JP2003192749A - Liquid polymer composition having double bonds and preparation method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing liquid copolymer composition having double bonds excellent in antifouling property, water and oil repellency, chemical resistance and weather resistance where the composition is one-pack type which can be cured by light or heat. <P>SOLUTION: The liquid polymer composition having double bonds is a liquid composition where a polymer having double bonds and a reactive diluent coexist but a gelled component is not included. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer liquid containing a double bond containing no gelling component, in which a polymer <α> containing a double bond and a reactive diluent <β> coexist. The present invention relates to a composition and a method for producing a polymer liquid composition containing the double bond. Further, the present invention is characterized in that it can be cured by light or heat with one liquid when forming a coating film, and a fluorine-containing copolymer <αf> containing a double bond and a reactive diluent <β. The invention relates to a fluorine-containing copolymer composition containing a double bond consisting of> and a method for producing the same.

[0002]

2. Description of the Related Art Solvent-soluble fluororesin paints are generally obtained by copolymerizing hydroxyalkyl vinyl ether and fluoroolefin, and if necessary, alkyl vinyl ether, alkyl vinyl ester and the like. A coating material based on such a fluorine-containing copolymer has a hydrocarbon monomer content of 50 to obtain solubility in a general organic solvent.
It contains about%. As a result, the fluorine content in the fluororesin decreases, and the water- and oil-repellency and stain resistance required for the fluororesin cannot be sufficiently obtained. On the other hand, by mixing a small amount of an organic silicon compound such as silicone oil with the fluorine-containing copolymer, the water / oil repellency is improved. However, it is difficult to maintain the water / oil repellency in the long term. Furthermore, depending on the application, silicone oil cannot be used because it bleeds out from the surface of the coating film. Furthermore, Japanese Patent Laid-Open No.
In No. -17535, a copolymer of a fluorine-containing monomer and a monomer containing a silyl group is examined. However, since the side chain of the silyl group is short, stain resistance, water repellency, oil repellency, etc. This is a situation in which the coating film characteristics are not sufficiently obtained.

On the other hand, the hydroxyl group-containing fluorine-containing copolymer can be cured at room temperature, but it is necessary to mix two liquids of a main agent and a curing agent immediately before use. This is not convenient in terms of work, and it is necessary to pay attention to the pot life.

Up to now, the present inventors have conducted extensive studies to solve the above problems, and as a polymerized unit, 15 to 85 mol% of a fluoroolefin, represented by the general formula (1) or (2), is used. The reactive silicone oil shown is 0.
001 to 30 mol% and 1 to 50 mol% of the hydroxyl group-containing unsaturated ether represented by the general formula (3) as essential constituent components, and if necessary, copolymerization with any other copolymerizable monomer. Hydroxyl group-containing fluorocopolymer obtained by polymerization [A]
And a fluorine-containing copolymer containing a double bond, which is produced by the reaction of unsaturated isocyanate [B] and is excellent in long-term water and oil repellency, antifouling property, repetitive stain removal property, chemical resistance, and weather resistance. A polymer was found (Japanese Patent Application No. 2000-1048).
37).

R ^1- [Si (CH ₃ ) _2- O] _n -Si (CH ₃ ) _2- R ² (1) (wherein R ¹ is an alkyl group having 1 to 6 carbon atoms or
_{(CH 2) r -OOC (CH} 3) C = CH 2 or - (C
H _{2) r} -OOCHC = CH ₂ or -CH = CH ₂
Indicates. R ² is _{- (CH 2) r -OOC (} CH 3) C = CH
₂ or - indicates a _{(CH 2) r -OOCHC = CH} 2 or -CH = CH _2. n is an integer from 1 to 420, r is 1
Indicates an integer of ˜6. ^{) R 2 -Si [OSi (CH} 3) 3] 3 (2) CH 2 = CH (CH 2) m -O-R 3 -OH (3) ( wherein, ^{R 3} is alkylene of 1 to 6 carbon atoms Group or cyclohexyl group, m represents an integer of 0 to 10.) However, the varnish and the coating material containing the above-mentioned fluorine-containing copolymer contain an organic solvent in the composition. Therefore, a large amount of organic solvent volatilizes at the time of application, which is not suitable for VOC (volatile organic compound) measures, and improvement has been demanded. Further, since it contains a large amount of organic solvent, thick coating cannot be performed and workability is poor.

In order to solve these problems, a study was made to replace the organic solvent in the composition with a reactive diluent, but a double bond was contained during the operation of removing a part or all of the organic solvent. A cross-linking reaction between the polymer and the reactive diluent occurs to cause gelation, making it difficult to obtain a liquid composition in which the organic solvent is replaced.

[0007]

SUMMARY OF THE INVENTION One of the objects of the present invention is to provide a polymer liquid composition and a method for producing the same for solving the above problems. Specifically, a polymer <α> containing an unsaturated double bond curable by light or heat with one liquid and a reactive diluent <β> containing a similar unsaturated double bond coexist. And a polymer liquid composition containing a double bond without gelling by mixing the polymer and the reactive diluent. And a liquid mixture of a polymer solution containing an organic solvent and containing a double bond and a reactive diluent, wherein a part or all of the organic solvent is removed and a double bond containing a double bond is removed. It is to provide a method for producing a polymer liquid composition without causing a cross-linking reaction between the coalesced product and the reactive diluent.

Another object of the present invention is to provide a fluorocopolymer liquid composition which solves the above problems. In other words, it contains a novel double bond that is excellent in water and oil repellency, antifouling property, repetitive stain removal property, chemical resistance, and weather resistance when formed into a coating film and can be cured by light or heat with one liquid. And the compatibility with the reactive diluent <β> is also good, the fluorine-containing copolymer <αf>
And a reactive diluent <β>, and the organic solvent content is 10
The present invention relates to a fluorine-containing copolymer liquid composition containing a double bond, which is less than or equal to% by weight, and a method for producing the same.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a polymer <α> containing a double bond containing a large amount of an organic solvent is obtained. From a liquid mixture consisting of a reactive diluent <β>, under the conditions for inhibiting or suppressing the polymerization of the liquid mixture, by removing a part or all of the organic solvent, without causing gelation, It was found that a polymer liquid composition containing a double bond can be produced. As a specific means for inhibiting or suppressing the polymerization, it is usual to use a polymerization inhibitor. However, when the amount of the organic solvent is reduced or removed, <α> and <β> are crosslinked. It was easy to react and cause gelation, and it was difficult to retain and store the liquid mixture in the coexisting state.

However, in this study, it was possible to obtain a particularly preferable result that gelation does not occur by using a polymerization inhibitor and introducing oxygen gas. It was also found that it is effective for safety to use an oxygen-containing gas of 10 to 30 vol% diluted with an inert gas such as nitrogen.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer <α> containing a double bond used in the present invention is not limited as long as it is soluble in an organic solvent and contains a double bond in the composition. The polymer or the copolymer can be used without particular limitation. Specifically, olefins such as ethylene, propylene, isobutylene, and butadiene, haloolefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and hexafluoro-1,3-butadiene, ethyl vinyl ether, isopropyl vinyl ether. , Alkyl vinyl ethers such as cyclohexyl vinyl ether and hydroxybutyl vinyl ether, alkyl allyl ethers such as ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, ethylene glycol monoallyl ether and glycerol-α-monoallyl ether, methyl acrylate, 2 , 2,2-trifluoroethyl acrylate, dicyclopentanyl acrylate, 2-hydroxyethyl acrylate and 2-
Acrylic esters such as hydroxybutyl acrylate, methyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, dicyclopentanyl methacrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate Examples thereof include unsaturated carboxylic acids such as methacrylic acid esters, acrylic acid and methacrylic acid.

