JPH10101739A - Production of fluorocopolymer, and fluororesin coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorocopolymer which has the weatherability and chemi cal resistance inherent in fluororesins and is soluble in a petroleum-derived solvent scarcely having a petroleum odor and to provide a coating compsn. prepd. therefrom. SOLUTION: This process comprises producing a fluorocopolymer soluble in a petroleum-derived solvent and having an OH value of 5-120mgKOH/g by copolymerizing 20-47 mol% fluoroolefin, 1-25mol% hydroxylated polymerizable compd., 0.1-10mol% 10-15C linear unsaid. fatty acid, and 15-75mol % other copolymerizable vinyl compds. The copolymn. is conducted in a petroleum- derived solvent which mainly comprises isoparaffins having initial boiling points of 150 deg.C) or higher and does not substantially contain an arom. compd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fluorine-based copolymer soluble in a petroleum solvent containing isoparaffin as a main component, and a composition for a fluororesin coating comprising the fluorine-based copolymer and a petroleum-based solvent. About.

[0002]

2. Description of the Related Art Conventionally, fluororesin coatings utilizing the excellent weather resistance of a fluorocopolymer have been industrialized. Particularly recently, a solvent-soluble fluorine-based copolymer having a cured site has been synthesized (for example, JP-A-57-34107, JP-A-61-57609, etc.), and is used for construction, automobile, and chemical. It is widely used as a weather-resistant paint in fields such as industry. The main components of these paint resins are fluorine-based monomers such as chlorotrifluoroethylene, tetrafluoroethylene, and vinylidene fluoride, and use hydrocarbon-based monomers such as vinyl esters and vinyl ethers as copolymerization components. This increases the solubility of the resin.

[0003] However, in the current tide of the regulation of organic solvent emission, there are cases where synthetic resins soluble in petroleum solvents such as mineral terpenes and solvent naphtha are used for coatings, and in particular, petroleum solvent-soluble acrylics are used. Urethane resin continues to expand the market. As a result, there is a growing demand for repainting properties coated with such petroleum-based solvent-soluble resins.However, conventional fluororesin paints use organic solvents such as xylene and butyl acetate as the main component of the thinner. The surface of the coating film coated with the soluble resin was damaged, and repelling and discoloration were likely to occur, making it difficult to use. To address this problem, mineral turpen-soluble fluorine coatings are also commercially available, but because of the non-crosslinked lacquer type, the solvent resistance, water resistance, stain resistance and the like were insufficient. In recent years, water-based or powder-type paints that place importance on the environment and suppress the emission of organic solvents have been put into practical use, but have not yet surpassed solvent-type paints in terms of coating film performance. More recently, a mineral terpene-soluble polyisocyanate has been developed, and a mineral terpene-soluble fluororesin paint having a cured site is being developed.

[0004] However, mineral turpen has a gasoline odor, and painting in urban areas or indoors requires environmental consideration. Solvent-soluble fluororesin coatings have the disadvantage that they are excellent in weather resistance but they are easily stained. However, as a solution to this, an alkyl silicate compound is mixed to achieve a low contact angle and stain resistance. Fluororesin paints that exhibit this have been put to practical use.

[0005]

The present invention relates to a fluororesin paint for forming a coating film having excellent physical properties such as weather resistance and chemical resistance, which is not only soluble in petroleum-based solvents. The present invention provides a composition for a fluororesin coating which is free of petroleum odor and is considered for a working environment, and a method for producing a fluorocopolymer used therefor.

[0006]

Means for Solving the Problems The present inventors have studied the fluororesin for paint in detail and found that polymerization is carried out using a solvent mainly composed of a petroleum-based solvent having a low odor and containing no aromatic compound. As a result, it has been found that a fluororesin having low odor and soluble in a petroleum solvent containing no aromatic compound can be obtained, and the present invention has been completed.

