JPH1171546A - Production of composition for coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of forming coating a film having high weather resistance and high gloss and excellent in storage stability of the composition. SOLUTION: This method for producing a composition for coating materials comprises mixing (A) a pigment dispersion obtained by dispersing (ii) a pigment into (i) an organic solvent solution of a fluorine-containing copolymer having hydroxy group with (B) (iii) an organic solvent solution of a fluorine-containing copolymer having hydrolyzable silyl group, preferably in the weight ratio of the component (i) to the component (iii) of (10/90) to (90/10). Furthermore, it is preferable that the component (i) consists of a fluoroolefin, a vinyl ether and/or a vinyl ester and an olefin monomer having hydroxyl group and has 3,000-200,000 number-average molecular weight expressed in terms of polystyrene by GPC, and the component (iii) consists of a fluoroolefin, (meth)acrylate and an olefinic monomer having hydrolyzable silyl group and has 3,000-500,000 number-average molecular weight expressed in terms of polystyrene by GPC.

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 coating composition, and more particularly to a method for forming a highly glossy coating film.
The present invention also relates to a method for producing a composition for a fluorine-containing paint having excellent storage stability.

[0002]

2. Description of the Related Art Conventionally, fluorine-containing paints have been widely used in the fields of construction, civil engineering and heavy-duty corrosion as high-performance paints which give coatings which do not deteriorate over a long period of time and which do not require repainting. Generally, a fluorine-containing resin containing a hydroxyl group is used for the fluorine-containing paint, but a curing agent is required to form a tough coating film at room temperature, and it is used as a so-called two-pack paint. In recent years, the toxicity of isocyanate used as a curing agent has been regarded as a problem, and the development of a one-pack type fluorine-containing resin paint that does not use isocyanate has been desired. Liquefaction is possible and has been studied diligently (Japanese Patent Publication 1-16)
405). However, the fluororesin solution based on the hydrolyzable silyl group-containing fluororesin has problems in storage stability and gloss, and in particular, various kinds of pigments are added to the resin solution for toning a paint. mixture·
There is a problem that gelation and color separation occur in a dispersed solution (a so-called pigment dispersion).

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to form a coating film having not only high weather resistance but also excellent gloss.
Another object of the present invention is to provide a method for producing a coating composition having excellent storage stability.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a pigment dispersion obtained by dispersing a pigment in a resin solution of a hydroxyl-containing fluorine-containing copolymer has been obtained. A coating composition obtained by mixing a resin solution of a fluorine-containing copolymer containing a hydrolyzable silyl group forms a coating film having high weather resistance and high gloss, and has a high storage stability. Was also found to be excellent, and the present invention was completed. That is, the present invention provides a method of mixing a pigment dispersion obtained by dispersing a pigment in an organic solvent solution of a fluorine-containing copolymer having a hydroxyl group, with an organic solvent solution of a hydrolyzable silyl group-containing fluorine-containing copolymer. A method for producing a coating composition characterized by the following.

[0005]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The composition of the fluorine-containing copolymer having a hydroxyl group in the present invention is not particularly limited as long as it is dissolved in an organic solvent described later. Preferably, (a) a fluoroolefin, (b) a vinyl ether and / or Or a fluorine-containing copolymer comprising a vinyl ester and (c) an olefinic monomer having a hydroxyl group. Examples of the (a) fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, dichlorodifluoroethylene, trifluoroethylene, vinylidene fluoride, and vinyl fluoride. Among these, tetrafluoroethylene, chlorotrifluoroethylene and hexafluoropropylene are preferred from the viewpoint of polymerizability.

The vinyl ether (b) includes methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether, neopentyl vinyl ether,
Examples thereof include phenyl vinyl ether and tetraethylene glycol monomethyl vinyl ether. Also,
Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl caproate, vinyl pivalate, Vova-9 (trade name, manufactured by Shell Chemical Co., Ltd.), vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl laurate and the like. Is done. Vinyl ether and / or
Alternatively, two or more vinyl esters may be used.