Of these, a halogen-containing copolymer having a haloolefin as a constituent unit is preferable. That is, a chlorine-containing olefin, which contains a fluorine-containing olefin, a copolymer of a chlorine-containing olefin and a monomer copolymerizable with the chlorine-containing olefin,
Alternatively, a copolymer of a fluorinated olefin and a monomer copolymerizable with the fluorinated olefin can be used.

Particularly, the fluorine-containing olefin is an olefin having one or more fluorine atoms in the molecule, and for example, vinylidene fluoride, tetrafluoroethylene, chlorofluoroethylene, hexafluoropropylene and the like are preferable. Each of these fluorine-containing olefins may be constituted alone or in combination of two or more kinds.

As a method for introducing a double bond into a polymer such as a saturated hydrocarbon containing a hydroxyl group, a method of reacting an unsaturated isocyanate or an unsaturated carboxylic acid is known. If used, a double bond can be easily introduced.

The molecular weight of the polymer <α> containing a double bond can be changed according to the use, but it is usually about 1,000 to 100,000 in number average molecular weight. When aiming at low viscosity, it is possible to prepare an oligomer having a number average molecular weight of 1,000 or less.

As a result of intensive studies, the present inventors have found that a fluoroolefin, a reactive silicone oil represented by the general formula (1) or (2), and a hydroxyl group-containing unsaturated monomer are used as essential constituents. Produced by introducing a double bond into the fluorocopolymer by reacting the fluorocopolymer containing [Af] with the unsaturated isocyanate [B], as proposed in Japanese Patent Application No. 2000-104837. Fluorine-containing copolymer <αf> containing double bond
Has been found to have properties such as long-term water and oil repellency, antifouling properties, and repetitive stain removal properties. However, by combining with a reactive diluent <β>, these properties can be further improved. Found to improve.

In addition, the double bond-containing fluorine-containing copolymer liquid composition comprising the double bond-containing fluorine-containing copolymer <αf> and the reactive diluent <β> is Since the composition contains 10% by weight or less of the organic solvent, it is suitable for recent VOC measures and energy saving, and has a relatively low viscosity, so the work such as a mixing process and a painting work for forming a paint. We found that it helps improve the environment.

R ^1- [Si (CH ₃ ) _2- O] _n -Si (CH ₃ ) _2- R ² (1) (wherein R ¹ is an alkyl group having 1 to 6 carbon atoms or-
_{(CH 2) r -OOC (CH} 3) C = CH 2 or - (C
H _{2) r} -OOCHC = CH ₂ or -CH = CH ₂
Indicates. R ² is _{- (CH 2) r -OOC (} CH 3) C = CH
₂ or - indicates a _{(CH 2) r -OOCHC = CH} 2 or -CH = CH _2. n is an integer from 1 to 420, r is 1
Indicates an integer of ˜6. ^{) R 2 -Si [OSi (CH} 3) 3] 3 (2) That is, the present invention provides, as polymerized units, fluoroolefin 1
5 to 85 mol%, 0.001 to 30 mol% of the reactive silicone oil represented by the general formula (1) or (2), and 1 to 50 mol% of the hydroxyl group-containing unsaturated monomer are essential constituent components, If necessary, a hydroxyl group-containing fluorocopolymer [Af] obtained by copolymerization with another copolymerizable monomer, and a double bond-containing copolymer produced by the reaction of unsaturated isocyanate [B]. It also provides a fluorine-containing copolymer liquid composition containing a double bond in which a fluorine copolymer <αf> and a reactive diluent <β> are combined.

The coating film of such a fluorine-containing copolymer liquid composition has the effects of being excellent in long-term water and oil repellency, antifouling property, repetitive stain removal property, chemical resistance and weather resistance. .

In addition to the polymer units of [Af], the hydroxyl group-containing fluorocopolymer [Af] is one or more polymer units selected from alkyl vinyl ether, alkyl allyl ether, methacrylic acid ester and acrylic acid ester. And a fluorine-containing copolymer <αf> containing a double bond produced by a reaction with the unsaturated isocyanate [B].

Further, the double bond-containing fluorocopolymer liquid composition comprising the double bond-containing fluorocopolymer <αf> and the reactive diluent <β> is in the composition thereof. Since the organic solvent contained in is less than 10% by weight,
It has the effect of contributing to VOC reduction and work environment improvement, and is suitable for recent VOC measures and energy saving.

The hydroxyl group-containing fluorocopolymer of the present invention [A
In f], the fluoroolefin is an olefin having one or more fluorine atoms in the molecule, and for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like are preferable. These fluoroolefins may be used alone or in combination of two or more.

The reactive silicone oil represented by the general formula (1) or (2) is methacryl-modified polydimethylsiloxane at one end, acrylic-modified polydimethylsiloxane at one end, and vinyl-modified at one end. Polydimethylsiloxane, methacryl-modified polydimethylsiloxane at both ends, vinyl-modified polydimethylsiloxane at both ends, and the like are preferable. These reactive silicone oils may be used alone or in combination of two or more. The number average molecular weight of these reactive silicone oils is 200 to 30,000.
0 is preferred.

As the reactive silicone oil, silicone oils represented by the following formulas (4), (5), (6), (7) and (8) are particularly preferable.

CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si (CH ₃ ) _2- [O-Si (CH ₃ ) ₂ ] _p -R ⁴ (4) (wherein R ⁴ is Indicates an alkyl group having 1 to 6 carbon atoms.
Represents an integer of 1 to 250. _{) CH 2 = CH-COO-} C 3 H 6 -Si (CH 3) 2 - [O-Si (CH 3) 2] s -R 5 (5) (Here, R ⁵ represents an alkyl group having 1 to 6 carbon atoms.
Represents an integer of 1 to 250. ^{_{) R 6 -C 3 H 6 -Si}} (CH 3) 2 - [O-Si (CH 3) 2] q -C 3 H 6 -R 6 (6) (Here, R ⁶ represents —OOC (CH ₃ ) C═CH ₂ or —OOCHC═CH _2, and q represents an integer of 1 to 250.) CH ₂ ═C (CH ₃ ) —COO _{-C 3 H 6 -Si [O-} Si (CH 3) 3] 3 (7) CH 2 = CH-Si (CH 3) 2 - [O-Si (CH 3) 2] t -R 7 (8) (wherein R ⁷ is an alkyl group having 1 to 6 carbon atoms or-
CH = CH ₂ is shown. t shows the integer of 1-250. ) Specific examples of the hydroxyl group-containing unsaturated monomer include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, ethylene glycol monoallyl ether, cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, and 3-allyloxy-.
1,2-Propanediol, glycerol-α-monoallyl ether, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like are preferable. These hydroxyl group-containing unsaturated monomers may be used alone or in combination of one or more.

Specific examples of the alkyl vinyl ether include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and octadecyl vinyl ether.

Specific examples of the alkyl allyl ether include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether and the like.

Specific examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate and the like.

Specific examples of the methacrylic acid ester include:
Examples thereof include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like.

The hydroxyl group-containing fluorine-containing copolymer of the present invention [A
f] is capable of forming a coating film having excellent water and oil repellency, antifouling property, repetitive stain removal property, chemical resistance, and weather resistance for a long period of time. Other copolymerizable monomer units may be contained within a range not exceeding 20 mol% according to the above.

Examples of the copolymerizable monomer include olefins such as ethylene and propylene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl n-butyrate, vinyl isobutyrate and vinyl propionate. Examples thereof include esters of alkanecarboxylic acid and vinyl alcohol.

The hydroxyl group-containing fluorocopolymer [Af]
In the case where the polymerized unit fluoroolefin is less than 15 mol%, sufficient stain resistance cannot be obtained when used as a paint base, which is not preferable. On the other hand, if it is more than 85 mol%, the solubility in various solvents decreases, which is not preferable. More preferably, it is 30 to 80 mol%.