That is, the present invention relates to a polymerizable compound 1 containing 20 to 47 mol% of a fluoroolefin and containing a hydroxy group.
OH value is obtained by copolymerizing a monomer consisting of 0.1 to 25 mol%, 0.1 to 10 mol% of a linear unsaturated fatty acid having 10 to 15 carbon atoms and 15 to 75 mol% of another copolymerizable vinyl compound. Is a petroleum-based solvent-soluble fluorine-based copolymer having a boiling point of 5 to 120 mgKOH / g, which is mainly composed of isoparaffin having an initial boiling point of 150 ° C. or higher and substantially containing no aromatic compound. This is a method for producing a fluorine-based copolymer, which is characterized by copolymerizing in a solvent. It has also been found that a hydroxy group-containing vegetable oil, a saturated fatty acid, an alkyl silicate compound or the like can be added to the fluorine-based copolymer.

Hereinafter, the present invention will be described in detail.

The polymerization solvent used in the present invention is a petroleum solvent mainly comprising isoparaffin having an initial boiling point of 150 ° C. or higher and containing substantially no aromatic compound. As the petroleum solvent having an initial boiling point of 150 ° C. or higher and containing substantially no aromatic compound, a solvent consisting of a single component of isoparaffin having a boiling point of 150 ° C. or higher may be used. It is preferable to use a commercially available mixed solvent for paint, for polymerization, and for dissolving various substances. Examples of such materials include Shellsol 70 (initial boiling point: 156 ° C., aromatic content = 0.1% or less) and Shellsol 71 (initial boiling point: 179 ° C., aromatic content) manufactured by Shell Japan Co., Ltd. Amount = 0.1% or less), Shellsol 72 (initial boiling point: 215 ° C., aromatic content = 0.1% or less), Shellsol S, Isopar G manufactured by Exxon Chemical
(Initial boiling point 156 ° C, aromatic content = 0.08%), Isopar H (initial boiling point 176 ° C, aromatic content = 0.04)
%), Isopar L (initial boiling point 188 ° C., aromatic content =
0.1%), Isopar M (initial boiling point 208 ° C., aromatic content = 0.08%) and the like.

The fluoroolefin used in the present invention is
Examples thereof include chlorotrifluoroethylene, tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoropropene, and hexafluoroisobutene, which accounts for 20 to 47 mol% of all monomers. If it is less than 20 mol%, the weather resistance is low, and if it exceeds 47 mol%, the solubility in petroleum solvents is reduced. Copolymers for fluororesin paints that have been developed in the past include:
In many cases, the fluoroolefin unit is about 50 mol% and is arranged alternately in the molecule and is difficult to be dissolved in isoparaffin. However, the fluorocopolymer according to the present invention is excellent in that the fluoroolefin unit is less than 47 mol%. It is considered that the obtained solubility was obtained. A unit amount of fluoroolefin of less than 43% is more preferred.

The polymerizable compound having a hydroxy group used in the present invention includes allyl ether, vinyl ether, crotonic acid-modified compound and the like. For example, alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, and hydroxyalkyl allyl ethers such as hydroxybutyl allyl ether , Hydroxyalkyl vinyl ethers such as hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether and hydroxyhexyl vinyl ether; alkylene glycol monovinyl ethers such as diethylene glycol monovinyl ether and polyethylene glycol monovinyl ether; Crotonic acid-modified compounds such as hydroxyethyl acrylate is employed. Among them, since allyl ether increases the solubility of the copolymer, it is preferable to use it for part or all of the hydroxy-containing polymerizable compound. The composition ratio of these hydroxy group-containing polymerizable compounds is 1 to 25 mol% of all monomers, and the OH value is 5 to 120 mg KO.
It is copolymerized so as to be in the range of H / g. The composition ratio of the hydroxy group-containing polymerizable compound is less than 1 mol% or OH
When the value is less than 5 mgKOH / g, the amount of the crosslinked site is small, the weather resistance and the solvent resistance are not sufficient, and the effect as a two-part crosslinked paint is not exhibited. In addition, 25 mol% or an OH value of 12
If it exceeds 0 mgKOH / g, the solubility in isoparaffin decreases, which is not preferable.