The (c) olefinic monomer having a hydroxyl group includes 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, allyl alcohol, cinnamon alcohol, N-methylol (meth) acrylamide, 2-hydroxyethyl crotonate, 4-hydroxybutyl crotonate, 2-
Compounds obtained by ring-opening addition of ε-caprolactam or ethylene oxide to hydroxyethyl allyl ether and these hydroxyl-containing monomers, and unsaturated compounds such as (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid and itaconic acid Carboxylic acid and ethylene glycol,
Examples include monomers that are a reaction product with polyhydric alcohols such as ethylene oxide, propylene glycol, propylene oxide, butylene glycol, cyclohexanedimethanol, glycerin, and trimethylolpropane.

The fluorine-containing copolymer having a hydroxyl group may be copolymerized with another monomer as long as the physical properties are not impaired. Such monomers include α-olefins such as ethylene, propylene and isobutylene,
Chloroethylenes such as vinyl chloride and vinylidene chloride, (meth) acrylamides, olefinic monomers such as styrene and α-methylstyrene, and acid groups such as (meth) acrylic acid, crotonic acid, vinyl acetic acid and vinyl sulfonic acid Monomer containing allyl, glycidyl ether, glycidyl vinyl ether, glycidyl (meth)
A monomer containing an epoxy group such as acrylate is exemplified.

The ratio of each monomer is (a) is 3
0 to 70 mol%, (b) is preferably 30 to 70 mol%, and (c) is preferably 2 to 30 mol%. When other monomers are copolymerized, the proportion is 0 to 30 mol%. Is preferred.

In the present invention, gel permeation chromatography (G) of the fluorine-containing copolymer having a hydroxyl group is carried out.
PC), the number average molecular weight in terms of polystyrene is 300.
The range is preferably from 0 to 200,000, and more preferably from 5,000 to 50,000. The glass transition temperature (Tg) of the fluorinated copolymer is from -20 ° C to 6 ° C.
The temperature is preferably 0 ° C, particularly preferably 0 to 50 ° C.

The fluorine-containing copolymer having a hydroxyl group can be easily produced by subjecting the above monomer to radical copolymerization in the presence of a polymerization initiator. As the polymerization method,
Conventional methods such as solution polymerization in an organic solvent can be adopted. As the polymerization initiator, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, peroxides such as benzoyl peroxide and lauroyl peroxide, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile And inorganic peroxides such as ammonium persulfate and potassium persulfate. These polymerization initiators are preferably used in an amount of 0.0001 to 10 parts by weight based on 100 parts by weight of the total monomers. In the case of emulsion polymerization, emulsifiers include potassium perfluorooctanoic acid and ammonium salts, ammonium perfluorooctane sulfonate,
Higher alcohol sulfate sodium salt, polyethylene glycol ether and the like are exemplified.
It is desirable to use 0.1 to 50 parts for 00 parts. In the case of emulsion polymerization, the fluorinated copolymer is isolated and purified, and then dissolved in an organic solvent to prepare a resin solution. As the organic solvent in the solution polymerization, cyclic ethers such as tetrahydrofuran and dioxane; n-hexane, cyclohexane, mineral spirit, industrial gasoline 4
Aliphatic hydrocarbons such as No. 3 volatile oil, No. 3 volatile oil, kerosene and turpentine; aromatic hydrocarbon compounds such as toluene and xylene; esters such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone and cyclohexanone Ketones; alcohols such as ethanol, isopropanol, n-butanol and n-butyl cellosolve are exemplified, and one or more of these can be used. The organic solvent is preferably used in an amount of 20 to 200 parts by weight based on 100 parts by weight of all monomers. After the completion of the polymerization, it may be used as it is as a resin solution. In this case, the reaction solvent is used as it is as an organic solvent. Alternatively, the fluorocopolymer may be once isolated and purified, and then redissolved in an organic solvent to prepare a resin solution. Although the polymerization conditions are not particularly limited, a preferable polymerization temperature is 20 to 100 ° C., and a suitable pressure is 1 to 20.
It is 0 kg / cm ² . The monomers used in the polymerization may be initially charged in batches at the beginning, or some of the monomers may be added sequentially as the polymerization proceeds. Also, if necessary,
Potassium carbonate, sodium hydrogen carbonate, hydrotalcite, anion exchange resin, inorganic ion exchanger, and the like may be added as a pH adjuster.