When the proportion of the reactive silicone oil represented by the general formula (1) or (2) is less than 0.001 mol%, sufficient water / oil repellency and antifouling property cannot be obtained for a long time, which is preferable. Absent. If it is more than 30 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable.
Further, when polymerizing a polymer having a large molecular weight (n = 200 to 420), the ratio cannot be increased in production. For these reasons, the ratio is more preferably 0.005 to
25 mol%.

When the amount of the hydroxyl group-containing unsaturated monomer is less than 1 mol%, the amount of double bonds is reduced, sufficient curing does not occur, and the chemical resistance and solvent resistance of the cured coating film are reduced, which is not preferable. . On the other hand, when it is more than 50 mol%, the fluorine content in the fluorinated copolymer is reduced, and sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable.

The hydroxyl group-containing fluorocopolymer [Af]
Can be produced by copolymerizing a predetermined mixture of monomers with a polymerization initiator.

As the polymerization initiator in the hydroxyl group-containing fluorocopolymer [Af], an oil-soluble one or a water-soluble one is appropriately used depending on the polymerization mode and the kind of solvent used as desired.

Examples of the oil-soluble initiator include peroxyester type peroxides such as t-butylperoxyisobutyrate and t-butylperoxyacetate, diisopropylperoxydicarbonate and dinormal propylperoxydicarbonate. Dialkyl peroxydicarbonate, benzoyl peroxide, azobisisobutyronitrile and the like are used.

As the water-soluble initiator, for example, a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator composed of a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and further, A small amount of iron, ferrous salt, silver nitrate, or other inorganic initiators or succinic acid peroxides, diglutaric acid peroxides, dibasic acid organic initiators such as monosuccinic acid peroxides are used. To be

The amount of these polymerization initiators to be used is appropriately selected depending on the kind, the conditions of the copolymerization reaction, etc., but 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the total amount of the monomers usually used. It is selected in the range of 0.05 to 2% by weight.

There is no particular limitation on the polymerization method for the hydroxyl group-containing fluorocopolymer [Af], and for example, bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method and the like can be used, but methyl ethyl ketone, etc. As ketones, acetic acid esters such as butyl acetate, aromatic hydrocarbons such as xylene, ethylbenzene, and amylbenzene, alcohols such as t-butanol, and halogenated saturated hydrocarbons having at least one fluorine atom as a solvent. The solution polymerization method and the emulsion polymerization method in an aqueous solvent are preferable.

The hydroxyl group-containing fluorocopolymer of the present invention [A
Particularly preferred solvents for obtaining f] by the solution polymerization method include ethyl acetate, butyl acetate, xylene, toluene, Solvesso (registered trademark), methyl ethyl ketone, methyl isobutyl ketone, methanol and butanol. These solvents can be used alone or in combination of two or more.

In the case of copolymerization in an aqueous solvent (emulsion polymerization method, suspension polymerization method), a suspending agent or an emulsifying agent is usually used as a dispersion stabilizer, and a basic buffer is added to carry out the polymerization. It is desirable that the pH value of the reaction solution is 4 or more, preferably 6 or more.

The reaction temperature in each of the copolymerization reactions is usually in the range of -30 ° C to 150 ° C and is appropriately selected according to the kind of the polymerization initiator or the polymerization medium. For example, when the copolymerization is carried out in a solvent, it is usually selected in the range of 0 ° C to 100 ° C, preferably 10 ° C to 90 ° C. The reaction pressure is not particularly limited, but is usually 0.1 to 10 MPa,
It is preferably selected in the range of 0.1 to 5 MPa. Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.

The reaction between the hydroxyl group-containing fluorine-containing copolymer [Af] and the unsaturated isocyanate [B] is not particularly limited, but it may be reacted with a solution of the hydroxyl group-containing fluorine-containing copolymer in a solvent. It is preferable that the saturated isocyanate is added dropwise and the stirring is performed.

The reaction ratio between the hydroxyl group-containing fluorocopolymer [Af] and the unsaturated isocyanate [B] is selected in the range of 0.1 to 1 in terms of isocyanate group / hydroxyl group ratio.

When the ratio of isocyanate group / hydroxyl group is less than 0.1, the amount of double bonds is reduced and sufficient curing does not occur, and the chemical resistance and solvent resistance of the cured coating film are reduced, which is not preferable. On the other hand, when it is more than 1, unreacted unsaturated isocyanate remains and there is a possibility that the coating film characteristics are deteriorated.

Specific examples of unsaturated isocyanates include:
2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, 4-isocyanate butyl acrylate, reaction product of 1 mol of unsaturated monoalcohol and 1 mol of diisocyanate compound, unsaturated monoalcohol 2
A reaction product of 1 mol of the triisocyanate compound and 1 mol of the triisocyanate compound may be mentioned. Specific examples of the unsaturated monoalcohol include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxybutyl methacrylate, hydroxybutyl acrylate and allyl alcohol.

Specific examples of the diisocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and dicyclohexylmethane diisocyanate. Specific examples of the triisocyanate compound include isocyanurate-bonded HDI, isocyanurate-bonded IPDI, TMP-modified HDI, TMP-modified IPDI and the like.

The reaction temperature at this time is 10 to 130.
C., preferably in the range of 25 to 85.degree. 10 ° C
If it is lower than 130 ° C, the reaction does not proceed sufficiently, and if it is higher than 130 ° C, gelation tends to occur during the reaction, which is not preferable.

The solvent used in the reaction is preferably ketones such as methyl ethyl ketone, acetic acid esters such as butyl acetate, aromatic hydrocarbons such as xylene. Since unsaturated isocyanate is used, if a solvent having a hydroxyl group such as water or alcohol is used, the reaction between the hydroxyl group-containing fluorocopolymer [Af] and the unsaturated isocyanate [B] does not proceed. When a solvent having these hydroxyl groups is used, the hydroxyl group-containing fluorocopolymer [A
Before reacting f] with the unsaturated isocyanate [B], it is necessary to remove the solvent having a hydroxyl group in advance. When the hydroxyl group-containing fluorine-containing copolymer [Af] has a high hydroxyl value, it is necessary to use an alcohol solvent, and therefore it is required to remove such a solvent before the reaction with the unsaturated isocyanate. Of.

As the reaction catalyst, it is preferable to use an organic tin compound such as dibutyltin dilaurate.

The reactive diluent <β> contains a functional group (such as a double bond) capable of being crosslinked by light or heat in the molecule, and is capable of itself performing a crosslinking reaction. Becomes At the same time, like the solvent, the fluorinated copolymer can be brought into a solution state and has a role of replacing the solvent. Therefore, as compared with the case of using the organic solvent, there is an advantage that the amount of the organic solvent discharged into the atmosphere can be reduced. Furthermore, since the reactive diluent has a low viscosity, it is possible to reduce the viscosity of the fluorocopolymer composition and improve the workability.
As such a reactive diluent <β>, specifically,
One or more selected from the group of the following acrylate compounds, methacrylate compounds and ethers can be mentioned.

Examples of monofunctional acrylates include isobutyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate. ) Acrylate, 2-methoxyethyl (meth) acrylate,
3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Methoxytripropylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-acryloyloxyethyl 2-
Hydroxypropyl phthalate, 2-hydroxy-3-
Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, β-carboxyethyl (meth) acrylate, isobornyl (meth)
Examples thereof include acrylate, oxyethylated phenol acrylate, phenol EO-modified (meth) acrylate, paracumylphenol EO-modified (meth) acrylate, nonylphenol EO-modified (meth) acrylate and the like.

As the bifunctional acrylate, 1,
6-hexanediol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene Examples thereof include glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol A EO-modified di (meth) acrylate, and isocyanuric acid EO-modified di (meth) acrylate.

As trifunctional or higher functional acrylates, pentaerythritol tri (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate , Glycerin PO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth)
Examples thereof include acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

Further, epoxy (meth) acrylates such as bisphenol A-modified epoxy (meth) acrylate, aliphatic / aromatic epoxy (meth) acrylate, novolac epoxy (meth) acrylate and the like can also be mentioned.

