JPH0532728A - Fluorine-containing copolymer containing ethylene carbonate group and paint containing the copolymer as main component - Google Patents

Abstract

PURPOSE:To provide the subject copolymer composed of specific constituent components, excellent in gloss, solubility, compatibility, chemical resistance and weather resistance and useful for paint, etc. CONSTITUTION:The objective composition contains (A) 20-95mol% of the unit of formula I (V, X, Y and Z are H, F, Cl, 1-6C alkyl, etc.) and (B) 1-50mol% of the unit of formula II (R<1> and R<2> are H or 1-5C alkyl; R<3> is bivalent organic group) as essential components. The copolymer can be produced by reacting the epoxy group of a fluorine-containing copolymer having epoxy group with carbon dioxide or by copolymerizing a monomer mixture composed of a vinyl monomer having ethylene carbonate group and a fluorine-containing vinyl monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorine-containing copolymer and a paint containing it as a main component.

[0002]

Fluorine-containing resins have hitherto been widely used in many fields because they are extremely excellent in heat resistance, mechanical properties, chemical resistance, weather resistance and the like. One of its uses is as a coating film forming component of paint.
For example, a fluororesin paint using a tetrafluoroethylene polymer or a vinylidene fluoride polymer is known,
Since it has excellent lubricity, non-adhesiveness, weather resistance and chemical resistance, it is used as a coating material in the fields of chemical industry, food, construction, machinery and the like.
However, the fluororesin coating composition has a drawback that it needs to be baked at a high temperature and the range of use is unavoidable. Therefore, in recent years, it is soluble in an organic solvent and can be cured at room temperature. Attempts have been made to develop solvent-based paints using a fluorine-containing copolymer having a reactive group.

By the way, examples of fluorine-containing copolymers soluble in organic solvents include those disclosed in JP-A-57-34107.
JP-A-61-275311, JP-A-61-576
No. 09, JP-A-62-174213, JP-A-63-182312 and the like are known copolymers of fluoroolefins with vinyl monomers copolymerizable therewith.

However, when a urethane coating film excellent in weather resistance, chemical resistance and the like is formed using these copolymers, a polyisocyanate compound is usually used as a cross-linking agent, and the polyisocyanate compound is included in this polyisocyanate compound. The toxicity of free isocyanate groups is a problem. By the way, examples of the non-isocyanate type urethane paint include, for example, JP-A-63-168423 and JP-A-1-14669.
Although coating compositions comprising an acrylic resin having an ethylene carbonate group as a side chain and a polyamine compound as known in Japanese Patent No. 68, etc. are known, these coating compositions have the drawback that the weather resistance is still insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a fluorine-containing copolymer in which the above-mentioned problems of the prior art are solved, that is, a urethane coating excellent in weather resistance, chemical resistance, etc. without using a polyisocyanate compound. A fluorinated copolymer capable of forming a film,
And to provide a fluorine-based coating material containing this as a main component.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above points, the present inventors can solve the above problems by introducing a functional group having a specific structure into a fluorocopolymer. After finding things, the present invention was completed. That is,
The present invention is an ethylene carbonate group-containing fluorinated copolymer having the following components as essential components. Formula (A)

[0007]

[Chemical 5]

A unit represented by 20 to 95 mol% (B) formula

[0009]

[Chemical 6]

Unit represented by 1 to 50 mol%
And a coating material containing an ethylene carbonate group-containing fluorocopolymer having the above-mentioned constituents as essential components as a main component. Hereinafter, the present invention will be described in detail.

The ethylene carbonate group-containing fluorinated copolymer according to the present invention can be produced by the following methods (a) to (b). (A) The epoxy group of the fluorine-containing copolymer containing an epoxy group is reacted with carbon dioxide to convert it into an ethylene carbonate group. (B) Copolymerize a monomer mixture containing an ethylene carbonate group-containing vinyl monomer and a fluorine-containing vinyl monomer as essential components.

