxypropylene, polyoxyethylene, polyoxytetramethylene, polyoxypropylene / polyoxyethylene and the like. Particularly, in the presence of an organic elastic polymer having a polyoxypropylene main chain, a fluoropolymer obtained by polymerizing a polymerizable monomer having a fluoroolefin as a main component is known, but in the present invention, By using an organic elastic polymer other than the organic elastic polymer having such a long-chain polyoxyalkylene as a main chain, a novel polymer having excellent physical properties is provided.

The organic elastic polymer not having a long chain polyoxyalkylene as a main chain in the present invention is specifically a polysulfide polymer, an olefin polymer, an acrylic polymer, a polysiloxane polymer, and Polymers selected from polyester polymers are preferred. By using these polymers, the fluorine-containing polymer of the present invention can have improved heat resistance, acid resistance, weather resistance and solvent resistance as compared with the organic elastic polymer itself.

The molecular weight of the organic elastic polymer is not particularly limited, but from the viewpoint of the polymerization operation of the present invention, those soluble or swellable in a solvent are preferably liquefied with a solvent. Alternatively, a liquid having a medium to low molecular weight is preferable, and a liquid having a molecular weight of about 300 to 50,000 is preferable. More preferably 500 to 30,000, particularly preferably 1000.
~ 20,000.

In the present invention, the organic elastic polymer is
It is preferable to have an active site capable of copolymerizing with a polymerizable monomer containing a fluoroolefin as a main component. Examples of the active site include 1) unsaturated group, 2) chain transfer point, 3) radical initiation point and the like.

The chain transfer point includes a group capable of causing a chain transfer reaction in general radical polymerization. Examples of groups that are particularly susceptible to chain transfer include mercapto groups, disulfide bonds, halogenated alkyl groups, and nitrogen-containing compounds. In addition to these, compounds having a hydroxyl group in which hydrogen is bonded to α carbon, a carbonyl group, a phenyl group, an ether bond, or the like can be given, but the compound is not particularly limited as long as it has activity for radicals. .

Examples of the radical initiation point include groups that generate radicals by heat, light, radiation or the like, or by mixing with other compounds, and examples thereof include polymers having a peroxide, a diazo bond, an amino group or the like. However, the present invention is not limited to these.

In the present invention, it is most preferable that the organic elastic polymer has an unsaturated group copolymerizable with the fluoroolefin.

In this case, it is preferable that the content of the polymer in the unsaturated group is 0.05 to 80 mol%. If it is more than this, it is difficult to insert the fluoroolefin-based polymer between the above-mentioned polymers, and even if it is inserted, the molecular length does not reach a sufficient length to exert the effect and the effect as the present invention is exerted. It can be difficult. On the other hand, if it is less than the above range, there arises a problem that it is difficult to sufficiently graft the fluoroolefin-based polymer. More preferably 1-5
0 mol%, more preferably 1 to 20 mol%,
This is not the case when, for example, a chain transfer point is present in the polymer other than the polymerizable group, or in the case of polymerization in which radical active sites are forcibly generated in the polymer such as radiation polymerization.

Hereinafter, each of the above-mentioned polymers as preferable polymers as the organic elastic polymer will be described.

(Polysulfide Polymer) As the polysulfide polymer in the present invention, for example,-(SC ₂
H ₄ -O-CH ₂ -OC ₂ H ₄ -S) _p -,-(SC ₂ H ₄ -S) _p -,-(S-CH ₂ -CH (C
H ₃ ) -S) _p − (p is an integer), a polymer having a molecular chain thereof, or a copolymer thereof.

These were excellent in weather resistance, stain resistance and solvent resistance as compared with the polyoxyalkylene polymer, but on the other hand, in heat resistance, deterioration after heating was large. However, it was found that the use of the fluoropolymer as in the present invention significantly improved the heat resistance and the weather resistance, and was excellent in the stain resistance as compared with the case of the polyoxyalkylene type. It was also found that it has excellent moisture permeation resistance and is suitable as a sealing material for double glazing.

Since this polymer has a disulfide bond even as it is, it is chain-transferred during the polymerization of the polymerizable monomer containing fluoroolefin as a main component (hereinafter, also referred to simply as the polymerizable monomer) to form a graft body. To generate. Further, the terminal group is generally an SH group, but, for example, one having an unsaturated bond (also referred to as an unsaturated group) introduced at the terminal may be used.

As a method for synthesizing such a polymer, halogenated compounds at both ends, specifically ClC ₂ H ₄
OCH ₂ 0C ₂ H ₄ Cl, ClC ₂ H ₄ Cl, ClC ₃
Reacting a compound such as H ₆ Cl with sodium polysulfide,
There is a method of condensation polymerization. Further, as a method of adjusting the molecular weight, there is a method of oligomerization by a reduction reaction with a reducing agent such as NaSH or Na ₂ SO ₃ .
Unsaturation of vinyl chloride, allyl chloride, 2-chloroethyl vinyl ether, (meth) acrylic acid chloride, crotonic acid chloride, or those in which these chlorines are replaced with other halides (bromine, iodine, etc.) during condensation polymerization An unsaturated group can be introduced at the terminal by coexisting an appropriate amount of a group-containing halogen compound, and an oligomeric low to medium molecular weight product can be synthesized in one step. Further, it is possible to introduce the unsaturated group at the end to jointly an unsaturated group-containing compound such as CH ₂ = CH-CH ₂ -SNa in the reduction reaction step.

Further, the resulting polymer terminal SH group may be modified later into various functional groups. For example, under alkali, epichlorohydrin, vinyl chloride, allyl chloride, chloroethyl vinyl ether or those in which these chlorine are substituted with other halogen, mercaptoethanol, mercaptopropyl group-containing silane compounds such as condensation reaction with a mercapto compound, etc. It is possible to modify the terminal SH group into another reactive group by the reaction. When this modified product is used, the resulting polymer is reactive at the end and can be used as a curable site, so that it can be used as it is or as a curable composition in combination with a curing agent or a catalyst. preferable.

Preferred curable moieties include hydrolyzable silyl groups, hydroxyl groups, isocyanate groups, amino groups, epoxy groups, mercapto groups or unsaturated groups.

Here, the hydrolyzable silyl group is represented by the following formula (1)
What is represented by is preferable.