The straight-chain unsaturated fatty acid having 10 to 15 carbon atoms used in the present invention has a general formula X-CH = CH- (CH ₂ ) _q -COOH (where X is a hydrogen atom or CH ₃ , q is 6-1
It is an integer of 1. And specific examples thereof include 9-hendecenoic acid, 10-hendecenoic acid, 11-dodesenic acid, and 14-pentadecenoic acid, and more preferably an unsaturated double bond at the terminal. And highly polymerizable 10-hendesenoic acid. The acid component in the fluorocopolymer introduced by the linear unsaturated fatty acid acts as a catalyst for the crosslinking reaction or improves the pigment dispersibility, but when a linear unsaturated fatty acid having 9 or less carbon atoms is used. Decreases the solubility of the fluorine-based copolymer in isoparaffin, and the fluorine-based copolymer tends to gel during polymerization or during coating, or the surface of the coating film is poor, resulting in yellow skin and poor gloss. It is not preferable because it may occur. The copolymerization amount of the linear unsaturated fatty acid used in the present invention is 0.1 to 10 mol% of all monomers. If the amount is less than 0.1 mol%, the pigment dispersibility is not improved. If the amount exceeds 10 mol%, the solubility in isoparaffin is reduced and the pot life after the addition of the curing agent is undesirably reduced. When an alkyl silicate is blended in the coating composition, this linear unsaturated fatty acid particularly plays an important role in promoting the hydrolysis of the alkyl silicate, and its copolymerization amount is 0.1% of the total monomers. 2 to 10 mol% is preferred. When an aluminum chelate compound is further added, the carboxyl group serves as a crosslinking site.

The copolymerizable vinyl compound used in the present invention is not particularly limited, but preferably includes vinyl esters, vinyl ethers, allyl ethers, olefins and the like. As the vinyl ester, an ester compound having a carbonyl group in the molecule which is polymerizable, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl laurate, myristic acid Vinyl, vinyl palmitate, vinyl stearate, vinyl versatate 9, vinyl versatate 10 and vinyl benzoate. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether. Further, as the allyl ether, for example, ethyl allyl ether, butyl allyl ether, benzyl allyl ether, allyl glycidyl ether, cyclohexyl allyl ether and the like are used. Ethylene, propylene and the like are used as olefins. Further, vinyl silane-based compounds, (meth) acrylic acid esters and the like can be used. These monomers are 2
More than one kind may be used in combination, and the composition thereof is 15 to 75 mol% of the total monomers. If it is less than 15 mol%, solubility in isoparaffin is not exhibited, and if it exceeds 75 mol%, the weather resistance of the coating film is undesirably reduced.

The process for producing a fluorine-based copolymer of the present invention comprises:
An ordinary radical polymerization method can be adopted, and the polymerization form is solution polymerization using a polymerization solvent comprising the above-mentioned specific isoparaffin. By using isoparaffin as the polymerization solvent, a fluorine-based copolymer growing radical is chain-transferred to the isoparaffin during polymerization and bonded to a molecular end, and a structural unit derived from isoparaffin is introduced into the fluorine-based copolymer. Conceivable. In fact, it will be shown later that a fluorine-based copolymer polymerized in a polar solvent such as xylene or butyl acetate is hardly soluble in isoparaffin. Although the temperature of the polymerization step depends on the radical polymerization initiator used, it is usually from 0 to 13
0 ° C. Examples of the radical initiator include dicarbonates such as diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate and di-2-ethylhexylperoxydicarbonate, or n-heptafluorobutyric peroxide and lauroylperoxide. Oxypivalates, diacyl peroxides such as t-butyloxyneodecanate, alkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, t-butylperoxypivalate, t-butyl Conventional radical initiators such as peroxyesters such as peroxyneodecanoate can be used.

The molecular weight of the fluorine-based copolymer thus polymerized is not particularly limited, but may range from 1,000 to 50,000 (number average molecular weight; in terms of styrene) depending on the required strength and flexibility of the coating film. It is desirable to use in the range, more preferably about 3,000 to 30,000. If it is less than 1,000, the weather resistance and flexibility of the coating film will be reduced, and if it exceeds 50,000, it will have a disadvantage that it has a high viscosity when it is made into a coating material and is difficult to handle.