It is also possible to use glycidyl ethers as the other reactive diluent <β>, for example,
Examples thereof include polypropylene glycol diglycidyl ether, butyl glycidyl ether, 1,6-hexanediol diglycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, etc., but the viscosity is slightly higher than that of the above-mentioned (meth) acrylate. From the viewpoint of workability, the above-mentioned (meth) acrylate is preferable.

These reactive diluents <β> may be used alone or in combination of two or more.

Polymer <α> containing a double bond of the present invention
In producing a polymer liquid composition containing no gelling component, in which the organic solvent and the reactive diluent <β> coexist, removal of the organic solvent is performed by using a device such as an evaporator, a flask, an autoclave, and a thin film distiller. To do.

As a method for producing the polymer liquid composition containing a double bond, a polymer containing a double bond <
α> and the reactive diluent <β> are mixed in a liquid state under the conditions that inhibit or suppress the polymerization of the both, and they are allowed to coexist.
A method of forming a liquid composition without causing gelation of α> and <β> can be mentioned. This liquid state is one of the characteristics, and particularly <α> exists as a polymer solution in combination with an organic solvent. From a liquid mixture consisting of such a polymer solution and a reactive diluent <β>,
By removing a part or all of the above organic solvent under the condition of inhibiting or suppressing the polymerization of the liquid mixture, <α> and <β> are allowed to coexist as a liquid mixture without causing a cross-linking reaction. A polymer liquid composition containing a heavy bond can be used. In order to inhibit or suppress the polymerization, a method of using oxygen gas or using oxygen gas in combination with a polymerization inhibitor can be mentioned.

More specifically, a polymer solution containing an organic solvent and containing a double bond, that is, a <α> solution containing an organic solvent and <β> are mixed in the presence of a polymerization inhibitor, A method of coexisting <α> and <β> as a liquid composition by removing part or all of the organic solvent while introducing (blowing) oxygen gas into the liquid mixture is adopted.

As a method for removing the organic solvent, a temperature of 0 is used.
The method by distillation operation is used at ˜150 ° C. under normal pressure or reduced pressure.

The amount of the organic solvent in the <α> solution containing the organic solvent is not particularly limited, but the polymer containing the double bond is 9 to 81% by weight, and the reactive diluent is 9 to 91% by weight. % And the organic solvent is 0 to 10% by weight, to prepare a polymer liquid composition containing a double bond, the amount of the organic solvent is more than 10% by weight and the amount of the double solvent is less than 90% by weight. It is necessary to start a liquid mixture consisting of a polymer solution containing a bond-containing polymer and a reactive diluent, and to remove part or all of the organic solvent by the above-mentioned method.

Further, as a method for producing the above-mentioned fluorine-containing copolymer liquid composition containing a double bond, a fluorine-containing copolymer containing a double bond <soluble in an organic solvent <
αf> and the reactive diluent <β> are removed in the presence of a polymerization inhibitor under the conditions of a temperature of 0 to 150 ° C. and atmospheric pressure or reduced pressure to remove a part or all of the organic solvent. I do. Soluble in organic solvent due to polymerization inhibitor <α
It inhibits or suppresses the polymerization of both f> and <β>.

As the polymerization inhibitor, a general-purpose polymerization inhibitor can be used. For example, hydroquinone (HQ), hydroquinone monomethyl ether (MEH
Q) etc. are mentioned. These polymerization inhibitors may be used alone or in combination of two or more.

Further, in the present invention, oxygen gas is used to inhibit or suppress the polymerization, thereby inhibiting or suppressing the crosslinking reaction between the fluorine-containing copolymer <αf> and the reactive diluent <β>. It was found that the effect of forming a fluorocopolymer liquid composition containing a double bond without gelation is very excellent. That is, while bringing the polymerization inhibitor and oxygen gas into contact with a mixed solution in which the fluorine-containing copolymer <αf> containing a double bond containing an organic solvent and the reactive diluent <β> coexist, It has been found that by removing a part or the whole, a fluorine-containing copolymer liquid composition containing a double bond can be produced in a good state without causing gelation.

That is, a fluorine-containing copolymer containing a double bond containing an organic solvent in an amount of more than 10% by weight (a fluorine-containing copolymer in an amount of less than 90% by weight, based on the total amount of the organic solvent). At atmospheric pressure or under reduced pressure, the polymerization inhibitor is added and the reactive diluent is added to form a liquid mixture. In order to inhibit or suppress the polymerization in the liquid mixture, while further introducing oxygen gas, by distilling at a temperature of 0 to 150 ° C. to remove a part or all of the organic solvent, the amount of the organic solvent is The content of the produced double bond-containing fluorocopolymer liquid composition is reduced to 10 to 0% by weight, and at the same time, the crosslinking reaction between these copolymers and the reactive diluent is changed to the organic solvent thereof. Is prohibited or suppressed during the removing step and during the subsequent use period (preservation period) to prevent gelation.

In particular, the oxygen gas can be diluted with an inert gas such as nitrogen and introduced as an oxygen-containing gas.
In that case, the gas concentration is preferably about 1 to 50 vol%, and particularly preferably 10 to 30 vol% in terms of safety and the like.
If it is less than 1 vol%, the effect of suppressing the crosslinking reaction is weak,
On the other hand, if it exceeds 50 vol%, the explosiveness becomes extremely high due to mixing with solvent vapor, which is dangerous. Further, as the oxygen-containing gas, oxygen gas in the atmosphere, that is, air can be used. In this case, since the air in the atmosphere may be introduced as it is, the equipment becomes simpler and the cost can be reduced as compared with the case where the oxygen cylinder is used. However, whether an oxygen cylinder or air is used, it is necessary to pay particular attention to the explosive limit of the organic solvent.

Furthermore, in order to inhibit or suppress the polymerization, oxygen gas may be used and other polymerization inhibitors may be used in combination. The polymerization inhibitor used in combination is preferably hydroquinone or hydroquinone monomethyl ether. The amount of the polymerization inhibitor used is 10 to 10% of the total amount of the polymer containing the double bond and the reactive diluent.
It is about 5000 ppm, and the effect can be expected with this amount.

The organic solvent in the fluorine-containing copolymer <αf> containing a double bond containing an organic solvent in an amount of more than 10% by weight can be partially or wholly removed by extraction. The organic solvent in the obtained fluorine-containing copolymer liquid composition containing a double bond can be 10% by weight or less.

That is, by the method described above, the fluorine-containing copolymer <αf> containing a double bond is 9 to 81% by weight, the reactive diluent <β> is 9 to 91% by weight, and the organic solvent is 0%. A fluorinated copolymer composition containing a double bond having a composition of 10 to 10% by weight can be produced.

Here, as a condition for achieving 0% by weight of the amount of the organic solvent, <αf> is 9% by weight and <β> is 91% by weight, or <αf> is 81% by weight and <β>. Is 19
It is necessary to be the weight%. <Αf> is 81% by weight
When it exceeds, it becomes necessary to make the organic solvent-containing state, and gelation occurs when the organic solvent is not contained. Further, when <αf> is less than 9% by weight, when formed into a coating film, the coating film characteristics such as excellent water / oil repellency, antifouling property, chemical resistance, and weather resistance, which are the effects of the present invention, are obtained. I will not be able to.
On the other hand, when the amount of organic solvent is 10% by weight, <αf> is 8
A liquid composition can be prepared without gelation up to a state where <β> is 9% by weight at 1% by weight, but when <β> is less than 9% by weight, the viscosity is high, and therefore work is performed. The above problem arises.

The fluorine-containing copolymer liquid composition containing the double bond produced as above was measured at 25 ° C. with a B-type viscometer (BL type, Toki Sangyo Co., Ltd.). The viscosity is 1 to 100,000 CPS, and it is preferable to set it to 10 to 50,000 CPS from the viewpoint of workability in forming a coating material.