SiR ¹ _m X _3-m (1) where m is an integer of 0 to 2, R ¹ is an organic group, X is halogen or CH ₃ O, C ₂ H ₅ O, CH ₃ O-. C ₂ H ₄
O, an alkoxy group such as PhO, a carboxyl group such as CH ₃ COO, an aminoxime group such as (CH ₃ ) ₂ C═N—O, an amide group such as CH ₃ CONH, CH ₃ CON (C ₂ H ₅ ) —, CH ₃ C (= CH ₂₎ a hydrolyzable group such as ketoxime groups O-, and the like.

When a polysulfide polymer is used,
Since it has a disulfide bond, which is a group with chain transferability, as an active site that can be copolymerized with a polymerizable monomer containing fluoroolefin as a main component, the polymer obtained can be highly grafted if the polymerization conditions are appropriately set. It can be a body.

(Olefin Polymer) Examples of the olefin polymer include ethylene, propylene, 1-butene, isobutylene, cyclohexadiene, isoprene,
Polymers containing olefin compounds such as butadiene and chloroprene as a main component are preferable, and examples thereof include ethylene-propylene copolymers, ethylene-propylene-butadiene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic copolymers. , Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene- (meth) acrylic copolymer, polyisobutylene-based polymer, hydrogenated polybutadiene-based polymer and the like. .

Of these, a polymer using butadiene is preferable because it has an unsaturated bond in the molecule and forms a graft product when polymerizing a polymerizable monomer containing a fluoroolefin as a main component. There is also a method of forcibly grafting a fluoroolefin onto the polymer by radiation or the like. However, in those containing a large amount of butadiene component, the unsaturated bond in the system may remain after the polymerization of the polymerizable monomer, which may not be preferable for applications requiring high weather resistance. Particularly, a polymer containing butadiene in an amount of 50 mol% or less is preferable, and more preferably 30 mol% or less.

A copolymer of ethylene with propylene, a (meth) acrylic monomer, acrylonitrile or a vinyl ester has few unsaturated bonds in the system. Therefore, a polymerizable monomer containing fluoroolefin as a main component is added to these polymers. When it is desired to highly graft the body, it is preferable that the polymer mainly containing these components has a radical active site introduced at its terminal or side chain. Also from the viewpoint of handling, a telechelic type having a hydroxyl group, an amino group, a carboxyl group, etc. at the liquid end is grafted by chain transfer at the time of polymerization of a polymerizable monomer containing a fluoroolefin as a main component even if the functional group remains as it is. This is particularly preferable because it can be a point, and it is easy to introduce another unsaturated group or chain transfer group that is active with respect to the polymerization radical.

Specific examples of such a method of introducing a radical active site at the terminal include the following three methods.

Those having a hydroxyl group at the terminal include a compound containing a carboxyl group / acid halide group and an unsaturated group such as (meth) acrylic acid or (meth) acrylic acid chloride, an isocyanate group such as allyl isocyanate and an unsaturated group. A method of introducing an unsaturated group by reacting a containing compound or a halogen such as allyl chloride or chloromethylstyrene and a compound containing an unsaturated group.

Those having an amino group at the terminal include epoxy group- and unsaturated group-containing compounds such as allyl glycidyl ether, glycidyl (meth) acrylate and glycidyl vinyl ether, maleic anhydride, (meth) acrylic acid or (meth) acrylic acid chloride. React with carboxyl group / acid halogenated group and unsaturated group containing compounds such as, isocyanate group and unsaturated group containing compounds such as allyl isocyanate or halogen and unsaturated group containing compounds such as allyl chloride and chloromethylstyrene , A method of introducing an unsaturated group.

Those having a carboxyl group at the terminal include epoxy group- and unsaturated group-containing compounds such as allyl glycidyl ether, glycidyl (meth) acrylate and glycidyl vinyl ether, isocyanate group- and unsaturated group-containing compounds such as allyl isocyanate, and allyl amine. Amino group- and unsaturated group-containing compounds such as or hydroxyethyl (meth) acrylate, allyl alcohol, hydroxyethyl allyl ether, hydroxyethyl crotonate, hydroxybutyl vinyl ether and other hydroxyl- and unsaturated group-containing compounds are reacted to form unsaturated groups How to introduce.

Not limited to these, for example, a polymer end group and a compound containing a reactive group and an unsaturated group,
For example, a method in which the compound is appropriately reacted and introduced through a compound such as polyisocyanate, polybasic acid, or polyfunctional epoxy compound may be used.

As a copolymerization component, a monomer having a reactive group such as a hydrolyzable silyl group, a hydroxyl group, a carboxyl group, a non-hydroxyl group, an epoxy group or a halogen-containing group is used, or a vinyl ester is copolymerized. Those subjected to post-hydrolysis treatment are also preferable.

If a polyisobutylene-based polymer is also synthesized by cationic polymerization, it is easy to modify the terminal group, and an unsaturated group, a mercapto group, or other group that can be a grafting point in the polymerization of fluoroolefins is used. It is preferable because various reactive groups such as other hydroxyl group, amino group, epoxy group and the like can be easily introduced.

As the liquid telechelic type,
Liquid butadiene having a reactive group such as an amino group, a hydroxyl group, a carboxyl group, and a hydrolyzable silyl group, ethylene,
Examples of the oligomer include propylene and isobutylene as components.

When a polymer having any of these functional groups is used, the resulting polymer has a reactive terminal and can be used as a curable site. Therefore, the curable composition can be used as it is or in combination with a curing agent or a catalyst. It is preferable because it can be used as a product.

Preferred curable moieties include hydrolyzable silyl groups, hydroxyl groups, isocyanate groups, amino groups, epoxy groups, mercapto groups or unsaturated groups.

The composite of an olefin polymer and a polymer of a polymerizable monomer containing a fluoroolefin as a main component gives a polymer having higher weather resistance than that of a polyoxyalkylene polymer, and polysulfide is also used. It was found that, like the polymer, it has excellent moisture permeation resistance and is suitable as a sealing material for double glazing.

(Acrylic Polymer) The acrylic polymer is preferably an acrylic polymer having Tg of 30 ° C. or lower. The acrylic polymer is an elastic polymer whose main component is acrylic acid, methacrylic acid or their esters. When the Tg point is higher than 30 ° C, elasticity at room temperature is not sufficiently exhibited, which is not preferable. Preferred polymers are those having a (meth) acrylic acid ester having 2 to 4 carbon atoms as a main component, particularly preferably those having butyl acrylate and / or ethyl acrylate as a main component, and more preferably 40 these components. It contains more than weight%.