The method for producing the ethylene carbonate group-containing fluorine-containing copolymer of the present invention includes the above (a) to (b).
The method can be arbitrarily selected. First, the method (a) (when the epoxy group of the epoxy group-containing fluorocopolymer is reacted with carbon dioxide to convert it into an ethylene carbonate group) will be described. In this case, in the ethylene carbonate group-containing fluorine-containing copolymer of the present invention, as the epoxy group-containing fluorine-containing copolymer to be a starting material,
For example, those having the units represented by the following formulas (A) and (C) as essential constituents can be mentioned. Formula (A)

[0013]

[Chemical 7]

20 to 95 mol% of the structural unit represented by Formula (C)

[0015]

[Chemical 8]

1 to 50 mol% of structural unit represented by the above formula (A) and (C) to be starting materials in the ethylene carbonate group-containing fluorine-containing copolymer of the present invention.
The epoxy group-containing fluorine-containing copolymer having the formula as an essential component can be obtained by copolymerizing vinyl monomers corresponding to the formulas (A) and (C).

That is, specific examples of the fluorine-containing vinyl monomer corresponding to the formula (A) are, for example,

[0018]

[Chemical 9]

Fluoroethylene such as;

[0020]

[Chemical 10]

A fluoropropene system such as;

[0022]

[Chemical 11]

Examples thereof include fluoroolefin compounds having 4 or more carbon atoms, among which (a)
formula

[0024]

[Chemical 12]

The fluoroethylene compounds and fluoropropene compounds are preferable represented by, in particular tetrafluoroethylene (CF ₂ = CF _2), chlorotrifluoroethylene (CF ₂ = CFCl) and hexafluoropropene (CF ₂ = CFCF ₃₎ is It is suitable. These fluoroolefins may be used alone or in combination of two or more.

In the ethylene carbonate group-containing fluorine-containing copolymer of the present invention, the content of the (A) unit is 20-.
It must be in the range of 95 mol%, preferably 30 to 70 mol%. If this content is less than 20 mol%, the weather resistance is insufficient, and if it exceeds 95 mol%, the solubility in organic solvents will decrease. Next, as specific examples of the vinyl monomer corresponding to the formula (C),

[0027]

[Chemical 13]

Epoxy group-containing vinyl ethers such as;

[0029]

[Chemical 14]

Epoxy group-containing allyl ethers such as;

[0031]

[Chemical 15]

Epoxy group-containing (meth) acrylates such as;

[0033]

[Chemical 16]

Examples thereof include epoxy group-containing crotonic acid esters. These may be used alone or in combination of two or more. In the ethylene carbonate group-containing fluorine-containing copolymer of the present invention,
The epoxy group-containing fluorocopolymer to be used as a starting material includes, in addition to the constituents represented by the above formulas (A) and (C), other vinyl monomers within a range not exceeding 50 mol%. It is preferable to contain a copolymerized (D) unit.

Specific examples of the vinyl monomer forming the unit (D) include olefins such as ethylene, propylene and isobutylene; haloolefins such as vinyl chloride and vinylidene chloride; vinyl acetate, n-butyrate vinyl, Carboxylic acid vinyl esters such as vinyl benzoate, vinyl p-t-butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatate and vinyl laurate; carboxyne such as isopropenyl acetate and isopropenyl propionate. Acid isopropenyl esters; ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, neopentyl vinyl ether, 2
-Chain alkyl vinyl ethers such as ethylhexyl vinyl ether and octyl vinyl ether; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and 4-hydroxycyclohexyl vinyl ether; pentafluoroethyl vinyl ether, 2-perfluorooctyl ethyl vinyl ether And other fluorovinyl ethers; cyclopentyl vinyl ether, cyclohexyl vinyl ether and other cycloalkyl vinyl ethers; phenyl vinyl ether and other aryl vinyl ethers;
Aralkyl vinyl ethers such as benzyl vinyl ether and phenethyl vinyl ether; vinyl-9-aza-3
-Ethyl-8,8,9,10,10-pentamethyl-
1,5-dioxaspiro [5,5] -3-undecylmethyl ether, vinyl-9-aza-3-ethyl-8,
Piperidinyl group-containing vinyl ethers such as 8,10,10-tetramethyl-1,5-dioxaspiro [5,5] -3-undecylmethyl ether; aromatic vinyl compounds such as styrene and vinyltoluene Allyl formate, allyl acetate, Allyl butyrate, Allyl benzoate, Allyl cyclohexanecarboxylate, Allyl cyclohexylpropionate, 2
-Hydroxyallyl vinyl ether, 4-hydroxybutyl allyl ether, 4-allyloxy-2,2,6,
6, -Tetramethylpiperidine, 4-allyloxy-
Allyl esters such as 1,2,2,6,6-pentamethylpiperidine; allyl ethers such as allyl ethyl ether and allyl phenyl ether; butyl (meth) acrylate, methyl (meth) acrylate, cyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
4-hydroxypropyl (meth) acrylate, 2-hydroxy-4- (2-methacryloxyethoxy) benzophenone, 4- (meth) acryloyloxy-2,2
6,6, -Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6, -pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoro Esters of acrylic acid and methacrylic acid such as propyromethyl (meth) acrylate, perfluoromethylmethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate and perfluoroisononylmethyl (meth) acrylate; acrylamide; N
-Acrylamides such as methylolacrylamide; carboxyl group-containing vinyl monomers such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid; Japanese Patent Application No. 1-237122. Vinyl monomers having a cyclic hydrocarbon group introduced through a urethane bond; and endocyclic vinyl ethers such as those disclosed in Japanese Patent Application No. 2-101695.