With respect to 100 parts by weight of the fluorocopolymer obtained by the method of the present invention, 30 parts by weight or less of a hydroxy group-containing vegetable oil and / or 10 parts by weight or less of a saturated fatty acid can be blended. The addition of the hydroxy group-containing vegetable oil has the effects of reducing the viscosity of the isoparaffin solution of the fluorine-based copolymer and increasing the solubility when the degree of dilution is increased.
The hydroxy group-containing vegetable oil according to the present invention is a vegetable oil having a hydroxy group by partial hydrolysis or modification by reaction with an alkylene oxide or the like,
The type of vegetable oil is not particularly limited. Examples of the vegetable oil include castor oil, soybean oil, and linseed oil. Specific examples include a partially hydrolyzed product of these vegetable oils and a modified castor oil modified by reacting castor oil with ethylene oxide. The hydroxy group in the molecule of the vegetable oil functions as a crosslinking site together with that of the fluorine-based copolymer. Hydroxy group-containing vegetable oil is a fluorocopolymer 10
30 parts by weight or less is added to 0 parts by weight. If it exceeds 30 parts by weight, the weather resistance of the coating film is undesirably reduced.

The saturated fatty acids according to the present invention include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid,
Fatty acids having tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid or higher carbon atoms are exemplified. Fatty acids having a carbon number equal to or greater than heptanoic acid are preferred because the odor of the fluororesin coating composition can be further reduced. Also, branched alkanoic acids such as isovaleric acid, trimethylpropanoic acid, methyldecanoic acid, and 2-butyl-5-methylpentanoic acid can be used. The addition amount of these fatty acids is 10 parts by weight or less based on 100 parts by weight of the fluorocopolymer. If the amount exceeds 10 parts by weight, the weather resistance of the coating film and the solubility of the fluorine-based copolymer decrease, which is not preferable.

In the present invention, for the purpose of improving the stain resistance, 1 to 15 parts by weight of an alkyl silicate is contained based on 100 parts by weight of a fluorine-based copolymer, and a polyoxyalkylene group and an alkoxysilyl group are contained in the molecule. Compound 0.1 ~
10 parts by weight can be blended. Here, alkyl silicate is a general formula

[0019]

Embedded image

Wherein Y is an alkyl group having 1 to 8 carbon atoms;
m represents 0 or an integer of 11 or less. Or a condensate thereof, specifically, for example, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-2-silane
Methoxyethoxysilane, tetra-2-ethylhexyloxysilane and the like, or a partial hydrolyzate thereof can be mentioned. Although the structure of these partial hydrolysates is not clear, it is a polysilicate ester composed of a skeleton composed of Si—O bonds and an alkoxy group. In some cases, it may have a ring structure. Although any production method may be used, for example, it can be obtained by adding water, an acid, and / or a solvent to tetraalkoxysilane and partially hydrolyzing and condensing the resultant. Such partially hydrolyzed alkyl silicates have a degree of condensation, structure,
A variety of different alkoxy groups are commercially available, for example, M silicate 51, ethyl silicate 40,
Ethyl silicate 45 (product of Tama Chemical Industry Co., Ltd.), Ethyl silicate 40 (product of Colcoat Co., Ltd.)
Having an effective silica content of about 28 to 52% by weight, and further hydrolyzing them to reduce the silica content to 57% by weight.
It is also possible to use alkyl silicates concentrated to.

Further, the compound according to the present invention having a polyoxyalkylene group and an alkoxysilyl group in the molecule is represented by the general formula: R- (OR ') _n -O- A saturated or unsaturated linear hydrocarbon group of 28, R ′ is an alkylene group having 1 to 4 carbon atoms, and n is an integer of 1 to 30), and a general formula: —SiA _p B _(3-p) (wherein B is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, A
Represents an alkoxy group having 1 to 3 carbon atoms, and p represents an integer of 1 to 3. )). As such a compound, for example, a glycol monoalkyl ether represented by the general formula: R- (OR ') _n- OH (wherein R and R'n are the same as described above); A compound obtained by reacting an isocyanate group-containing alkoxysilane represented by the formula: OCN (CH ₂ ) ₃ SiA _p B _(3-p) (where A, B and p are the same as those described above); _{- (O-R ') n} -O-CO-NH- (CH 2) 3 Si
_{A p B (3-p)} ( wherein, R, R'n, A, B , p is the same. As defined above) can be mentioned.