The viscosity of the fluorine-containing copolymer liquid composition containing a double bond can be changed by the combination of the fluorine-containing copolymer <αf> and the reactive diluent <β> or the organic solvent. Although the viscosity changes depending on the size of each molecular weight and the amount combined, in order to further improve the work efficiency, a low viscosity of about 10 to 5,000 CPS is preferable, and a high viscosity of tens of thousands CPS or more is required depending on the application. In some cases, these can be adjusted appropriately.

The fluorine-containing copolymer liquid composition containing a double bond of the present invention can be cured in a short time because it can be cured by irradiation with light. Therefore, it is very useful for coating a substrate such as plastic which is not heated so much.

When the hydroxyl group-containing fluorocopolymer is to be cured at room temperature, a curing agent must be mixed at the time of use, which is not convenient in terms of work.
The liquid composition of the fluorine-containing copolymer containing a double bond of the present invention is a single liquid and is very useful in terms of work since it can be used without mixing a curing agent.

The fluorine-containing copolymer composition containing a double bond obtained by such a method can be cured by irradiation with light (ultraviolet rays, electron beams, etc.) or heating.

Examples of the photopolymerization initiator include benzoin ether, benzophenone, 1-hydroxyl-cyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropanone-1,2.
-Benzyl-2 dimethylamino-1- (4-morpherinophenyl) -butanone-1,2,2-dimethoxy-
1,2-diphenylethan-1-one or the like is used.

As the thermal polymerization initiator, benzoyl peroxide, azobisisobutyronitrile, t-butylperoxy-2-ethylhexanate, t-butylperoxyisopropyl monocarbonate and the like are used.

The fluorine-containing copolymer liquid composition containing a double bond of the present invention is characterized in that it can be cured without being mixed with an initiator when cured by electron beam irradiation. .

The fluorine-containing copolymer liquid composition containing a double bond of the present invention may be added with a commercially available photocurable resin or the like. The fluorine-containing copolymer containing a bond can be adjusted to be used in an amount of 5 to 80% by weight, particularly 20 to 60% by weight in the coating material, which is particularly preferable in terms of usability.

The fluorine-containing copolymer liquid composition containing a double bond of the present invention and a commercially available photocurable resin are mixed with each other to form a usual coating material such as a ball mill, a paint shaker, a sand mill, a three roll mill, a kneader or the like. Can be performed by using various devices used for. At this time, if necessary, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, etc. may be added and mixed.

[0083]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 After degassing, in an autoclave (withstand pressure 10 MPa) made of stainless steel with an internal volume of 1 L, 96 g of vinylidene fluoride (hereinafter abbreviated as VDF), 84 g of tetrafluoroethylene (hereinafter abbreviated as TFE), 84 g of ethyl vinyl ether (hereinafter EVE) 14.9 g, hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE) 52.2 g, reactive silicone oil A (number average molecular weight of about 3,500) 10.5 g represented by the following structural formula, butyl acetate 400 g,
And 1.3 g of t-butyl peroxypivalate,
The internal temperature was raised to 60 ° C. with stirring.

CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si (C
_{H 3) 2 - [O-} Si (CH 3) 2] 44 -OSi (CH 3) 3 then continued stirring reaction, stirring after 20 hours was stopped, the reaction was terminated. The resulting copolymer was isolated by vacuum drying. Polymer yield was 242 g, polymer yield was 9
It was 4%. The obtained hydroxyl group-containing fluorocopolymer (hereinafter referred to as [A-1]) had a hydroxyl value of 104 mgKOH / g resin as measured by an acetylation method with acetic anhydride, and a fluorine content of 47% by weight as measured by a combustion method. It was

Next, in a dark place, stirrer, reflux condenser,
In a 1 L round bottom three-necked flask equipped with a dropping funnel and a calcium chloride tower, 600 g of a 30% butyl acetate solution of the obtained [A-1] and hydroquinone monomethyl ether (ME
HQ) 0.05 g was added. While maintaining the temperature at 40 ° C. and stirring, a mixed solution containing 51.8 g of 2-isocyanatoethyl methacrylate (hereinafter referred to as [B-1]) and 17.3 g of butyl acetate was dropped little by little with a dropping funnel.
After completion of dropping, stirring was continued for 2 hours to obtain a polymer containing a double bond.

The infrared absorption spectrum of the above reaction solution was measured. As a result, 2,260cm ^{- 1} of absorption of an isocyanate group was confirmed that disappeared completely. This confirmed that the reaction between the hydroxyl group of [A-1] and the isocyanate group of [B-1] proceeded. The number average molecular weight of the obtained double bond-containing polymer (referred to as <α-1>) measured by GPC was 1.9 × 10 ⁴ .

Subsequently, 100 g of a 30% butyl acetate solution of the polymer <α-1> containing a double bond obtained in a 1 L eggplant flask and 1,6-hexanediol diacrylate (<β-1> Yes) 70g, MEHQ 0.02g
Was charged, and butyl acetate was removed by an evaporator while introducing 20% oxygen gas diluted with an inert gas into the mixed solution. The obtained fluorine-containing copolymer liquid composition containing a double bond is a colorless transparent liquid, and has <α-1> and <β-1.
>, The compatibility was good. Further, the amount of butyl acetate in the obtained liquid polymer composition containing a double bond was measured by GC analysis and found to be 2% by weight. Example 2 125.2 g of methyl methacrylate, n-butyl acrylate 96.
1 g, 2-hydroxyethyl methacrylate 65.1 g,
400 g of butyl acetate and 1.4 g of t-butyl peroxypivalate were added, and the internal temperature was raised to 60 ° C. with stirring.

Thereafter, the reaction was continued with stirring, and after 20 hours, the stirring was stopped and the reaction was completed. The resulting copolymer was isolated by vacuum drying. The polymer yield was 281 g, and the polymer yield was 98%. The hydroxyl group value of the obtained hydroxyl group-containing polymer (hereinafter referred to as [A-2]) measured by an acetylation method with acetic anhydride was 100 mgKOH / g resin.

Next, in a dark place, a stirrer, a reflux condenser,
In a 1 L round bottom three-necked flask equipped with a dropping funnel and a calcium chloride tower, 600 g of a 30% butyl acetate solution of the obtained [A-2] and hydroquinone monomethyl ether (ME
HQ) 0.05 g was added. While maintaining the temperature at 40 ° C. and stirring, a mixed solution containing 49.8 g of [B-1] and 16.6 g of butyl acetate was added little by little with a dropping funnel. After completion of dropping, stirring was continued for 2 hours to obtain a polymer containing a double bond.

The resulting double bond-containing polymer (<α
-2>) and the number average molecular weight measured by GPC is 1.
It was 1 × 10 ⁴ .

Subsequently, 100 g of a 30% butyl acetate solution of a polymer <α-2> containing a double bond obtained in a 1 L eggplant flask and trimethylolpropane ethoxytriacrylate (referred to as <β-2>). 70g, MEHQ
Butyl acetate was removed by an evaporator while introducing 0.02 g and introducing 20% oxygen gas diluted with an inert gas into the mixed solution. The obtained polymer liquid composition containing a double bond is a colorless transparent liquid, and has <α-2> and <β-2.
>, The compatibility was good. Further, the amount of butyl acetate in the obtained liquid polymer composition containing a double bond was measured by GC analysis and found to be 3% by weight. Example 3 167 g of 30% butyl acetate solution of polymer <α-1> containing double bond and <β-1> 50 g, MEHQ 0.0
5 g was added, and butyl acetate was removed by an evaporator while introducing air into the mixed solution. The obtained polymer liquid composition containing a double bond is a colorless transparent liquid, <α-
The compatibility between 1> and <β-1> was good. Further, the amount of butyl acetate in the obtained liquid polymer composition containing a double bond was measured by GC analysis and as a result, it was 4% by weight. Example 4 167 g of a 30% butyl acetate solution of a polymer <α-1> containing a double bond, <β-1> 50 g, and hydroquinone (hereinafter abbreviated as HQ) 0.05 g were added and diluted with an inert gas. While introducing 20% oxygen gas into the mixed solution, butyl acetate was removed by an evaporator. The obtained polymer liquid composition containing a double bond is a colorless transparent liquid,
The compatibility between α-1> and <β-1> was good. Also,
The amount of butyl acetate in the obtained liquid polymer composition containing a double bond was measured by GC analysis and found to be 3% by weight. Examples 5-10 Using the monomers shown in Table 1, according to the procedure of Example 2,
A polymer containing a double bond of α-3> to <α-5> was produced.