As the fluorine-containing copolymer containing a hydroxyl group, commercially available products such as Zaflon (trade name: manufactured by Toagosei Co., Ltd.) and Lumiflon (trade name: Asahi Glass Co., Ltd.)
), Fluorate (trade name: manufactured by Dainippon Ink and Chemicals, Inc.), Sefral Coat (trade name: manufactured by Central Glass Co., Ltd.) and Zeffle (trade name: Daikin Industries, Ltd.).

The fluorinated copolymer obtained by the above method is
Examples of the organic solvent used when the resin solution is newly dissolved in the organic solvent include the organic solvent used in the solution polymerization, and the amount of the organic solvent used is the fluorinated copolymer 10
The amount is preferably 20 to 200 parts by weight, more preferably 50 to 100 parts by weight, based on 0 parts by weight.

Next, a pigment and, if necessary, other paint additives are dispersed in the organic solvent solution of the hydroxyl group-containing fluorocopolymer obtained above to prepare a pigment dispersion. As pigments, titanium oxide, iron oxide, graphite, inorganic pigments such as baked pigments and pearl pigments, phthalocyanine blue, quinacridone red, organic pigments such as isoindolinone and carbon black, volume pigments such as calcium carbonate and barium sulfate, Examples include metallic pigments such as aluminum flakes and stainless steel flakes. Further, as a matting agent which is one kind of pigment, polyethylene wax, polypropylene wax and silica-based matting agent can be added. These pigments may be used alone or as a mixture of two or three as necessary. The amount of the pigment used is preferably 0.5 to 200 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of the fluorine-containing copolymer having a hydroxyl group. As other paint additives, pigment dispersants, sedimentation inhibitors, anti-peeling agents, thickeners, defoamers, leveling agents, slip agents and ultraviolet absorbers can be used, and these paint additives are It is suitably used in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the fluorine-containing copolymer having a hydroxyl group. Further, a curing accelerator such as dibutyltin dilaurate and a hardness modifier such as a partial hydrolyzate of alkoxysilane may be added. The method for dispersing the above pigment and other paint additives is not particularly limited, and ordinary dispersion methods such as a paint shaker, a ball mill, a sand mill, a roll mill, and a disper are used.

The composition of the fluorine-containing copolymer having a hydrolyzable silyl group in the present invention is not particularly limited as long as it is dissolved in an organic solvent described below. A) a fluorinated copolymer comprising an acrylate ester and (c) an olefinic monomer having a hydrolyzable silyl group. Here, (a) the fluoroolefin is the same as the fluoroolefin in the fluorine-containing copolymer having a hydroxyl group.

The (b) alkyl (meth) acrylate is preferably one having an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and a halogen-containing alkyl group as an ester chain, as long as the physical properties are not impaired. The chain may contain atoms such as oxygen, nitrogen and sulfur. Specific examples of the compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth)
Butyl acrylate, isobutyl (meth) acrylate,
S-butyl (meth) acrylate, t- (meth) acrylate
-Butyl, neopentyl (meth) acrylate, (meth)
2-ethylhexyl acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate,
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecynyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, Examples thereof include alkyl (meth) acrylates such as chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and pentafluoropropyl (meth) acrylate. Among these, acrylic esters are preferred due to their polymerizability with fluoroolefins, flexibility of the copolymer, and the like. Also,
These monomers can be used alone or as a mixture of several types.

The (c) olefinic monomer having a hydrolyzable silyl group is a compound represented by the following formula (1). _{R-SiX n Y 3-n} (1) ( wherein, R is a group having an olefinic unsaturated bond, X represents an alkyl group having 1 to 20 carbon atoms, Y represents a hydrolyzable radical, n Is 0, 1 or 2. When there are a plurality of X or Y, they may be the same or different.) In the above formula (1), R represents a vinyl group, an allyl group,
Butenyl group, vinyloxy group, allyloxy group, acryloyl group, methacryloyl group, CH ₂ ＣＨCHO (CH ₂ )
_{3 -, CH 2 = CHCOO (} CH 2) 3 -, CH 2 = C
_{HOCO (CH 2) 3 -,} CH 2 = C (CH 3) COO
(CH ₂ ) ₃ — and CH ₂ ＣC (CH ₃ ) COO (C
H ₂ ) ₂ —O— (CH ₂ ) ₃ — and the like. X in the formula (1) includes a methyl group, an ethyl group, a propyl group, an octyl group and an octadecyl group. Examples of Y in the formula (1) include hydrolyzable groups such as an alkoxy group, an amino group, an acyloxy group, a phenoxy group, a mercapto group, and an iminooxy group, and among these, an alkoxy group is particularly preferable. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a methoxyethoxy group. Among them, those in which R is a vinyl group are preferable, and those in which Y is a methoxy group and an ethoxy group are particularly preferable.