As a synthetic method, an ordinary radical polymerization is possible,
At this time, it is also preferable to add a compound containing a reactive group as a copolymerization component. Preferred reactive groups include, for example, epoxy groups, hydroxyl groups, carboxyl groups, amide groups, N-methylol groups, hydrolyzable silyl groups, unsaturated groups and halogen-containing groups. For example, epoxy compounds such as glycidyl (meth) acrylate, glycidyl allyl ether, and glycidyl vinyl ether, hydroxyl group-containing compounds such as hydroxyethyl (meth) acrylate, maleic anhydride, and carboxyl group-containing compounds such as (meth) acrylic acid, ( Amide compounds such as (meth) acrylamide and N-methylol (meth) acrylamide, hydrolyzable silyl group-containing compounds such as methacryloxypropyltrimethoxysilane and methacryloxypropylmethyldimethoxysilane, unsaturated group-containing compounds such as allyl methacrylate or 2 And halogen-containing compounds such as chloroethyl vinyl ether, allyl chloride and chloromethylstyrene.

It is also preferable to use a polymerization initiator or a chain transfer agent containing a reactive group. Specific examples of such a compound include compounds that can be added during the polymerization of the polymerizable monomer and are the same as the reactive group-containing polymerization initiator and / or the chain transfer agent described later.

(Polysiloxane-based polymer) The polysiloxane-based polymer has a structure in which the main chain is essentially composed of repeating units consisting of-(Si-0) _n-.
The following structure is possible.

[0045]

Embedded image

In the chemical formula 1, R ² and R ³ are the same or different organic groups, and p is an integer.

The structure (2) is preferable from the viewpoint of easy availability and easy synthesis. Especially when R ² is a methyl group,
General silicone oil consisting of phenyl group, vinyl group, fluoroalkyl group, polyoxyalkylene group, etc.,
Vinyl group, hydrogen, terminal amino group, epoxy group, carboxyl group, hydroxyl group, hydroxyalkyl group,
A silicone oil in which part or all of R ² is an OH group (silanol group) or a part or all of R ² is a hydrolyzable group that forms a silanol group by hydrolysis is preferable.

Further, a polymer having a reactive group at its terminal is also preferable when the polymer of the present invention is used as a curable composition. Such things as hydrogen R ³ above may, OH group, hydrolysis to SiOH groups become such groups, terminal amino group, a carboxyl group, a mercapto group, a hydroxyl group, a vinyl group, an unsaturated group, a halogen group, etc. And an alkyl group having Specific examples of R ³ include the following.

H, OH, C _p H _2p NH ₂ , C _p H _2p NH
C ₂ H ₄ NH ₂ , C _p H _2p SH, C _p H _2p Cl, C _p H
_{2p OH, C p H 2p COOH} , CH = CH 2, C p H 2p O
_{CH = CH 2, C p H} 2p OCOCH = CH 2, C p H 2p
_{OCOC (CH 3) = CH 2} , C p H 2p COOCH = C
_{H 2, C p H 2p CH} = CH 2, C p H 2p OCOCH = C
HCH ₃ .

[0050]

Embedded image

SiR ¹ _m X _3-m m, R ¹ and X are as defined above, and p is an integer.

Among these, those having a vinyl group or a mercapto group are highly effective in obtaining a fluorine-containing polymer and a polysiloxane polymer when a polymerizable monomer containing a fluoroolefin as a main component is polymerized. Grafting is preferred. Especially because of its polymerizability with fluoroolefins, R ³
There _{CH = CH 2, C p H} 2p OCH = CH 2, C p H 2p C
_{OOCH = CH 2, C p H} 2p CH = CH 2, C p H 2p O
Those having a group such as COCH = CHCH ₃ are preferable,
In this case, CH = CH ₂ or p due to availability.
Is more preferable.

Further, a hydrolyzable silyl group, a hydroxyl group, an isocyanate group, an amino group, an epoxy group, a mercapto group,
When a siloxane-based polymer containing an unsaturated group or the like is used, the resulting polymer has a reactive terminal and can be used as a curable site, so that the curable composition can be used as it is or in combination with a curing agent or a catalyst. It is preferable because it can be used as a product.

The fluorine-containing polymer thus obtained has an effect such that when it is used as a sealant, the stain resistance of the surroundings is significantly reduced and the adhesiveness of the coating is improved as compared with the polysiloxane polymer itself. It was found that Although the cause is not clear, it is considered that the fluorine-containing polymer is probably concentrated on the surface of the cured product and prevents the surface bleeding of the siloxane oligomer, which causes the contamination of the periphery and the poor adhesion of the paint.

(Polyester Polymer) The polyester polymer is substantially-(R ⁴ --COO) _p --or (-
OCOR ⁴ COOR ⁵ ) _p (p is an integer) is a polymer having a repeating unit as a main chain, and R ⁴ and R ⁵ are divalent organic groups, and are particularly aliphatic as having good elasticity. Hydrocarbons are preferred.

Specifically, C ₂ or more aliphatic dicarboxylic acids such as succinic acid, adipic acid and suberic acid, or acid chlorides or acid anhydrides thereof and ethylene glycol, propylene glycol, 1,4-butanediol, Examples thereof include condensation products with diols such as 1,6-hexanediol and those obtained by ring-opening polymerization of cyclic esters such as γ-butyrolactone, ε-caprolactone and lactide.

Since these terminals generally have a hydroxyl group or a carboxyl group at their ends, an unsaturated group or a mercapto group, which becomes an active site of radical polymerization, other epoxy groups capable of curing reaction, or a hydrolyzable silyl group. , Easy modification to isocyanate groups and the like.

Further, at the time of polymer synthesis, unsaturated bonds such as glycerin monoallyl ether, maleic acid, maleic anhydride, allyl glycidyl ether, glycidyl methacrylate, a reaction product of allyl glycidyl ether and dicarboxylic acid and two or more Using a compound having an active hydrogen group capable of reacting with a hydroxyl group or a carbonyl group as an initiator,
It is also preferable to use it as a copolymerization component.

Further, hydroxybutyl vinyl ether,
Hydroxyethyl vinyl ether, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxyethyl crotonic acid, allyl alcohol, 2-hydroxyethyl allyl ether,
(Meth) acrylic acid, (meth) acrylic acid chloride,
It is also preferable to use an unsaturated group-containing compound capable of reacting with a hydroxyl group or a carboxyl group such as crotonic acid or vinylacetic acid as an initiator for polymerization.

It has been found that the fluorine-containing polymer of the present invention is remarkably improved in water resistance, which is a drawback of conventional polyester polymers.