The straight-chain hydrocarbon group represented by R has 8 to 28 carbon atoms, preferably 12 to 22 carbon atoms, and may be saturated or unsaturated, for example, lauryl to achieve solubility in isoparaffin. Groups, palmityl group, stearyl group, oleyl group, linole group, linolene group and the like.

Examples of the alkylene group having 1 to 4 carbon atoms represented by R ′ include an ethylene group, a propylene group and a tetramethylene group, and n representing the number of repeating units of the oxyalkylene group is an integer of 1 to 30. Yes, about 6 to 20 is preferable.

The alkoxysilane containing an isocyanate group is not particularly restricted but includes, for example, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltrimethoxysilane And the like.

These alkyl silicates and the compound having a polyoxyalkylene group and an alkoxysilyl group in the molecule reduce the contact angle of the coating film surface immediately after coating due to the synergistic effect of the fluorine-based copolymer, and cause rain streaks. This is considered to have the effect of making it difficult. The amount of the alkyl silicate to be added is as follows.
It is preferably used in an amount of 1 to 15 parts by weight based on parts. If the amount is less than 1 part by weight, the stain resistance is not sufficient, and
If the amount is more than the weight part, there is a disadvantage that the coating film is easily damaged. The compound having a polyoxyalkylene group and an alkoxysilyl group in the molecule can be used in the range of 0.1 to 10 parts by weight. If the amount is less than 0.1 part by weight, the stain resistance of the coating film is not sufficient, and if it exceeds 10 parts by weight, the weather resistance of the coating film decreases.

The fluororesin coating composition of the present invention can be diluted with only a petroleum solvent. The petroleum-based solvent referred to here is a mixture of paraffin and naphthene, which is commercially available as a low-odor solvent, including the isoparaffin or a mixed solvent thereof already mentioned in the polymerization solvent, for example,
Examples include Shellsol D40, Shellsol D70, and Shellsol D100 from Shell Japan Co., Ltd., and Exol D30, Exol D40, Exol D80, and Exol D110 from Exxon Chemical Co., Ltd. Mineral terpenes or naphtha-based solvents containing aromatic compounds can also be used as thinners. Further, when it is not necessary to consider the problem of odor, it is possible to use xylene, butyl acetate and the like which are ordinary synthetic thinners.

In the fluororesin coating composition of the present invention, general-purpose crosslinkers such as polyisocyanate crosslinkers and melamine crosslinkers which are soluble in petroleum solvents can be used without limitation. In particular, a polyisocyanate whose polarity is reduced from the viewpoint of solubility in isoparaffin and petroleum solvent is preferably employed. Specifically, as a polyisocyanate, petroleum solvent, hexamethylene diisocyanate soluble in mineral terpene, etc., non-yellowing polyisocyanate such as isophorone diisocyanate or polycisocyanurate prepared therefrom, polyisocyanate adduct, polyisocyanate block For example, TP-100 and TP-703 of Nippon Polyurethane Industry, TPLS2071 of Sumitomo Bayer Urethane, Duranate TSA100 and TSS100 of Asahi Kasei Kogyo Co., Ltd. may be mentioned as preferable examples. Naturally, equivalent or similar products can be used. However, the present invention is not limited to these.

The fluororesin coating composition of the present invention may contain an aluminum chelate compound soluble in a petroleum solvent as a curing agent. Specific examples include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, and aluminum monoacetylacetonate bis (ethyl acetoacetate), but are not necessarily limited thereto. . The crosslinking reaction with the aluminum chelate is performed by a reaction with a carboxyl group in the fluorine-based copolymer.