Specific examples of the olefinic monomer having a hydrolyzable silyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltris (β- Methoxyethoxy) silane, trimethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl vinylether, trimethoxysilylpropylvinylether, vinyltriisopropenyloxysilane, vinylmethyldiisopropenyloxysilane, triisopropenyloxysilylethyl Vinyl ether, triisopropenyloxysilylpropyl vinyl ether, triisopropenyloxysilylbutyl vinyl ether, Rutorisu (dimethyl imino oxy) silane, vinyltris (methyl ethyl imino-oxy) silane, vinyl methyl bis (dimethyl imino oxy) silane, vinyl dimethyl (dimethyl imino oxy)
Silane, tris (dimethyliminooxy) silylethyl vinyl ether, methylbis (dimethyliminooxy)
Silylethyl vinyl ether, tris (dimethyliminooxy) silylbutyl vinyl ether, γ- (meth) acryloyloxypropyltrimethoxysilane, γ-
(Meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldiethoxysilane and γ- (meth) acryloyloxypropyltriisopropenyloxysilane.

Other monomers may be copolymerized with the fluorine-containing copolymer having a hydrolyzable silyl group as long as the physical properties are not impaired. Such monomers include olefins such as ethylene, propylene, isobutylene, norbornene and norbornadiene, chloroethylenes such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl propionate, vinyl caproate, vinyl pivalate,
Veova-9 (manufactured by Shell Chemical), vinyl carboxylate such as vinyl cyclohexanecarboxylate, vinyl benzoate and vinyl laurate; vinyl ethers such as ethyl vinyl ether and butyl vinyl ether; allyl ethers such as ethyl allyl ether and cyclohexyl vinyl ether Is exemplified.

Further, it is also possible to copolymerize the fluorine-containing copolymer with a monomer having a functional group such as an epoxy group and a carboxyl group. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, and glycidyl vinyl ether. Examples of the monomer having a carboxyl group include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid.

In the fluorine-containing copolymer having a hydrolyzable silyl group in the present invention, the ratio based on the total amount of the above essential constituent monomers is (a) a fluoroolefin: 10 to 10%.
70 mol%, (b) (meth) acrylate: 20
To 80 mol% and (c) an olefinic monomer having a hydrolyzable silyl group: preferably 0.5 to 20 mol%, more preferably (a): 20 to 60 mol%.
Mol%, (b): 30-75% mol% and (c): 2
-10 mol% (however, a + b + c = 100). The other monomers can be used in the range of 0 to 30 mol%.

The fluorine-containing copolymer having a hydrolyzable silyl group in the present invention preferably has a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 3,000 to 500,000, more preferably 5,000. ~ 30000.
Further, the glass transition temperature (Tg) of the fluorinated copolymer is preferably from -20 ° C to 60 ° C, particularly preferably from 0 ° C to 50 ° C.

The fluorine-containing copolymer having a hydrolyzable silyl group can be produced by a method similar to the method for producing a fluorine-containing copolymer having a hydroxyl group described above.

When the fluorinated copolymer having a hydrolyzable silyl group obtained above is re-dissolved in an organic solvent to form a resin solution, the organic solvent used in the solution polymerization may be used. The amount of the organic solvent used is 20 to 20 parts by weight based on 100 parts by weight of the fluorocopolymer.
0 parts by weight, more preferably 50 parts by weight.
１００100 parts by weight.