(Polymerizable Monomer) In the present invention, a polymerizable monomer containing a fluoroolefin as a main component is used.
The weight ratio of the organic elastic polymer (A) to the polymerizable monomer containing fluoroolefin as a main component in the present invention is 10/9.
The range of 0 to 90/10 is preferable. If the amount of the polymerizable monomer is larger than this, problems such as good elasticity cannot be obtained, and if it is smaller than this, curing such as compression recovery, weather resistance and the like as in the present invention is sufficiently exhibited. Not done. It is more preferably 20/80 to 80/20.

Examples of the fluoroolefin include the followings. Tetrafluoroethylene,
Chlorotrifluoroethylene, trifluoroethylene,
At least one of unsaturated carbons such as vinylidene fluoride, vinyl fluoride, hexafluoropropylene, pentafluoroethylene, and perfluoropropyl vinyl ether is substituted with fluorine, and has 2 to 10 carbon atoms, particularly 2 to 2 carbon atoms. About 6 fluoroolefins are preferably employed. Of these, perhalofluoroolefins in which hydrogen is completely replaced by halogen are most preferable.

Further, a polymerizable monomer which can be copolymerized with the fluoroolefin together with the fluoroolefin can be used. Examples of the polymerizable monomer copolymerizable with the fluoroolefin include compounds having a polymerizable site such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Specifically, olefins, vinyl ethers, vinyl esters,
Examples include allyl ethers, allyl esters, acrylic acid esters, methacrylic acid esters, crotonic acid esters and the like.

As such a polymerizable monomer, a part or all of hydrogen bonded to carbon may be replaced with fluorine. 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.

Of these, vinyl ethers, vinyl esters, allyl ethers, allyl esters, α-olefins, and crotonic acid esters are preferred from the viewpoint of weather resistance because they have a high probability of alternating copolymerization with fluoroolefins. . 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 or Veova 10 (manufactured by Shell Chemical Co., Trade name of vinyl ester of branched fatty acid having 9 or 10 carbon atoms), fatty acid vinyl ester such as vinyl versatate, ethyl acrylate, methyl methacrylate Butyl acrylate, butyl methacrylate, acrylic acid or methacrylic acid esters such as cyclohexyl methacrylate, ethyl crotonate, butyl crotonate, cyclohexyl crotonate, 2-hydroxy ethyl crotonate, crotonic acid-2
Examples include crotonic acid esters such as hydroxylbutyl.

It is also preferable that the polymerizable monomer having a fluoroolefin as a main component has a curable site when the polymer of the present invention is used as a curable composition. Examples of such a curing site include a hydrolyzable silyl group, a hydroxyl group, an isocyanate group, an amino group, an epoxy group, a mercapto group, a non-hydroxyl group or an N-methylol unsaturated group.

Particularly preferred from the viewpoint of curing reactivity are hydrolyzable silyl groups, hydroxyl groups, isocyanate groups, amino groups, epoxy groups, mercapto groups or unsaturated groups.

By containing these groups, the copolymer of the present invention can be used as a curable composition by using a catalyst, heat, light, a curing agent or the like. In addition, even when the composition is not a curable composition, it is preferable because it exhibits the performance as an adhesive or a pressure-sensitive adhesive.
In addition, it is also preferable to convert each of the above functional groups into another group, if necessary.

Examples of the polymerizable monomer having such a curing site are as follows. For example, A-
SiR ¹ _m X _3-m (A is an organic group containing a polymerizable unsaturated group,
m, X and R ¹ are the same as those defined above, and specifically, for example, dimethoxymethylvinylsilane, trimethoxyvinylsilane, diethoxymethylvinylsilane,
Examples thereof include dimethoxymethylallylsilane, dimethoxymethylsilylpropyl acrylate, trimethoxysilylpropyl methacrylate, dimethoxymethylsilylpropyl vinyl ether, and dimethoxymethylsilylpropyl allyl ether.

Specific examples of the polymerizable monomer having a curable site other than the hydrolyzable silyl group include 2-hydroxyethyl vinyl ether and 4-hydroxyethyl vinyl ether.
Hydroxybutyl vinyl ether, allyl alcohol,
2-hydroxyethyl allyl ether, 2-hydroxyethyl (meth) acrylate, hydroxyl group-containing polymerizable unsaturated group-containing monomers such as 2-hydroxyethyl crotonic acid, glycidyl allyl ether, glycidyl vinyl ether, glycidyl acrylate, glycidyl methacrylate and other epoxies Group-containing polymerizable unsaturated group-containing monomer,
Examples thereof include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, and maleic anhydride.

Further, in polymerizing the above-mentioned polymerizable unsaturated group-containing monomer, a chain transfer agent having a curable site,
It is also preferable to use an initiator having a curable site in order to improve the physical properties and adhesiveness of the resulting polymer. Specific examples of these compounds include the following.

Examples of the chain transfer agent having a curable site include a hydroxyl group-containing chain transfer agent such as mercaptoethanol and thioglycerol, a mercapto-based chain transfer agent such as mercaptoacetic acid, (H ₂ N—C ₆ H ₄ —S) ₂ , (HOOC-C ₆ H
₄ -S) _2, (HOOC-CH ₂ -S) disulfide chain transfer agent such as _2, the following equation (4), a chain transfer agent represented by (5).

[0074]

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However, Z is an organic group containing a group-polymerizable unsaturated group which is activated by free radicals, and R ⁶ is a carbon number of 1 to
20 divalent hydrocarbon groups, a is 0 to 1, b is 0 to 2, provided that a + b ≦ 1, m is an integer of 0 or more, X, R ² , R ³
Is the same as above.

Specifically, a compound in which Z is a mercapto group, a chlorine group, a bromine group or an amino group is preferable, and for example, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, 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 an initiator having a curable site, HO-C
₃ H ₆ -C (CH ₃ ) (CN) -N = NC (CH ₃ ) (CN) -C ₃ H ₆ -OH, HO-CH ₂ -C (C
_{H 3) (CN) -N =} NC (CH 3) (CN) -CH 2 -OH, HOOC-C 2 H 4 -C (CH 3) (C
N) -N = NC (CH ₃ ) (CN) -C ₂ H ₄ -COOH, such as an azo initiator having a carboxyl group and a carboxyl group, an azo system having a hydrolyzable silyl group as shown in the following formula (6) There is an initiator, and specific examples thereof include compounds represented by (6) and (7).

[0078]

[Chemical 4]

However, R ⁶ , a, b, m, X, R ² , R
³ is the same as above.

The polymerization method can be the same as in the case of polymerizing a normal fluoroolefin. 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. It is particularly preferable when the organic elastic polymer (A) having a small number of active sites capable of copolymerizing with a polymerizable monomer containing a fluoroolefin as a main component is used and high grafting is required.