Among these, as described in Japanese Patent Application No. 1-237122, a vinyl monomer having a cyclic hydrocarbon group introduced through a urethane bond, and Japanese Patent Application No. 2-237122.
An ethylene carbonate group-containing fluorine-containing copolymer using an endocyclic vinyl ether, as disclosed in Japanese Patent No. 101695, is suitable because it has excellent compatibility with a curing agent, hardness and gloss.

Further, an ethylene carbonate group-containing fluorine-containing copolymer containing a unit obtained by copolymerizing a carboxyl group-containing vinyl monomer is particularly preferable since it has a particularly good compatibility with an amine type curing agent described later. These vinyl monomers may be used alone or in combination of two or more.

In the ethylene carbonate group-containing fluorine-containing copolymer of the present invention, the epoxy group-containing fluorine-containing copolymer to be the starting material is used in the presence or absence of a solvent in the above formula (A) and ( Produced by copolymerizing a predetermined proportion of a vinyl monomer mixture containing a vinyl monomer corresponding to the constitutional unit represented by the formula C) with a polymerization initiator or an ionizing radiation as a polymerization initiation source. can do.

As the polymerization initiator, a water-soluble one or an oil-soluble one is appropriately used depending on the type of polymerization or desired. Examples of the oil-soluble initiator include azo compounds such as azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile); t-butylperoxypivalate and t-butylperoxyiso. Peroxyester type peroxides such as butyrate; Diacyl peroxide type peroxides such as octanoyl peroxide and lauroyl peroxide; Dialkyl peroxydicarbonate type peroxides such as diisopropyl peroxydicarbonate; Benzoyl peroxide And the like, such as dialkyl peroxide type peroxides.

As the water-soluble polymerization 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; ,
Inorganic initiators such as those in which small amounts of iron, ferrous salts, silver nitrate, etc. coexist; dibasic peroxides such as disuccinic acid peroxide, diglutaric acid peroxide, and monosuccinic acid peroxide, azobi Examples include organic initiators such as perisobutylamidine dibasic acid salt. The amount of these polymerization initiators to be used is appropriately selected depending on the type, the copolymerization reaction conditions, etc., but 0.005 to 5% by weight, preferably 0.05 to the total amount of the monomers usually used.
To 0.5% by weight.

The polymerization method is not particularly limited and, for example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be used. From the viewpoint of stability of the polymerization reaction operation, etc. Lower alkyl-substituted benzenes such as xylene and toluene; esters such as butyl acetate; ketones such as methyl isobutyl ketone; alcohols such as t-butanol; saturated halogenated hydrocarbons having at least one fluorine atom as a solvent. The solution polymerization method, the emulsion polymerization method in an aqueous medium, the bulk polymerization method that does not require separation from the solvent, and the like are preferably used.

Further, the polymerization system is not particularly limited, and any of batch system, semi-continuous system and continuous system can be used. The reaction temperature in the copolymerization reaction is usually -30.
Within the range of to + 150 ° C, it is appropriately selected depending on the type of the polymerization initiation source and the polymerization medium, and is usually 0 to 100 ° C, preferably 1
It is selected in the range of 0 to 90 ° C. The reaction pressure is not particularly limited, but is selected from the range of normal pressure to 100 kg / cm ² . Further, the copolymerization reaction can be carried out by adding an appropriate chain transfer agent.