The fluororesin coating composition of the present invention is a resin soluble in other petroleum solvents, such as acrylic polyols and vinyl esters, if the fluorocopolymer produced by the method of the present invention is the main component. Resin, silicone compound,
Oxyalkylene resins and alkyd resins can be added. In addition, UV absorbers, light stabilizers, rust inhibitors, dispersants,
Anti-dripping agents, pigments, dyes and the like can also be added.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

[0031]

【Example】

[Example 1] SU with an internal capacity of 2 liters equipped with an electromagnetic stirrer
In an S-made autoclave, 63 g (10 mol%) of ethylene glycol monoallyl ether, 10-hendecenoic acid 2
2.9 g (2 mol%), 80 g of vinyl pivalate (10
Mol%), 434 g (38 mol%) of vinyl versatate 9 and 300 g of Shellsol 70 (isoparaffin manufactured by Shell Japan; initial boiling point: 156 ° C) (35 parts by weight based on 100 parts by weight of all monomers), t- 8 g of butyl peroxypivalate (manufactured by NOF CORPORATION) was charged, and degassing was repeated three times with degassing and replacement with nitrogen gas. Then, 288 g (40 mol%) of chlorotrifluoroethylene was charged, and 3 g of sodium carbonate decahydrate was added. Polymerization was performed at 55 ° C. for 20 hours. After completion of the polymerization, the content was taken out after purging the remaining monomer. The resin had almost no odor, and the resin was obtained as a varnish dissolved in a solvent. The obtained varnish was filtered and the concentration was adjusted with Shellsol 70 to obtain a transparent fluororesin varnish having a solid content of 60% by weight. Table 1 shows the OH value and acid value of the obtained fluororesin.

[0032]

[Table 1]

CTFE: chlorotrifluoroethylene TFE: tetrafluoroethylene VPv: vinyl pivalate V-9: versatic vinyl catenate EVE: ethyl vinyl ether CHVE: cyclohexyl vinyl ether EGMAE: ethylene glycol monoallyl ether HBVE: hydroxybutyl vinyl ether HDA: 10 -Hendesenic acid Shelsol 70: isoparaffin manufactured by Shell Japan Solubility: soluble, x insoluble [Examples 2 to 3] Polymerization was carried out in the same manner as in Example 1 with the monomer composition shown in Table 1. In each case, after the end of polymerization,
When the content was taken out after purging the residual monomer, there was almost no odor, and in each case, the resin was obtained as a varnish dissolved in a solvent. The obtained varnish was filtered, and the concentration was adjusted with Shellsol 70 to obtain a transparent solid content of 60%.
% By weight of a fluororesin varnish. Table 1 shows the OH value and acid value of the obtained fluororesin.

Comparative Examples 1 and 2 Polymerization was carried out in the same manner as in Example 1 with the monomer compositions shown in Table 1. In each case, after the polymerization was completed, the remaining monomer was purged and the content was taken out. As a result, the content was opaque and the resin was not completely dissolved. In each case, there was almost no odor. Comparative Example 1 was a system in which the copolymerization amount of fluoroolefin was as large as 50 mol% of all monomers and did not contain a linear unsaturated fatty acid, and Comparative Example 2 was a copolymer in which the copolymerization amount of fluoroolefin was 50 mol% of all monomers. %.

Comparative Example 3 The polymerization of Example 1 was repeated except that 300 g of butyl acetate was used as the polymerization solvent. After completion of the polymerization, the content was taken out after purging the remaining monomer. As a result, the content was translucent and the resin was not completely dissolved. [Application Example 1] 100 parts by weight of the fluororesin varnish (solid content 60% by weight) manufactured in Example 1 was uniformly mixed with 48 parts by weight of titanium oxide CR90 manufactured by Ishihara Sangyo using a dispersion mill,
A white paint base was prepared.