The solvent may be added if necessary, but the organic elastic polymer (A) having substantially no ether bond.
However, when it is liquid at the temperature during the polymerization operation, the characteristic is that the polymerization solvent required for polymerizing the polymerizable monomer containing a fluoroolefin as a main component is not necessarily required. 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.

(Application Example of Curing) An application example of curing of the curable portion of the fluoropolymer of the present invention having the thus obtained curable portion will be given.

Hydrolyzable silyl group: As it is, or by moisture curing with a catalyst such as an acid, alkali, organic tin or organic titanium compound.

Hydroxyl group: Urethane cure using a compound having two or more isocyanate groups in the molecule as a curing agent (in this case, the isocyanate group is blocked with ketoxime or phenol, or the hydroxyl group is trialkylsilyl group). When one that is blocked with a group is used, a one-pack type curable composition can be formed), and epoxy curing using a compound having two or more epoxy groups in the molecule as a curing agent.

Isocyanate group: a two-pack type curing system using as a curing agent an active hydrogen group-containing compound such as two or more hydroxyl groups, carboxyl groups, amino groups and mercapto groups in the molecule, One-component curing type that uses one blocked with an alkylsilyl group.

Amino group: Two-component curing type compound having a compound having two or more isocyanate groups, epoxy groups, carbonyl groups, etc. in the molecule as a curing agent, and the amino groups are blocked by trialkylsilyl groups, carbonyl groups, etc. The one-component curing type, and the one-component curing type in which the isocyanate group in the curing agent is blocked.

Epoxy group; two or more hydroxyl groups in the molecule,
Two-component type curing system using a compound containing active hydrogen group such as carboxyl group, amino group and mercapto group as a curing agent, or one-component system using the active hydrogen containing group blocked with trialkylsilyl group, carbonyl group, etc. Curing type.

Mercapto group; air curing by oxygen in air and, if necessary, catalyst, two-component curing type using a compound having two or more isocyanate groups in the molecule as a curing agent.

Unsaturated group; radical curable type using a catalyst that generates radicals by light or heat, oxidative curable type with oxygen in the air in the case of a conjugated unsaturated group, two or more HS in the molecule.
Examples thereof include hydrosilylation-curable type compounds having an i group.

Among them, curing with a hydrolyzable silyl group is excellent in curing property at a low temperature. The curing system by reaction of urethane bond, mercapto group, amino group and epoxy group is a polar group to be formed, so that a wide range of adherends can be obtained. Has good adhesiveness, and air-curing with a mercapto group is not moisture-curing, so that it can be cured under a wide range of humidity conditions.

(Additive) Further, the polymer of the present invention includes a curing agent, a curing catalyst, a filler, a solvent, a light stabilizer, an ultraviolet absorber, a heat stabilizer, an adhesiveness imparting agent, a plasticizer, and air oxidation. A curable compound, a photopolymerization initiator, a polymerizable monomer polymerized by the initiator, a photopolymerizable monomer, a leveling agent physical property adjusting agent, and the like may be added and blended. The main ones will be described.

(Filler) As the filler, reinforcing fillers such as fumed silica, precipitable silica, silicic acid anhydride, hydrous silicic acid and carbon black; calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, Talc, titanium oxide, bentonite, organic bentonite,
Fillers such as ferric oxide, zinc oxide, activated zinc oxide, hydrogenated castor oil and shirasu balloons; fibrous fillers such as asbestos, glass fibers and filaments can be used.

In order to obtain a hardened composition having high strength with these fillers, mainly fumed silica, precipitated silica, silicic acid 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,
A filler selected from calcium carbonate, ground calcium carbonate, surface-treated calcium carbonate, colloidal calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon and the like is used as the curable composition 10 of the present invention.
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.

(Solvent) Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol and t-butanol, ketones such as methyl ethyl ketone, and aromatic solvents such as xylene and toluene.

(Light Stabilizer, Ultraviolet Absorber, Thermal Stabilizer) A hindered amine type, benzotriazole type, benzophenone type, benzoate type, cyanoacrylate which is generally used as a light stabilizer, an ultraviolet ray absorber and a heat stabilizer. Each compound such as a phenol-based compound, a phenol-based compound, an acrylate-based compound, a hindered phenol-based compound, a sulfur-based compound, and a phosphorus-based compound can be appropriately used.

(Adhesiveness imparting agent) As an adhesiveness imparting agent, a silane coupling agent or an epoxy resin which is generally used,
Examples thereof include a curing agent for an epoxy resin and a curing catalyst. Specific examples of the silane coupling agent include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraphenoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-amino. Propyldimethoxymethylsilane, 3- (2-aminoethylaminopropyl)
Aminosilanes such as trimethoxysilane and 3- (2-aminoethylaminopropyl) dimethoxymethylsilane,
γ-glycidoxypropyltrimethoxysilane, γ-glyzidopropyldimethoxymethylsilane, β- (3,4
-Epoxycyclohexyl) ethyltrimethoxysilane and other epoxysilanes, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyldimethoxymethylsilane and other methacrylsilanes, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethyl Examples thereof include vinylsilanes such as silane and vinyltrichlorosilane. These compounds are used in the composition of the present invention in an amount of 0.01 or more, preferably 0.1 to 20.
By adding about parts by weight, excellent adhesiveness can be obtained.

Epoxy resins that can be added to the composition of the present invention include epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, tetrabromobisphenol A glycidyl ether, and other flame retardants. Type epoxy resin, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin,
Glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, diglycidyl ester type epoxy resin such as diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, and hexahydrophthalic acid diglycidyl ester, m-aminophenol epoxy resin,
Diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, etc. Commonly used epoxy resins such as glycidyl ethers of polyhydric alcohols, epoxidized unsaturated polymers such as hydantoin type epoxy resins, petroleum resins, and vinyl polymers containing epoxy groups are exemplified. However, it is not limited thereto.

Among these epoxy resins, those containing at least two epoxy groups in the molecule have high reactivity during curing, and the cured product easily forms a three-dimensional network. Preferred and more preferred are bisphenol A type epoxy resins, phthalic acid ester type diglycidyl esters, novolac type epoxy resins, and vinyl type polymers having at least two epoxy groups in the molecule.

The composition of the present invention may be used in combination with a curing agent or curing catalyst for the above epoxy resin. Examples of such a curing agent include generally used curing agents for epoxy resins. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 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 with respect to 100 parts by weight of the epoxy compound.