The molecular weight of the epoxy group-containing fluorocopolymer thus obtained was determined by using tetrahydrofuran as a solvent,
The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) method using monodisperse polystyrene having a known molecular weight as a standard substance is 500 to 1
0,000, preferably in the range of 1,000 to 50,000, the epoxy group content is 0.5 to 50% by weight,
The glass transition temperature (Tg) is usually -50 to 120 ° C, preferably -10 to 100 ° C.

Subsequently, the epoxy group of the obtained epoxy group-containing fluorocopolymer is reacted with carbon dioxide to be converted into an ethylene carbonate group to obtain the ethylene carbonate group-containing fluorocopolymer of the present invention. The reaction between the epoxy group of the fluorine-containing copolymer containing an epoxy group and carbon dioxide can be carried out in the presence of a catalyst at a temperature of 30 to ²⁰⁰ ° C. and atmospheric pressure to 50 kg / cm ² .

As a catalyst for the reaction of the above epoxy group and carbon dioxide,

[0046]

[Chemical 17]

A quaternary ammonium compound represented by, for example, triethylammonium bromide, triethylammonium chloride, tetraethylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, Examples thereof include tetrabutylammonium carbonate, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide and choline. Other catalysts include

[0048]

[Chemical 18]

A phosphonium compound represented by, for example, tetraethylphosphonium iodide, tetraethylphosphonium bromide, tetraethylphosphonium chloride, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium carbonate, tetrabutylphosphonium hydro Examples include side, benzyltriethylphosphonium chloride, benzyltriethylphosphonium bromide, methyltriphenylphosphonium chloride, methyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, and the like. As another catalyst, N,
Guanidine compounds such as N, N ′, N′-tetramethylguanidine, amidine compounds such as 1,5-diaza-bicyclo (4,3,0) non-5-ene, phosphine compounds such as tributylphosphine and triphenylphosphine 1
Examples include imidazole compounds such as -methylimidazole and 2-ethyl-4-methylimidazole, 1,4-diazabicyclo (2,2,2) octane, dimethylaminoethanol, dimethylaminomethylphenol, piperazine and the like.

Each of the above catalysts may be used alone, or
You may use it in combination of 2 or more type. The amount used is 0.02 to 10% by weight, preferably 0.05 to 5% by weight based on the epoxy group of the epoxy group-containing fluorocopolymer.
% By weight. The progress of the reaction can be traced by quantifying the epoxy group of the epoxy group-containing fluorocopolymer by titration or the like, and the reaction is stopped when the epoxy group disappears within the frame of analytical accuracy. If desired, the reaction can be stopped when the desired amount of epoxy groups is reached.

The reaction between the epoxy group of the fluorine-containing copolymer containing epoxy group and carbon dioxide is usually carried out in an appropriate organic solvent. Examples of the organic solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as n-butanol; esters such as ethyl acetate and n-butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethyl cellosolve. Glycol ethers such as; and various commercially available thinners and the like.

The amount of the organic solvent used is preferably 10 to 100 parts by weight per 100 parts by weight of the epoxy group-containing fluorocopolymer. Next, the method (b) (when copolymerizing a monomer mixture containing an ethylene carbonate group-containing vinyl monomer and a fluorine-containing vinyl monomer as essential components) will be described. In this case, the ethylene carbonate group-containing fluorine-containing copolymer of the present invention essentially comprises a fluorine-containing vinyl monomer (20 to 95 mol%) and an ethylene carbonate group-containing vinyl monomer (1 to 50 mol%). As a copolymerization component, if necessary, other vinyl monomer (0 to 50 mol%) is copolymerized by the same method as in the production of the epoxy group-containing fluorine-containing copolymer in the above-mentioned method (a). Can be obtained by Here, as a specific example of the ethylene carbonate group-containing vinyl monomer,

[0053]

[Chemical 19]

Ethylene carbonate group-containing vinyl ethers such as;

[0055]

[Chemical 20]

Ethylene carbonate group-containing allyl ethers such as;

[0057]

[Chemical 21]

Ethylene carbonate group-containing (meta) such as
Acrylates;

[0059]

[Chemical formula 22]

Examples include ethylene carbonate group-containing crotonic acid esters and the like. Among these, ethylene carbonate group-containing vinyl ethers and ethylene carbonate group-containing allyl ethers are particularly preferable from the viewpoint of copolymerizability with a fluorine-containing vinyl monomer. These may be used alone or in combination of two or more.