Then, 0.06 parts by weight of a leveling agent BYK301 of Big Chemie Co. and 7.8 of an isocyanurate-type polycisocyanate (duranate TSS100) prepared from hexamethylene diisocyanate manufactured by Asahi Kasei Kogyo Co., Ltd. were used as the main components of the obtained white paint. The mixture was diluted with Shellsol 70 and Exol D40 (paraffin / naphthene mixture with a low odor solvent manufactured by Exxon Chemical) to obtain a coating material. Next, this was spray-coated on an aluminum plate so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

With respect to the coated plate manufactured as described above,
Each item such as solvent resistance, water resistance, weather resistance, and color difference was evaluated. Table 2 shows the results.

[0038]

[Table 2]

CR90: Titanium oxide pigment manufactured by Ishihara Sangyo TSS100: Polyisocyanate aluminum chelate ALCH manufactured by Asahi Kasei Corporation Aluminum chelate compound manufactured by Kawaken Fine Chemicals ES40: Ethyl silicate 4 manufactured by Tama Chemical Industry
0 Newcol / Y9030: Nippon Emulsifier Industry Newc
ol1203 (polyoxyethylene oleyl ether)
Reaction product of Nippon Unicar Y9030 (isocyanate propyl triethoxysilane) Mineral terpene: Laws Exol D40 manufactured by Shell Japan: Low odor thinner manufactured by Exxon Chemical (paraffin / naphthene mixture) [Application Examples 2 to 4] Using the produced fluororesin varnish, titanium oxide CR90 was added to 100 parts by weight of the fluororesin varnish (solid content: 60% by weight) as in Application Example 1.
The mixture was uniformly mixed with an 8 parts by weight dispersion mill to prepare a white paint base material.

Next, 0.06 parts by weight of a leveling agent BYK301 manufactured by Big Chemie Co., Ltd. was added to the obtained white paint base material, and Duranate TSS100 manufactured by Asahi Kasei Corporation or aluminum chelate compound ALCH manufactured by Kawaken Fine Chemicals was used.
(Ethyl acetoacetate aluminum diisopropylate) was added in the amounts shown in Table 2.

Further, in application example 2, 5 parts by weight of castor oil,
In Application Example 4, 5 parts by weight of stearic acid was added, and each was diluted with a thinner to obtain a paint. Next, this was spray-coated on an aluminum plate so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

With respect to the coated plate manufactured as described above,
Each item such as solvent resistance, water resistance, weather resistance, and color difference was evaluated. Table 2 shows the results. [Application Example 5] Using the fluororesin varnish produced in Example 2, in the same manner as in Application Example 1, 48 parts by weight of titanium oxide CR90 was uniformly mixed with 100 parts by weight of a fluororesin varnish (solid content: 60% by weight) using a dispersion mill. Then, a white paint base was prepared.

Next, 0.06 parts by weight of a leveling agent BYK301 manufactured by Big Chemie Co. and 8 parts by weight of duranate TSS100 manufactured by Asahi Kasei Kogyo were added to the obtained white paint base material. Further, 2 parts by weight of stearic acid and 8 parts by weight of ethyl silicate 40 manufactured by Tama Chemical Industry were added and mixed.

Separately, polyoxyethylene oleyl ether Newcol-1203 manufactured by Nippon Emulsifier and isocyanate propyltriethoxysilane Y90 manufactured by Nippon Unicar.
30 in an autoclave at 80 ° C. while stirring under a nitrogen atmosphere so that the molar ratio of OH group / NCO group becomes 1/1.
Compound (A) was obtained by addition reaction for 0 hours.

After adding 2 parts by weight of the compound (A) to the white paint base obtained above, it was diluted with a thinner shown in Table 2 to obtain a paint. Next, the aluminum plate was spray-coated so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

With respect to the coated plate manufactured as described above,
Each item such as solvent resistance, water resistance, weather resistance, and color difference was evaluated. Table 2 shows the results. [Reference Examples 1 and 2] Using the fluororesin varnish produced in Examples 1 and 2, titanium oxide C was added to 100 parts by weight of the fluororesin varnish (solid content: 60% by weight) in the same manner as in Application Example 1.
48 parts by weight of R90 were uniformly mixed by a dispersion mill to prepare a white paint base material.

Next, 0.06 parts by weight of a leveling agent BYK301 manufactured by Big Chemie Co. and duranate TSS100 manufactured by Asahi Kasei Kogyo Co., Ltd. were added to the obtained white paint base material in the amounts shown in Table 2.