(Plasticizer) It is also preferable to add a plasticizer to the composition of the present invention in order to improve workability. As the plasticizer, commonly used plasticizers, for example, phthalates such as dioctyl phthalate, dibutyl phthalate, diallyl phthalate and butylbenzyl phthalate, dioctyl adipate, aliphatic dibasic acid esters such as isodecyl succinate, Diethylene glycol dibenzoate, glycol esters such as pentaerythritol ester, aliphatic esters such as butyl oleate, methyl acetyl silinoleate, tricresyl phosphate, trioctyl phosphate, phosphates such as octyl diphenyl phosphate, epoxidation Soybean oil, epoxy-based plasticizers such as benzyl epoxy stearate, and general plasticizers such as chlorinated paraffin can be used. In addition to these, polymer plasticizers can also be used to prevent contamination of the surrounding area due to migration of plasticizers. It preferred in order to prevent such.

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.

(Air Oxidation-Curable Compound) As the air-oxidation-curable compound, a drying oil typified by tung oil, linseed oil, etc., various alkyd resins obtained by modifying the compound, and a drying oil are modified. Acrylic polymers, silicone resins, 1,2-polybutadiene, 1,4-polybutadiene, diene-based polymers such as C _{5 to} C ₈ diene polymers and copolymers, and further the polymers and copolymers Examples of the modified products include maleic modification, boil oil modification, and the like. Among these, tung oil, liquids of diene polymers (liquid diene polymers), hydrogenated castor oil and its modifications. The thing is especially preferable. These air oxidation curable compounds may be used alone or in combination of two or more.

(Photopolymerization Initiator) As the photopolymerization initiator, compounds such as acetophenone compounds generally used can be mentioned. Examples of the photopolymerizable monomer include acrylic special monomers such as polyfunctional modified acrylates generally used for electron beam or ultraviolet 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.

(Use) The novel fluoropolymer of the present invention is
For adhesive sealant, waterproofing agent, coating agent, etc.
As it is, or mixed with other additives as raw materials,
Although it can be used, it is particularly suitable for applications requiring durability and weather resistance of the cured product.

[0107]

EXAMPLES Examples will be given below, but the present invention is not limited to the following Examples (parts indicate parts by weight).

Example 1 Polysulfide polymer containing terminal epoxy group (LP-32 manufactured by Torethiocol)
60 parts, tetrafluoroethylene 40 parts, ethyl vinyl ether 20 parts, γ-vinyloxypropylmethyldimethoxysilane 5 parts, xylene 10 parts, and azobisisobutyronitrile 2 parts were charged into an autoclave, and 2
Reaction was allowed for 0 hr.

After removing xylene from the obtained polymer, the yield was measured and found to be 105 parts. Chlorinated paraffin 15 as a plasticizer to 40 parts of the obtained polymer.
Parts, fatty acid treated calcium carbonate 40 parts, hydrogenated castor oil 1
After mixing the parts well kneaded with 3 paint rolls,
2 parts of tin octylate was added to prepare a test piece of 5 cm × 1.5 cm square and 1.5 cm thick, which was aged at 20 ° C. 60% RH condition for 1 week and 50 ° C. 60% RH condition for 1 week. An outdoor dynamic exposure test was conducted with a dynamic exposure tester.

Example 2 Polysulfide polymer containing terminal epoxy group (FLEP-6 manufactured by Torethiocol Ltd.)
70 parts of 0), 30 parts of tetrafluoroethylene, 20 parts of ethyl vinyl ether, 20 parts of xylene, and 2 parts of azobisisobutyronitrile were charged into an autoclave, added, and reacted at 60 ° C. for 20 hours. After removing xylene from the obtained polymer, the yield was measured to be 115.
It was a department. The epoxy equivalent of the obtained polymer is 1
It was 70. To 40 parts of the obtained polymer, 15 parts of chlorinated paraffin as a plasticizer, 40 parts of fatty acid-treated calcium carbonate and 1 part of hydrogenated castor oil were mixed, and then thoroughly kneaded with 3 paint rolls to obtain polyoxypropylene triol. Was added to 10 parts of an isocyanate group-terminated prepolymer obtained by reacting with hexamethylene diisocyanate and treated with 2-mercaptomethanol to prepare a test body similar to that of Example 1, and an outdoor dynamic exposure test was conducted.

(Comparative Example 1) Polysulfide polymer containing terminal epoxy group (LP-32 manufactured by Torrethiocol)
Chlorinated paraffin 15 as a plasticizer for 40 parts of
Parts, fatty acid treated calcium carbonate 40 parts, hydrogenated castor oil 1
After mixing 3 parts by weight, 3 parts of lead dioxide was added to a well kneaded mixture with 3 paint rolls to prepare a test body similar to that of Example 1,
An outdoor dynamic exposure test was conducted.

As a result, one year after the start of the dynamic exposure, in Comparative Example 1, a large crack was generated in the central part of the test body in a direction perpendicular to the mutation direction of the dynamic exposure, whereas in Examples 1 and 2, There were no abnormalities. Also, regarding the surface stain, almost no stain was found on the external appearance of each test body.

Example 3 Under a nitrogen atmosphere, 50 parts of polybutadiene having hydroxyl groups at both ends having a number average molecular weight of 3000, 20 parts of vinylidene fluoride, 30 parts of tetrafluoroethylene, 50 parts of methanol, and 2 parts of tert-butyl perisobutyrate were added. After charging into an autoclave and reacting at 30 ° C. for 60 hours, methanol was removed and the yield was measured.
It was 90 parts.

50 parts of the obtained polymer was added to 1 part each of 40 parts of fatty acid-treated calcium carbonate, 10 parts of titanium oxide, 5 parts of xylene, phenolic antioxidant, benzotriazole ultraviolet absorber, and hindered amine light stabilizer. After being mixed, it was well mixed with three paint rolls. Furthermore, 3.5 parts of hexamethylene diisocyanate and 1 part of dibutyltin dilaurate were added and mixed well to prepare a 3 mm thick sheet, which was stored at 20 ° C. and 60% RH for 1 week at 50 ° C. and 60 ° C.
An accelerated weather resistance test was carried out using a sunshine weatherometer by using the one aged for 1 week under the condition of% RH.

Comparative Example 2 50 parts of polybutadiene having hydroxyl groups at both ends used in Example 3, 40 parts of fatty acid-treated calcium carbonate, 10 parts of titanium oxide, 5 parts of xylene, phenolic antioxidant, benzotriazole ultraviolet absorber , After mixing 1 part each of the hindered amine light stabilizers,
Mix well with 3 paint rolls. Further, 6.0 parts of hexamethylene diisocyanate and 1 part of dibutyltin dilaurate were added and mixed well to prepare a 3 mm thick sheet, which was kept at 20 ° C. and 60% RH for 1 week, and 50 ° C. and 60% RH.
An accelerated weather resistance test was carried out using a sunshine weatherometer using the one that had been aged under the conditions for one week.