Specific examples of the fluorine-containing vinyl monomer, which is an essential monomer component in the method (b), have been described above in (a).
The same thing as the law is mentioned. Specific examples of the other vinyl monomers include the same as the above-mentioned method (a) and the epoxy group-containing vinyl monomers exemplified in the method (a). The ethylene carbonate group-containing fluorine-containing copolymer obtained by the above-mentioned method (a) or (b) has a number average molecular weight of 500 to 100,000.
0, preferably about 1000 to 50,000, fluorine content 5 to 70% by weight, Tg (glass transition temperature)
Is usually -50 to 120 ° C, preferably -20 to 100 ° C.
It is a degree.

The ethylene carbonate group-containing fluorine-containing copolymer of the present invention having such a molecular weight and a glass transition temperature is soluble in an organic solvent and excellent in compatibility with the amine curing agent described below. Becomes Further, the cured coating film obtained by curing the ethylene carbonate group-containing fluorine-containing copolymer of the present invention with an amine-based curing agent is glossy and has excellent hardness and weather resistance.

Here, as the amine-based curing agent, aliphatic polyamine, aromatic polyamine, complex polyamine,
Examples thereof include modified amine polyamines, polyamine compounds such as heterocyclic polyamines, and ketimine compounds in which active hydrogens of these polyamine compounds are temporarily protected in the form of ketimine groups. Specific examples of the polyamine compound include ethylenediamine, 1,2-diaminopropane,
1,3-diaminopropane, 1,4-diaminobutane,
1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane, 1,2-diaminocyclohexane, 1,4-bis (3-aminopropyl) piperazine, 3, 9-bis (3
-Aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Pentaethylenehexamine, isophoronediamine, N,
N'-bis (2-aminomethyl) ethylenediamine,
N, N'-bis (2-aminoethyl) ethylenediamine, N, N'-bis (2-aminopropyl) ethylenediamine, N, N'-bis (2-aminoethyl) -1,3
-Propanediamine, N, N'-bis (2-aminopropyl) -1,3-propanediamine, bis (4-aminocyclohexyl) methane, bis (4-amino-5-methyl-cyclohexyl) methane, 1,3 -Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl)
Cyclohexane, bis (4-aminophenyl) methane,
Bifunctional 1 such as 1,4-bis (aminomethyl) benzene
Primary amine compounds, trifunctional primary amine compounds such as trisaminoethylamine, 4-aminomethyl-1,8-diaminooctane, acrylic polyamines obtained by reacting acid group-containing acrylic resin with ethyleneimine or propyleneimine Etc.

Examples of the ketimine compound include the reaction products of the above-mentioned amine compound and ketone compound or aldehyde compound. Specific examples of these ketone compounds or aldehyde compounds include acetaldehyde, propionaldehyde, n-butyraldehyde, i-butyraldehyde, trimethylacetaldehyde, valeroaldehyde, acrolein, crotonaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone. , Diisobutyl ketone, methylheptenone, cyclohexanone, isophorone, acetophenone and the like. The reaction between the amine compound and the ketone compound or the aldehyde compound may be performed under conventionally known reaction conditions.

The above amine-based curing agents may be used alone or in combination of two or more. Also,
The mixing ratio of the amine-based curing agent and the ethylene carbonate group-containing fluorine-containing copolymer of the present invention is such that the amount of carbonate group / the amount of primary amino group = 2 to 0.5, preferably 1.2 to
0.8 gives good coating performance.

The present invention provides a fluorine-containing coating material containing the above-mentioned novel ethylene carbonate group-containing fluorine-containing copolymer as a main component, wherein the ethylene carbonate group-containing fluorine-containing copolymer is used as a solution. Various solvents can be used for forming the mold paint. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; alcohols such as n-butanol; esters such as n-butyl acetate; ketones such as methyl isobutyl ketone; glycol ethers such as ethyl cellosolve; Furthermore, various commercially available thinners and the like can be mentioned.

The solution type coating composition is usually prepared by using the ethylene carbonate group-containing fluorine-containing copolymer and a solvent, for example, a ball mill, a paint shaker, a sand mill, a jet mill, a three-roll mill, a kneader and the like. It can be carried out by homogeneously mixing using a mixing machine. At this time, an amine curing agent, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an antigelling agent, an ultraviolet absorber and the like can be added as desired.