Subsequently, with the composition shown in Table 2, the organic solvent was removed according to the operation of Example 1. The properties of the obtained polymer liquid composition were similarly examined. The results are shown in Table 2. Comparative Example 1 As a result of measuring the amount of butyl acetate in the polymer <α-1> containing the double bond of Example 1 by GC analysis, 70% by weight was obtained.
Met. Comparative Example 2 30 of polymer <α-1> containing double bond of Example 1
% Butyl acetate solution 100 g and <β-1> 70 g, MEH
When 0.02 g of Q was added and 20% oxygen gas diluted with an inert gas was not introduced and butyl acetate was removed by an evaporator, gelation occurred. Comparative Example 3 30 of the polymer <α-2> containing the double bond of Example 2
% Butyl acetate solution 100 g and <β-2> 70 g, MEH
When 0.02 g of Q was added and 20% oxygen gas diluted with an inert gas was not introduced and butyl acetate was removed by an evaporator, gelation occurred. Comparative Examples 4 to 6 According to the operation of Comparative Example 2, the monomers shown in Table 1 were used, 20% oxygen gas diluted with an inert gas was not introduced, and butyl acetate was removed by an evaporator. Turned into Example 11 An autoclave (withstand pressure of 10 MPa) made of stainless steel and having an internal volume of 1 L was deaerated, and then VDF 48
g, TFE 100g, EVE27.0g, HBVE4
3.5 g, the reactive silicone oil A (molecular weight about 3
500) 0.44 g, butyl acetate 400 g, and t-butyl peroxypivalate 1.3 g were added, and the internal temperature was raised to 60 ° C. with stirring.

Then, the reaction was continued with stirring, and after 20 hours, the stirring was stopped and the reaction was completed. The resulting copolymer was isolated by vacuum drying. The polymer yield was 204 g, and the polymer yield was 93%. The obtained hydroxyl group-containing fluorocopolymer (hereinafter referred to as [Af-1]) has a hydroxyl value of 103 mg as measured by an acetylation method with acetic anhydride.
KOH / g resin, fluorine content by combustion method was 48% by weight.

Next, in a dark place, a stirrer, a reflux condenser,
To a 1 L three-necked round bottom flask equipped with a dropping funnel and a calcium chloride tower, 600 g of a 30% butyl acetate solution of the obtained [Af-1] and 0.05 g of MEHQ were placed. Temperature 4
[B-1] 5 with a dropping funnel while maintaining at 0 ° C and stirring
A mixed solution containing 1.3 g and 17.1 g of butyl acetate was added dropwise little by little. After completion of dropping, stirring was continued for 2 hours to obtain a polymer containing a double bond.

The infrared absorption spectrum of the above reaction solution was measured. As a result, 2,260cm ^{- 1} of absorption of an isocyanate group was confirmed that disappeared completely. This confirmed that the reaction between the hydroxyl group of [Af-1] and the isocyanate group of [B-1] proceeded. GPC of the obtained polymer containing a double bond (referred to as <αf-1>)
The number average molecular weight measured by the method was 2.5 × 10 ⁴ .

Subsequently, 100 g of a 30% butyl acetate solution of the polymer <αf-1> containing a double bond obtained in a 1 L eggplant-shaped flask and <β-2> 70 g, MEHQ 0.0.
2 g was put in, and butyl acetate was removed by an evaporator while introducing 20% oxygen gas diluted with an inert gas into the mixed solution. The obtained fluorine-containing copolymer liquid composition containing a double bond is a colorless transparent liquid, and <αf-1> and <αf-1>
The compatibility of β-2> was good. Further, the amount of butyl acetate in the obtained fluorine-containing copolymer liquid composition containing a double bond was measured by GC analysis and found to be 3% by weight.

The coating film characteristics of the cured coating film of this fluorine-containing copolymer composition were examined by the following methods. The results are shown in Table 5. <Adhesion to Substrate> Fluorine-containing copolymer liquid composition 1
00g and commercially available photocurable resin: Ebecry1 810
230 g (manufactured by Daicel UCB) and 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropanone-1 (manufactured by Ciba Geigy) 15
g, and applied on a JISG-3141 steel plate with an applicator and dried at 80 ° C. for 1 minute, and then 2 in air.
It was irradiated with 70 mJ / cm ² of ultraviolet rays. The obtained thickness 4
The test piece of 0 μm was measured by JIS-K5400 6.15 (governed cellotape (registered trademark) test). <Pencil hardness> According to JIS-K5400 6.14 (pencil scratch test). <Acid resistance / alkali resistance> 10% HCl solution, 10% N
The appearance of the coating film after the 24-hour spot test with the aOH solution is visually observed. ◎: No abnormality ○: Almost no change △: Slightly attacked ×: Attacked <Oil-based magic repellency> The paint film surface is filled with oil-based magic (black / red / magic ink product name) and the repellency is evaluated. Further, this coating film is left at room temperature for 1 hour and then removed by dry wiping. After repeating this 20 times, the repellency of the coating film surface is evaluated. ◎: Well repelled ○: Repelled △: Slightly repelled ×: Not repelled at all <Repetitive removability of oil-based magic> Paint film surface was coated with oil-based magic (black / red / magic ink product name), left at room temperature for 1 hour, and then wiped dry Remove. After repeating this 20 times, the removability of the coating film surface is evaluated. ⊚: No traces are marked ○: Very slight marks are marked Δ: Significant marks are marked ×: Complete marks are left <Water repellency> Water contact angle (unit: degree) was used for evaluation. Example 12 Using the monomers shown in Table 4, a fluorocopolymer <αf-2> and a fluorocopolymer liquid composition were produced in accordance with the procedure of the above example, and the same characteristics were obtained. I checked. The results are shown in Table 5. Example 13 An autoclave (withstand pressure of 10 MPa) made of stainless steel and having an internal volume of 1 L was deaerated and then VDF 50
g, TFE 78 g, butyl vinyl ether (hereinafter BV
Abbreviated as E) 52.0 g, HBVE 45.2 g, reactive silicone oil C represented by the following structural formula (molecular weight of about 4)
20) 54.6 g of toluene, 400 g of toluene, and 1.4 g of t-butylperoxypivalate were added, and the internal temperature was raised to 60 ° C. while stirring.

CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si-
_{[O-Si (CH 3)} 3] 3 then continued stirring reaction, stirring after 20 hours was stopped, the reaction was terminated. The resulting copolymer was isolated by vacuum drying. Polymer yield 260 g, polymer yield 9
It was 3%. The hydroxyl group value of the obtained fluorine-containing copolymer containing hydroxyl group (hereinafter referred to as [Af-3]) was 86 mgKO.
The H / g resin and the fluorine content were 32% by weight.

Next, in a dark place, stirrer, reflux condenser,
In a 1 L round bottom three-necked flask equipped with a dropping funnel and a calcium chloride tower, 600 g of a 30% toluene solution of [Af-3].
And MEHQ 0.05 g were added. While maintaining the temperature at 40 ° C. and stirring, a mixed solution containing 30.0 g of [B-1] and 10.0 g of toluene was dropped little by little with a dropping funnel. After completion of the dropping, stirring was continued for 2 hours to obtain a fluorine-containing copolymer containing a double bond.