As a result, the polymer of Comparative Example 2 was cracked and the polymer was melted after 1000 hours, but the polymer of Example 3 had no abnormality even after 2000 hours.

Reference Example 1 ClC (CH ₃ ) ₂ C ₆ H ₄
Living cationic polymerization of isobutylene was carried out by using C (CH ₃ ) ₂ Cl and BCl ₃ as initiators to obtain liquid chlorinated polyisobutylene having a number average molecular weight of 4000, and the end was modified with a hydroxyl group by hydrolysis with sodium hydroxide. . Further, after the terminal was alcoholated with sodium metal and reacted with allyl chloride to allyloxylate, the by-produced salt was removed to obtain terminal allyloxylated polyisobutylene.

Example 4 Under a nitrogen atmosphere, 60 parts of terminal allyloxylated polyisobutylene obtained in Reference Example 1, 40 parts of chlorotrifluoroethylene, 30 parts of cyclohexyl vinyl ether, 10 parts of vinylmethyldimethoxysilane.
Parts, 3 parts mercaptopropylmethyldimethoxysilane,
30 parts of methanol, 2 parts of Kyowaad 500 manufactured by Kyowa Chemical Co., Ltd., and 2 parts of tert-butyl perisobutyrate were charged into an autoclave and reacted at 65 ° C. for 10 hours.

After filtering the obtained product, methanol was removed and the yield was measured to be 135 parts. To 50 parts of the obtained polymer, 5 parts of liquid paraffin, 40 parts of fatty acid-treated calcium carbonate, 10 parts of ground calcium carbonate
Parts, 5 parts of titanium oxide, 2 parts of a phenolic antioxidant, 1 part of a benzotriazole ultraviolet absorber and 1 part of a hindered amine light stabilizer were mixed, and then well mixed with three paint rolls. Furthermore, Shin-Etsu Silicone KBM9
1 part of 03 and 1 part of # 918 manufactured by Sankyo Kikai Kagaku Co. were added, and an H-type test piece was prepared using a glass according to JIS-A5758, which was well kneaded. Using the obtained test body, an accelerated weather resistance test was conducted for 2000 hours with a sunshine weatherometer.

Comparative Example 3 The terminal of the polyisobutylene obtained in Reference Example 1 was reacted with methyldimethoxysilane in the presence of a platinum catalyst to synthesize polyisobutylene containing a terminal dimethoxysilyl group. Liquid paraffin 5 parts, fatty acid-treated calcium carbonate 40 parts, heavy calcium carbonate 10 parts, titanium oxide 5 parts, phenolic antioxidant 2 parts, benzotriazole ultraviolet absorber, hindered amine to 50 parts of the obtained polymer. After mixing 1 part of each of the light stabilizers, they were thoroughly mixed with a three-roll paint roll. In addition, 1 part of KBM903 manufactured by Shin-Etsu Silicone Co., Ltd. and 1 part of # 918 manufactured by Sankyo Machine Chemical Co., Ltd. were added and well kneaded.
An H-type test body was prepared using a glass based on A5758 as a test body. Using the obtained test body, an accelerated weather resistance test was conducted for 2000 hours with a sunshine weatherometer.

As a result, in Comparative Example 3, a tensile adhesion test was conducted after the test, but the fracture state was interface fracture, and the elongation retention ratio to the initial stage was 30%. On the other hand, in the case of Example 4, the fracture state was cohesive failure, and the elongation retention ratio to the initial stage was 60%.

(Example 5) 80 parts of silanol-terminated polydimethylsiloxane having a molecular weight of 6000 and having an average of 1.5 vinyl groups in the molecule, 20 parts of hexafluoropropylene, 5 parts of perfluoropropyl vinyl ether, and vinyl pivalate. 8 parts, 50 parts of Freon 113, 10 parts of methanol and 3 parts of tert-butyl perpivalate were charged into an autoclave, reacted for 15 hours at 50 ° C., the solvent was removed, and the yield was measured to be 110 parts.

After thoroughly kneading 70 parts of the obtained polymer, 30 parts of heavy calcium carbonate and 10 parts of aerosil with a paint roll, 2 parts of dimethyldi (methylethylketoxime) silane and 3 parts of vinyltri (methylethylketoxime) silane were mixed. Was added to obtain a composition. And 8 cm
Marbles of 8 cm x 8 cm were placed on a 18 cm x 18 cm square plywood board to form a cross-shaped space with a width of 2 cm. After filling the cross-shaped space with the composition, 20 ° C 60
It was aged for 7 days under the conditions of% RH and for 7 days under the conditions of 50 ° C. and 60% RH. An exposure test was conducted on this sample at an angle of 45 ° on the south side. In addition, after making two sheets of 5 cm x 10 cm square and 5 mm thick, they were cured under the same conditions, one of them was coated with a fluororesin paint (Bonflon, a product name of Asahi Glass Coat And Resin Co., Ltd.), cured for one week, and then a cross-cut test. Do 1
The sunshine weatherometer test (WOM test)
Was performed. The results are shown in Table 1.

(Comparative Example 4) 70 parts of polydimethylsiloxane having a molecular weight of 6000 and having silanol groups at both ends, 30 parts of heavy calcium carbonate, and 10 parts of aerosil were sufficiently kneaded with three paint rolls, and then dimethyldi (methylethylketoxime) silane. The same test as in Example 5 was carried out using 2 parts and 3 parts of vinyltri (methylethylketoxime) silane added. The results are shown in Table 1.

[0125]

[Table 1]

Reference Example 2 50 parts of butyl acrylate,
50 parts of ethyl acrylate, 5 parts of methacryloxypropylmethyldimethoxysilane, 5 allyl methacrylate
Part, and 3 parts of azobisisobutyronitrile are gradually fed to a flask with a reflux condenser heated and stirred at 50 ° C. in a nitrogen atmosphere at a temperature of 80 ° C. over a period of 5 hours. 100 ° C 1h
A reaction with stirring was carried out to obtain a polymer varnish. The solid content concentration of the obtained varnish was 62%.