[0068]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to the embodiments. Molecular weights of various resins: Determined from a polystyrene standard calibration curve using gel permeation chromatography.

(Equipment used) Apparatus: Shimadzu LC-3A Column: Tosoh Corporation TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL Detector: Shimadzu RID-6A Data processing: Shimadzu C- R4A Carrier: Tetrahydrofuran Epoxy value: Measured according to ASTM-D1652. Determination of ethylene carbonate group: Ethylene carbonate group in infrared absorption spectrum (1800 cm ^-1 ).
It was quantified by the absorbance. Gloss, Flexibility, Pencil Hardness: Measured according to JIS K-5400. Weather resistance: Determined according to ASTM G-53.

[0070]

Example 1 The inside of a stainless steel autoclave equipped with a stirrer having an internal volume of 1 liter was replaced with nitrogen gas three times.
Then, 20 g of glycidyl vinyl ether, 14 g of 2.3-dihydrofuran, 14 g of ethyl vinyl ether, 40 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 205 g of butyl acetate and 1.7 g of t-butylperoxypivalate as an initiator were charged, and 6
Polymerization was performed at 7 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced epoxy group-containing fluorocopolymer solution was taken out and reprecipitated with n-hexane and dried. The yield of the fluorine-containing copolymer containing an epoxy group was 197 g.

The number average molecular weight of the obtained epoxy group-containing fluorine-containing copolymer was 9,800, and the fluorine content was 2
The epoxy value was 7.3% and was 0.98 mmol / g. 100 g of the obtained epoxy group-containing fluorocopolymer
Was dissolved in 100 g of xylene, 0.3 g of tetrabutylphosphonium chloride was added, and carbon dioxide was added to 40 g.
The reaction was carried out at 100 ° C for 24 hours while introducing at a rate of ml / min to obtain an ethylene carbonate group-containing fluorocopolymer solution having an ethylene carbonate group content of 0.90 mmol / g and a nonvolatile content (NV) of 50.7%.

[0072]

Example 2 The inside of an autoclave with a stirrer made of stainless steel and having an inner volume of 1 liter was replaced with nitrogen gas three times.
Then, 23 g of 4-hydroxybutyl vinyl ether,
25 g of cyclohexyl isocyanate, 50 g of isobutyl vinyl ether and 98 g of xylene were charged and reacted at 80 ° C. for 6 hours. Then, 34.2 g of glycidyl allyl ether, 117 g of chlorotrifluoroethylene, 151 g of xylene and 2.8 g of octanoyl peroxide as an initiator were charged, and polymerization was carried out at 73 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced epoxy group-containing fluorocopolymer solution was taken out and reprecipitated with n-hexane and dried. The yield of the fluorine-containing copolymer containing an epoxy group was 238 g. The number average molecular weight of the obtained epoxy group-containing fluorocopolymer was 8,400, the fluorine content was 22.8%, and the epoxy value was 1.12 mmol.
/ G.

100 g of the obtained epoxy group-containing fluorine-containing copolymer was dissolved in 100 g of xylene, 0.3 g of tetrabutylammonium chloride was added, and the reaction was carried out at 100 ° C. for 24 hours while introducing carbon dioxide at 40 ml / min. Let ethylene carbonate group content 1.09 mmol /
An ethylene carbonate group-containing fluorocopolymer solution containing 5 g of a non-volatile component (NV) was obtained.

[0074]

Example 3 The inside of an autoclave with an internal volume of 1 liter and made of a stainless steel and equipped with a stirrer was replaced with nitrogen gas three times.
Then, glycidyl crotonate vinyl ether 28
g, 25 g of vinyl pivalate, 60 g of isobutyl vinyl ether, 100 g of tetrafluoroethylene, 213 g of xylene and 1.7 g of t-butylperoxypivalate as an initiator, and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted tetrafluoroethylene was removed, the autoclave was opened, and the epoxy group-containing fluorocopolymer solution produced was taken out and reprecipitated with n-hexane for drying. The yield of the fluorine-containing copolymer containing an epoxy group was 167 g.