The infrared absorption spectrum of the above reaction solution was measured, and it was confirmed that the reaction between the hydroxyl group of [Af-3] and the isocyanate group of [B-1] proceeded. The number average molecular weight of the obtained fluorine-containing copolymer <αf-3> containing a double bond measured by GPC was 1.9 × 10 ⁴ .

Subsequently, 30% of the double bond-containing fluorocopolymer <αf-3> obtained in a 1 L eggplant-shaped flask was obtained.
% Toluene solution 100 g and <β-2> 70 g, MEHQ
Butyl acetate was removed by an evaporator while introducing 0.02 g and introducing 20% oxygen gas diluted with an inert gas into the mixed solution. The obtained fluorine-containing copolymer liquid composition containing a double bond is a colorless transparent liquid, <αf-
The compatibility of 3> and <β-2> was good. Further, the amount of butyl acetate in the obtained fluorine-containing copolymer liquid composition containing a double bond was measured by GC analysis and found to be 5% by weight.

The coating film characteristics of the cured coating film of this copolymer composition were examined in the same manner as in Example 11. The results are shown in Table 5. Examples 14 to 16 Fluorine-containing copolymers <αf-4> to <αf-6> and their fluorine-containing copolymer liquid compositions were prepared using the monomers shown in Table 4 in accordance with the procedure of the above-mentioned Examples. Were manufactured and their properties were similarly examined. The results are shown in Table 5. Comparative Example 7 Fluorine-containing copolymer containing the double bond of Example 11 <α
f-1> 100 g and <β-2> 70 g, MEHQ 0.
When 02 g was added and 20% oxygen gas diluted with an inert gas was not introduced and butyl acetate was removed by an evaporator, gelation occurred. Comparative Example 8 VDF 75 after deaeration in a stainless steel autoclave with a stirrer (pressure resistance 10 MPa) having an internal volume of 1 L
g, TFE 100g, EVE 5.4g, HBVE2
9.0 g, reactive silicone oil A 0.44 g, butyl acetate 400 g, and t-butyl peroxypivalate 1.0 g were added, and the internal temperature was raised to 60 ° C. with stirring.

Then, the reaction was continued with stirring, and after 20 hours, the stirring was stopped and the reaction was completed. The resulting copolymer was isolated by vacuum drying. The polymer yield was 183 g, and the polymer yield was 87%. The hydroxyl group value of the obtained fluorine-containing copolymer containing a hydroxyl group (hereinafter referred to as [Af-7]) was 77 mgK measured by an acetylation method with acetic anhydride.
OH / g resin, fluorine content by combustion method is 57% by weight
Met.

Next, in a dark place, stirrer, reflux condenser,
600 g of a 30% butyl acetate solution of the obtained [Af-7] and 0.05 g of MEHQ were placed in a 1 L round bottom three-necked flask equipped with a dropping funnel and a calcium chloride tower. While keeping the temperature at 40 ° C and stirring, [B-1] 3 was added using a dropping funnel.
A mixed solution containing 8.4 g and 12.8 g of butyl acetate was added dropwise little by little. After completion of the dropping, stirring was continued for 2 hours to obtain a fluorine-containing copolymer <αf-7> containing a double bond.
Fluorine-containing copolymer containing the obtained double bond <αf-
The number average molecular weight measured by GPC of 7> is 3.1 × 10 ^4.
Met.

Subsequently, the double-bond-containing fluorocopolymer <αf-7> 100 obtained in a 1 L eggplant flask was obtained.
g and <β-1> 70g, MEHQ 0.02g,
While introducing 20% oxygen gas diluted with an inert gas into the mixed solution, butyl acetate was removed by an evaporator. However, the compatibility between <αf-7> and <β-1> was poor, and it became a cloudy liquid. Comparative Example 9 Using the monomers shown in Table 4, a fluorinated copolymer <αf-8> and a fluorinated copolymer liquid composition were produced in accordance with the procedure of the above example, and these properties were the same. Examined. The results are shown in Table 6.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

In the table, CTFE: chlorotrifluoroethylene, HEMA: 2-hydroxyethyl methacrylate, MA: methyl acrylate, reactive silicone oil A: CH ₂ = C (CH ₃ ) -COO-C ₃ H _{6 -Si (CH 3) 2 - [} O-Si (CH 3) 2] 44 -OSi (CH
₃ ) ₃ Number average molecular weight: about 3500 Reactive silicone oil B: CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si (CH ₃ ) _2- [O-Si (CH ₃ ) ₂ ] ₆₄ -OSi (CH
₃ ) ₂ C ₄ H ₉ number average molecular weight: about 5000 ・ Reactive silicone oil C: CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si- [O-Si (CH ₃ ) ₃ ] ₃ number Average molecular weight: about 420 ・ Reactive silicone oil D: CH ₂ = C (CH ₃ ) -COO-C ₃ H ₆ -Si (CH ₃ ) _2- [O-Si (CH ₃ ) ₂ ] ₂₅ -OSi (CH
₃ ) ₃ Number average molecular weight: about 2000 ・ Reactive silicone oil E: CH ₂ = CH-Si (CH ₃ ) _2- [O-Si (CH ₃ ) ₂ ] ₄₄ -OSi (CH ₃ ) ₂ -CH = CH ₂ Number average molecular weight: about 3450 Solvesso (registered trademark): Solvesso 100J, exxon-mobile chemical company

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Egashira Keidai             1497 Shibukawa City, Gunma Kanto Denka Kogyo Co., Ltd.             Company Shibukawa factory (72) Inventor Nobuo Obayashi             1497 Shibukawa City, Gunma Kanto Denka Kogyo Co., Ltd.             Company Shibukawa factory F-term (reference) 4D075 BB26Z BB42Z CA13 CA32                       CA34 CA36 CA44 CA47 EA05                       EA19 EA21 EB13 EB15 EB16                       EB17 EB22 EB38 EB39 EB42                 4J027 AG01 AG06 AG36 AJ05 BA04                       BA07 CC03 CC05 CD08                 4J034 AA08 BA03 DA01 DB03 DD07                       DM01 DM12 DP04 DP12 DP15                       GA01 HA18 QA03 QC05 RA07                       SA02 SC04 SC09 SD03 SD04                       SD08

Claims (25)