Example 6 80 parts of the varnish of Reference Example 2 and 50 parts of tetrafluoroethylene, 20 parts of a vinyl ester of a carboxylic acid having 9 to 10 carbon atoms and a small number of branched chains (trade name: Veova 9 manufactured by Shell Co.), azo 5 parts of bisisobutyronitrile was charged into an autoclave and reacted at 60 ° C. for 20 hours. To 100 parts of the obtained varnish, 100 parts of heavy calcium carbonate, 15 parts of titanium oxide, 1 part of each of a phenolic antioxidant, an ultraviolet absorber and a light stabilizer were thoroughly kneaded with a paint roll, and further dibutyltin dilaurate was added. Add 1 part and after mixing, make a 4mm thick sheet, 50 ℃ 60%
It was cured for 2 weeks under RH conditions. Using this sheet, JIS
The tensile physical properties of No. 3 dumbbell according to K6301 were measured and found to be 150% modulus 3 kg / cm ² ,
The elongation was 200%. This was subjected to a sunshine weatherometer test, but no abnormality was found even after 3000 hours had passed.

Comparative Example 5 To the varnish of Reference Example 2, 0.5 mg of a solution of chloroplatinic acid in 100 times the amount of isopropanol and 3 parts of dimethoxymethylsilane were added, and 9
130 parts of the product reacted for 2 hours at 0 ° C., 100 parts of heavy calcium carbonate, 15 parts of titanium oxide, 1 part of each of a phenolic antioxidant, an ultraviolet absorber and a light stabilizer are sufficiently kneaded with three paint rolls, Further, 1 part of dibutyltin dilaurate was added, and after mixing, a 5 mm thick sheet was prepared, and the temperature was 50 ° C. 60
It was aged for 2 weeks under the condition of% RH. Using this sheet, JI
Tensile physical properties of No. 3 dumbbell according to S-K6301 were measured and found to be 150% modulus 4 kg / cm.
² , the elongation was 160%. When this product was subjected to a sunshine weatherometer test, cracks had occurred on the surface after 3000 hours.

Reference Example 3 Adipic acid and ethylene glycol were subjected to condensation polymerization using glycerol monoallyl ether as an initiator to obtain a polyester polyol having a hydroxyl group terminal molecular weight of 2000.

(Example 7) Polyol 50 of Reference Example 3
Parts, tetrafluoroethylene 60 parts, propylene 15
Parts, 30 parts of Freon 113, and 4 parts of isobutyryl peroxide were charged in an autoclave, and reacted with stirring at 40 ° C. for 24 hours. The solvent was removed from the obtained reaction mixture to obtain a liquid polymer. The yield was 100 parts. To 100 parts of this polymer, 10 parts of hexamethylene diisocyanate,
After adding 0.01 part of a phenolic antioxidant and degassing with stirring, a 3 mm thick sheet was prepared and cured at 80 ° C. for 2 days and at 50 ° C. for 5 days.

The obtained sheet was light yellow and transparent and was subjected to a tensile test to find that the 300% modulus was 30 kg /
It was cm ² and the elongation was 500%. This sheet was immersed in warm water at 80 ° C. for 1 week and stored at room temperature for 1 day, and there was almost no cloudiness.
%, And the elongation retention rate was 105%.

(Example 8) Polymer 1 obtained in Example 7
8 parts of γ-isocyanatopropylmethyldimethoxysilane hydroxybutyl vinyl ether was added to 00 parts,
The reaction was carried out at 80 ° C for 5 hours. 0.01 parts of a phenolic antioxidant, 0.75 parts of tin octylate were added to the obtained reaction product,
Add 0.25 parts of laurylamine, and after degassing with stirring, 3 mm
Create a thick sheet, 20 ℃ 60% RH 7 days 50 ℃ 60%
I was cured for 7 days at RH. The obtained sheet was light yellow and transparent. When a tensile test was performed, the 100% modulus was 20 kg / cm ² , and the elongation was 300%. This sheet was soaked in warm water at 80 ° C. for 1 week and stored at room temperature for another day. There was almost no cloudiness, and a tensile test showed that it had a modulus retention of 90% and an elongation retention of 90%.

Comparative Example 6 Polyol 100 of Reference Example 3
Parts, trimethylolpropane 1 part, hexamethylene diisocyanate 20 parts, phenolic antioxidant 0.01
Part is added, and after degassing with stirring, a 3 mm thick sheet is prepared and 80 ° C.
It was cured for 2 days at 50 ° C. for 5 days.

The obtained sheet was light yellow and transparent, and when subjected to a tensile test, the 300% modulus was 25 kg /
It was cm ² and the elongation was 470%. This sheet was soaked in warm water at 80 ° C. for 1 week and then stored at room temperature for another day. The white turbidity was severe, and a modulus test showed that the modulus retention was 50.
%, And the elongation retention rate was 60%.

[0135]

EFFECT OF THE INVENTION A polymer having elasticity and excellent weather resistance and stain resistance can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shunichi Kodama 3-474-2 Tsukakoshi, Sachi-ku, Kawasaki City, Kanagawa Prefecture Asahi Glass Co., Ltd. Tamagawa Branch Office

Claims (9)

[Claims] 1. A method for producing a fluoropolymer, which comprises polymerizing a polymerizable monomer containing a fluoroolefin as a main component in the presence of an organic elastic polymer having no long chain polyoxyalkylene as a main chain. . 2. The method according to claim 1, wherein the organic elastic polymer is a polymer having at least one active site in the molecule capable of copolymerizing with a polymerizable monomer containing a fluoroolefin as a main component. 3. The production method according to claim 2, wherein the active point which can be copolymerized with the polymerizable monomer containing fluoroolefin as a main component is an unsaturated group, a chain transfer point or a radical initiation point. 4. The production method according to claim 1, wherein the organic elastic polymer is a polymer having a curable site. 5. The method according to claim 1, wherein at least a part of the polymerizable monomer containing fluoroolefin as a main component is a polymerizable monomer having a curable site. 6. A polymerization initiator having a curable site and / or a chain transfer agent having a curable site is used when polymerizing a polymerizable monomer containing a fluoroolefin as a main component. Item 6. A manufacturing method according to any one of Items 1 to 5. 7. The curable site is at least one group selected from a hydrolyzable silyl group, a hydroxyl group, an isocyanate group, an amino group, an epoxy group, a mercapto group and an unsaturated group. Manufacturing method. 8. The organic elastic polymer is a polymer selected from a polysulfide polymer, an olefin polymer, an acrylic polymer, a polysiloxane polymer, and a polyester polymer. One of the manufacturing method of. 9. A curable composition comprising the fluoropolymer produced by the production method according to any one of claims 1 to 8.