The obtained epoxy group-containing fluorocopolymer had a number average molecular weight of 7,800 and a fluorine content of 3
The epoxy value was 5.3% and was 0.72 mmol / g. 100 g of the obtained epoxy group-containing fluorocopolymer
Was dissolved in 100 g of xylene, 0.2 g of triphenylphosphine and 0.1 g of potassium iodide were added, and carbon dioxide was introduced at 40 ml / min.
Reaction for 4 hours Ethylene carbonate group content 0.70m
An ethylene carbonate group-containing fluorine-containing copolymer solution having a mol / g and a nonvolatile content (NV) of 50.2% was obtained.

[0076]

Example 4 The inside of an autoclave with an internal volume of 1 liter and made of stainless steel and equipped with a stirrer was replaced with nitrogen gas three times.
Then, 43 g of (2-oxo-1,3-dioxolan-4-yl) methyl vinyl ether, 14 g of 2.3-dihydrofuran, 3 g of crotonic acid, 46 g of isobutyl vinyl ether, 117 g of chlorotrifluoroethylene, 223 g of butyl acetate, and as an initiator. 1.7 g of t-butyl peroxypivalate was charged and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced ethylene carbonate group-containing fluorine-containing copolymer solution was taken out and reprecipitated with n-hexane and dried. The yield of the fluorine-containing copolymer containing an ethylene carbonate group was 214 g.

The ethylene carbonate group-containing fluorine-containing copolymer obtained had a number average molecular weight of 11,800, a fluorine content of 25.3% and an ethylene carbonate group content of 1.32 mmol / g.

[0078]

Example 5 The inside of an autoclave with a stirrer made of stainless steel and having an internal volume of 1 liter was replaced with nitrogen gas three times.
Then, 23 g of 4-hydroxybutyl vinyl ether,
25 g of cyclohexyl isocyanate, 50 g of isobutyl vinyl ether and 98 g of xylene were charged and reacted at 80 ° C. for 6 hours. Then, 32 g of (2-oxo-1,3-dioxolan-4-yl) methyl allyl ether,
Glycidyl vinyl ether (10 g), chlorotrifluoroethylene (117 g), xylene (159 g) and octanoyl peroxide (2.8 g) as an initiator were charged at 73 ° C.
Polymerization was carried out for 8 hours. After completion of the polymerization, unreacted chlorotrifluoroethylene was removed, the autoclave was opened, and the produced ethylene carbonate group-containing fluorine-containing copolymer solution was taken out and reprecipitated with n-hexane and dried. The yield of the fluorine-containing copolymer containing an ethylene carbonate group was 238 g.

The ethylene carbonate group-containing fluorine-containing copolymer thus obtained had a number average molecular weight of 11,400, a fluorine content of 22.2% and an ethylene carbonate group content of 0.77 mmol / g.

[0080]

Example 6 The inside of a stainless steel autoclave with an agitator having an inner volume of 1 liter was replaced with nitrogen gas three times.
Then, 32 g of (2-oxo-1,3-dioxolan-4-yl) methyl vinyl ether, 14 g of 2.3-dihydrofuran, 60 g of isobutyl vinyl ether, 100 g of tetrafluoroethylene, 206 g of butyl acetate and t-butyl peroxy as an initiator. 1.7 g of pivalate was charged and polymerization was carried out at 67 ° C. for 8 hours. After completion of polymerization
Unreacted tetrafluoroethylene was removed, the autoclave was opened, and the produced ethylene carbonate group-containing fluorocopolymer solution was taken out and reprecipitated with n-hexane for drying. The yield of the fluorine-containing copolymer containing an ethylene carbonate group was 187 g.

The number average molecular weight of the obtained ethylene carbonate group-containing fluorocopolymer was 10,700, the fluorine content was 36.3%, and the ethylene carbonate group content was 0.94 mmol / g.

[0082]

Example 7 The inside of an autoclave with a stirrer made of stainless steel and having an internal volume of 1 liter was replaced with nitrogen gas three times.
Then, 43 g of (2-oxo-1,3-dioxolan-4-yl) methyl vinyl ether, 9 g of crotonic acid, 30 g of isobutyl vinyl ether, 22 g of ethyl vinyl ether, 150 g of hexafluoropropylene, 252 g of xylene and tert-butyl peroxypyroxy as an initiator. 1.7 g of barrate was charged and polymerization was carried out at 67 ° C. for 8 hours. After completion of the polymerization, unreacted hexafluoropropylene was removed, the autoclave was opened, and the produced ethylene carbonate group-containing fluorocopolymer solution was taken out n-
It was reprecipitated with hexane and dried. The yield of the ethylene carbonate group-containing fluorine-containing copolymer was 231 g.