[Claims] 1. A liquid composition containing a double bond, wherein the polymer containing a double bond and a reactive diluent coexist, which is a liquid composition containing no gelling component. . 2. A polymer containing a double bond is 9 to 81% by weight, a reactive diluent is 9 to 91% by weight, and an organic solvent is 0%.
The polymer liquid composition containing a double bond according to claim 1, wherein the polymer liquid composition comprises 10 to 10% by weight. 3. A polymer having a double bond and a reactive diluent are mixed in a liquid state with a polymer having a double bond and a reactive diluent under conditions that inhibit or suppress the polymerization of the both. The method for producing a polymer liquid composition containing a double bond according to claim 1 or 2, wherein the liquid composition coexists as a liquid composition without causing gelation. 4. A liquid composition is prepared by mixing a polymer solution obtained by combining a polymer having a double bond and an organic solvent with a reactive diluent and allowing them to coexist. Or a method for producing a polymer liquid composition containing a double bond according to item 2. 5. A liquid mixture comprising a polymer solution containing an organic solvent and containing a double bond and a reactive diluent, wherein a part of the organic solvent is added under the condition of inhibiting or suppressing the polymerization of the liquid mixture. 5. The double bond-containing polymer according to claim 4, wherein the polymer containing the double bond and the reactive diluent are allowed to coexist as a liquid composition without causing a crosslinking reaction by removing all or all of them. A method for producing a polymer liquid composition. 6. An organic solvent in an amount of more than 10% by weight and 90
A polymer mixture comprising a polymer containing less than wt% of double bonds, and a liquid mixture comprising a reactive diluent,
Under conditions that inhibit or suppress the polymerization of the liquid mixture,
By removing some or all of the organic solvent,
The polymer containing a double bond has a molecular weight of 9 to 81 without causing a crosslinking reaction between the polymer containing a double bond and the reactive diluent.
The double-bond-containing polymer liquid composition according to claim 2, wherein the liquid composition comprises 5% by weight, 9 to 91% by weight of the reactive diluent, and 0 to 10% by weight of the organic solvent. Manufacturing method. 7. The method for producing a polymer liquid composition containing a double bond according to claim 3, wherein oxygen gas is used to inhibit or suppress the polymerization. 8. A polymer liquid composition containing a double bond according to claim 3, wherein oxygen gas and a polymerization inhibitor are used in combination to inhibit or suppress the polymerization. Method of manufacturing things. 9. A polymer solution containing an organic solvent and containing a double bond, and a reactive diluent are mixed in the presence of a polymerization inhibitor, and a part or all of the organic solvent is mixed and then mixed. The double bond-containing polymer according to claim 5 or 6, wherein the polymer containing the double bond and the reactive diluent coexist as a liquid composition by removing while introducing oxygen gas. A method for producing a polymer liquid composition. 10. The method for producing a polymer liquid composition containing a double bond according to claim 9, wherein the organic solvent is removed by a distillation operation at a temperature of 0 to 150 ° C. 11. 10 to 30 v diluted with an inert gas
The method for producing a polymer liquid composition containing a double bond according to claim 9 or 10, wherein a part or all of the organic solvent is removed while introducing a gas containing ol% oxygen. 12. The organic solvent is at least one selected from butyl acetate, ethyl acetate, toluene, xylene, Solvesso (registered trademark), methyl ethyl ketone, methyl isobutyl ketone, methanol and butanol. A method for producing a polymer liquid composition containing a double bond according to claim 2. 13. The reactive diluent is one or more selected from the group of acrylates, methacrylates and ethers having at least one unsaturated double bond in the molecule, and the double diluent. It has a function of substituting an organic solvent that dissolves a bond-containing polymer, and further, due to the unsaturated double bond in the molecule, the unsaturated bond in the polymer containing the double bond The polymer liquid composition containing a double bond according to claim 1 or 2, which is crosslinked with the double bond. 14. The double-bond-containing halogen-containing copolymer according to claim 1, wherein the double-bond-containing polymer is a double-bond-containing halogen-containing copolymer. Combined liquid composition. 15. The double bond-containing fluorocopolymer according to claim 1 or 2, wherein the double bond-containing polymer is a double bond-containing fluorocopolymer. Combined liquid composition. 16. A fluorine-containing copolymer having a double bond is used as a polymerized unit in an amount of 15 to 85 mol% of a fluoroolefin and 0.001 to 0.001 of a reactive silicone oil represented by the general formula (1) or (2). Copolymer produced by the reaction of a hydroxyl group-containing fluorocopolymer [A] composed of 30 mol% and a hydroxyl group-containing unsaturated monomer 1 to 50 mol% with an unsaturated isocyanate [B] The fluorine-containing copolymer liquid composition containing a double bond according to claim 15, wherein _{^{R 1 - [Si (CH 3}} ) 2 -O] n -Si (CH 3) 2 -R 2 (1) ( wherein, ^{R 1} represents or an alkyl group having 1 to 6 carbon atoms -
_{(CH 2) r -OOC (CH} 3) C = CH 2 or - (C
H _{2) r} -OOCHC = CH ₂ or -CH = CH ₂
Indicates. R ² is _{- (CH 2) r -OOC (} CH 3) C = CH
₂ or - indicates a _{(CH 2) r -OOCHC = CH} 2 or -CH = CH _2. n is an integer from 1 to 420, r is 1
Indicates an integer of ˜6. ^{) R 2 -Si [OSi (CH} 3) 3] 3 (2) 17. The reactive diluent is one or more selected from the group of acrylates, methacrylates and ethers having at least one unsaturated double bond in the molecule, and It has a function of substituting an organic solvent in which a fluorine-containing copolymer containing a bond is soluble, and further, due to the unsaturated double bond contained in the molecule, the fluorine-containing copolymer containing a double bond is contained. The fluorine-containing copolymer liquid composition containing a double bond according to claim 15 or 16, which crosslinks with an unsaturated double bond in the polymer. 18. The method according to claim 15, wherein the polymerization inhibitor inhibits or suppresses the crosslinking reaction between the fluorine-containing copolymer having a double bond and the reactive diluent.
A method for producing a liquid composition of a fluorocopolymer containing a double bond according to any one of 1. 19. Oxygen gas is used to inhibit or suppress the polymerization.
A method for producing a liquid composition of a fluorocopolymer containing a double bond according to any one of 1. 20. A fluorine-containing copolymer containing a double bond according to any one of claims 15 to 17, wherein oxygen gas and a polymerization inhibitor are used in combination to inhibit or suppress the polymerization. Method for producing coalesced liquid composition. 21. The hydroxyl group-containing fluorine-containing copolymer [A] is constituted to further contain at least one polymerized unit selected from the group consisting of alkyl vinyl ether, alkyl allyl ether, methacrylic acid ester and acrylic acid ester as the balance. A liquid composition containing a fluorine-containing copolymer containing a double bond according to claim 16. 22. The reactive silicone oil has the following formula:
Indicated by (4), (5), (6), (7) or (8)
One-end type or both-end type modified silicone oil
The double bond according to claim 16 or 21, characterized in that
Liquid composition containing a fluorocopolymer. CH₂= C (CH₃) -COO-C₃H₆-Si (CH₃)₂-[O-Si (CH₃)₂]_p-R^Four (4) (Where R^FourRepresents an alkyl group having 1 to 6 carbon atoms. p
Represents an integer of 1 to 250. ) CH₂= CH-COO-C₃H₆-Si (CH₃)₂-[O-Si (CH₃)₂]_s-R^Five (5) (Where R⁵Represents an alkyl group having 1 to 6 carbon atoms. s
Represents an integer of 1 to 250. ) R⁶-C₃H₆-Si (CH₃)₂-[O-Si (CH₃)₂]_q-C₃H₆-R⁶   (6) (Where R⁶Is -OOC (CH_Three) C = CH_TwoOr
-OOCHC = CH_TwoIndicates. q is an integer from 1 to 250
Show. ) CH₂= C (CH₃) -COO-C₃H₆-Si [O-Si (CH₃)₃]₃       (7) CH₂= CH-Si (CH₃)₂-[O-Si (CH₃)₂]_t-R⁷          (8) (Where R⁷Is an alkyl group having 1 to 6 carbon atoms or-
CH = CH₂Indicates. t shows the integer of 1-250. ) 23. A polymer solution of a double bond-containing fluorocopolymer containing an organic solvent in an amount of more than 10% by weight of the whole is added with a reactive diluent in the presence of a polymerization inhibitor, and the temperature is increased. While introducing an oxygen-containing gas at 0 to 150 ° C., by removing a part or all of the organic solvent, the fluorine-containing copolymer containing a double bond is 9 to 81% by weight, and the reactive diluent is 9-91% by weight and 0-10% by weight of organic solvent
18. The method for producing a fluorine-containing copolymer liquid composition containing a double bond according to claim 16, wherein the liquid composition coexists as the liquid composition. 24. The double bond according to any one of claims 15 to 17 or 21 to 22, wherein the viscosity at 25 ° C. measured by a B type viscometer is 1 to 100,000 CPS. Liquid composition containing a fluorocopolymer. 25. A liquid composition containing a fluorine-containing copolymer containing a double bond containing an organic solvent in a proportion of 0 to 10% by weight and a reactive diluent is irradiated with light, or A method for forming a coating film of a fluorocopolymer composition, which comprises curing by heating to form a coating film.