Further, in Reference Example 1, castor oil was added in an amount of 20 parts by weight, and in Reference Example 2, stearyl acid was added in an amount of 7 parts by weight. Next, the aluminum plate was spray-coated so as to have a thickness of about 40 microns, and dried and cured at room temperature for 10 days.

With respect to the coated plate manufactured as described above,
Each item such as solvent resistance, water resistance, weather resistance, and color difference was evaluated. Table 2 shows the results. <Evaluation method>-Solvent resistance: Tarpen rubbing test. Rub 100 times with absorbent cotton containing a mineral turpentine and observe the coating film surface. No change, scratches, dissolution.

Water resistance: The coating film is immersed in water (50 ° C.) for 10
Immerse for days and observe the surface. No change ○, blistering △, no peeling or gloss ×. -Weather resistance: accelerated test by 5000 hours of sunshine weatherometer (60-degree gloss retention before and after the test)-Color difference: ΔE measurement. After 6 months of outdoor exposure, measure the color difference (JIS-Z8730) before and after exposure (exposure location, Kawagoe City, Saitama Prefecture)

[0051]

The coating film formed from the fluororesin paint prepared using the fluorocopolymer produced by the method of the present invention maintains the weather resistance and chemical resistance of the fluororesin, Since the paint has almost no petroleum odor, it has an effect that it is easy to paint in an urban area or indoors where the working environment must be considered.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 175/04 C09D 175/04 // (C08F 214/24 214: 26 216: 18 220: 04)

Claims (8)

[Claims] 1. 20 to 47 mol% of a fluoroolefin, 1 to 25 mol% of a polymerizable compound having a hydroxy group, 0.1 to 10 mol% of a linear unsaturated fatty acid having 10 to 15 carbon atoms and other copolymerizable compounds A monomer comprising 15 to 75 mol% of a vinyl compound is copolymerized to give an OH value of 5 to 120 m.
A method of producing a gKOH / g petroleum-based solvent-soluble fluorine-based copolymer, which is mainly composed of an isoparaffin having an initial boiling point of 150 ° C. or higher and containing substantially no aromatic compound. A method for producing a fluorocopolymer, comprising copolymerizing. 2. The process according to claim 1, wherein the polymerizable compound having a hydroxy group is at least one compound selected from alkylene glycol monoallyl ethers. 3. The method according to claim 1, wherein the linear unsaturated fatty acid having 10 to 15 carbon atoms is 1
The method for producing a fluorocopolymer according to claim 1, which is 0-hendesenoic acid. 4. A petroleum-based solvent mainly comprising isofluorin having an initial boiling point of 150 ° C. or higher and containing substantially no aromatic compound, and a fluorine-based copolymer obtained by the production method according to claim 1. A composition for a fluororesin paint, comprising: 5. A composition obtained by blending a hydroxy group-containing vegetable oil with the fluororesin paint composition according to claim 4, wherein the hydroxy group-containing vegetable oil is blended in an amount of 30 parts by weight or less based on 100 parts by weight of the fluorine-based copolymer. A composition for a fluororesin paint, comprising: 6. A composition obtained by blending a saturated fatty acid with the fluororesin coating composition according to claim 4, wherein 10 parts by weight or less of a saturated fatty acid is blended with respect to 100 parts by weight of a fluorine-based copolymer. A composition for a fluororesin coating, comprising: 7. A composition in which an alkyl silicate and a compound having a polyoxyalkylene group and an alkoxysilyl group are blended with the composition for a fluororesin coating composition according to claim 4, wherein the fluorocopolymer is 100 parts by weight. 1 to 15 parts by weight of an alkyl silicate and a compound having a polyoxyalkylene group and an alkoxysilyl group
A composition for a fluororesin paint, wherein the composition is blended in parts by weight. 8. A fluororesin coating composition comprising the composition for a fluororesin coating according to claim 4 and a curing agent, wherein the curing agent is a polyisocyanate or an aluminum chelate compound. Composition.