The ethylene carbonate group-containing fluorocopolymer thus obtained had a number average molecular weight of 7,800, a fluorine content of 44.3% and an ethylene carbonate group content of 1.12 mmol / g.

[0084]

Example 8 3,9-bis (3-aminopropyl)-
2,4,8,10-Tetraoxaspiro [5,5] undecane was heated to reflux with excess methyl isobutyl ketone, water produced was removed by a water drop separator, and then distilled to obtain a corresponding ketimine compound. .

[0085]

Examples 9 to 15 Ethylene carbonate group-containing fluorocopolymer solutions obtained in Examples 1 to 3 (solid content 50
%), And the ethylene carbonate group-containing fluorine-containing copolymers obtained in Examples 4 to 7 each having a solid content of 50% adjusted with xylene as a main agent, and the ketimine compound as a curing agent is an ethylene carbonate group / ketimine. Group = 1 /
After blending so as to be 1, each was coated with xylene as a thinner with Ford cup # 4 for 15 seconds. After baking the obtained coating film at 80 ° C. for 1 hour,
The coating film physical properties were measured.

The results of the coating film evaluations are shown in Table 1.

[0087]

Comparative Example 1 A 4-necked flask equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen gas inlet tube was used (2-oxo-1,3
-Dioxolan-4-yl) methyl methacrylate 20
g, styrene 20 g, butyl acrylate 27 g, methyl methacrylate 30 g, and methacrylic acid 3 g, 20 g of a monomer mixture is charged with toluene 50 g, isobutyl acetate 20 g, t-butyl peroctate 1 g, and azobisisobutyronitrile 0.5 g. At 90 ° C. for 1 hour, then 30 minutes to raise the temperature to 115 ° C.,
80 g of the remaining monomer mixture and 3 parts of isobutyl acetate at the same temperature
A mixture of 0 g, t-butyl peroctate 1 g, and azobisisobutyronitrile 0.5 g was added dropwise over 3 hours, and the mixture was kept at the same temperature for 10 hours. Thus, a resin solution having a number average molecular weight of 13,000 and a nonvolatile content of 50.2% was obtained.

[0088]

[Comparative Example 2] The resin solution obtained in Comparative Example 1 was used as a main component,
After blending the ketimine compound obtained in Example 8 as a curing agent so that ethylene carbonate group / ketimine group = 1/1, it was coated with xylene as a thinner with Ford cup # 4 for 15 seconds. The obtained coating film is 8
After baking for 1 hour at 0 ° C., the physical properties of the coating film were measured.

The results of coating film evaluation are shown in Table 1.

[0090]

[Table 1]

[0091]

As is clear from the above results, according to the present invention, a urethane coating film is formed without using a polyisocyanate compound, being soluble in an organic solvent and excellent in compatibility with a curing agent. The obtained ethylene carbonate group-containing fluorine-containing copolymer can be easily provided.

Further, the fluorine-based coating composition of the present invention containing the ethylene carbonate group-containing fluorine-containing copolymer as a main component is
It is possible to give a coating that is glossy and hard and has excellent chemical resistance and weather resistance under mild conditions.For example, it can be applied as a baking paint for color rigid plate, color aluminum plate, aluminum sash, or on-site construction. It is useful as a normal dry coating.

As for the material of the base material, in addition to metallic materials, inorganic materials such as glass and concrete, FRP,
It is preferably used for coating plastics such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride and polyvinylidene chloride, and organic materials such as wood. Further, the fluorine-based paint is also useful in specific applications such as automobile top coats, exterior colored glass, and cement roof tiles.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C09D 127/12 PFG 9166-4J 129/10 PFP 6904-4J

Claims (2)

[Claims] 1. A fluorine-containing copolymer containing an ethylene carbonate group, which comprises the following components as essential components. Formula (A) Unit represented by 20 to 95 mol% (B) Formula Unit represented by 1 to 50 mol% 2. A coating material containing an ethylene carbonate group-containing fluorine-containing copolymer as an essential component, which comprises the following components as essential components. Formula (A) Unit represented by 20 to 95 mol% (B) Formula Unit represented by 1 to 50 mol%