The coating composition of the present invention comprises a pigment dispersion obtained by dispersing a pigment in an organic solvent solution of a fluorine-containing copolymer having a hydroxyl group, and adding the water-decomposable silyl group-containing fluorine-containing copolymer to the pigment dispersion. It is characterized in that an organic solvent solution is mixed to adjust the viscosity, the pigment concentration and the resin concentration suitable for a coating composition, and the coating composition has a hydroxyl group-containing fluorinated copolymer and a hydrolyzate. The ratio of the fluorine-containing copolymer having a functional silyl group is from 10/90 by weight ratio.
90/10, particularly preferably 20/10.
/ 80 to 60/40. Furthermore, if necessary, the coating composition produced by the above method may contain a curing accelerator, an ultraviolet absorber, a light stabilizer, a flow regulator, a leveling agent, a slip agent, an antioxidant, and a silane coupling agent. And additives such as partially hydrolyzed condensates of alkoxysilanes and ortho acid esters.

The silane coupling agent is added for the purpose of improving the adhesiveness of the coating composition. As the silane coupling agent, a compound having an epoxy group and a hydrolyzable silyl group in one molecule is preferable. Further, the partially hydrolyzed condensate of the alkoxysilane, the coating composition is added for the purpose of further improving the stain resistance of the coating film,
As the partially hydrolyzed condensate of alkoxysilane, a self-condensate of alkoxysilane having two or more hydrolyzable alkoxy groups in one molecule is used.

The coating composition obtained by the production method of the present invention has extremely good storage stability, does not gel or precipitate the pigment during storage, and has high weather resistance and stain resistance. In addition, a coating film having high gloss and having no color separation or spots is formed.

[0028]

【Example】

Preparation Example of Fluorine-Containing Copolymer Solution A hydroxyl-containing fluorinated copolymer having the composition shown in Table 1 below was dissolved in xylene and adjusted to a solid content of 50% by weight.

[0029]

[Table 1] CTFE: chlorotrifluoroethylene V9: Veova 9 (manufactured by Shell Chemical Co., Ltd.) VCp: vinyl caproate HECR: 2-hydroxyethyl crotonate HEA: 2-hydroxyethyl acrylate CHVE: cyclohexyl vinyl ether EVE: ethyl vinyl ether HBVE: hydroxy Butyl vinyl ether

A fluorinated copolymer having a hydrolyzable silyl group having a composition shown in Table 2 below was dissolved in butyl acetate to adjust the solid content to 50% by weight.

[0031]

[Table 2] CTFE: chlorotrifluoroethylene CHA: cyclohexyl acrylate BA: butyl acrylate tBA: t-butyl acrylate VMS: vinyl trimethoxysilane

(Example 1) OF1 solution 22.7 g, Di
sperbyk165 (a pigment dispersant from BYK Chemie)
0.9 g, Nova Palm Red (a red organic pigment of BASF) 6.7 g, xylene 15.2 g and steel beads were put in a container and dispersed with a paint conditioner for 2 hours. Thereafter, 53.0 g of the SF1 solution and 1.5 g of trimethyl orthoformate were added to the obtained pigment dispersion, dispersed for 20 minutes, and then the steel beads were removed by filtration to obtain a coating composition.

Example 2 28.1 g of OF1 solution, Di
spybyk165 0.6g, perm yellow 5G
17.2 g of yellow lead from Kikuchi Color Co., Ltd. and steel beads were placed in a container and dispersed with a paint conditioner for 2 hours. Thereafter, SF2 was added to the obtained pigment dispersion.
After 52.3 g of the solution and 1.8 g of trimethyl orthoformate were added and dispersed for 20 minutes, the steel beads were removed by filtration to obtain a coating composition.

Example 3 21.9 g of OF2 solution, Di
0.6 g of sperbyk165, 24.3 g of Taipaque (rutile type titanium oxide of Ishihara Sangyo Co., Ltd.) and steel beads were put in a container and dispersed with a paint conditioner for 2 hours. Then, S was added to the obtained pigment dispersion.
1. F1.2 solution of 51.2 g and trimethyl orthoformate.
After adding 0 g and dispersing for 20 minutes, the beads were removed by filtration to obtain a coating composition.

Comparative Example 1 53.1 g of SF1 solution, Di
0.9 g of sperbyk165, 6.7 g of Nova Palm Red, 13.2 g of xylene, 2.0 g of trimethyl orthoformate and steel beads were placed in a container and dispersed with a paint conditioner for 2 hours. Thereafter, 22.7 g of the OF1 solution and 1.5 g of trimethyl orthoformate were added to the obtained pigment dispersion and dispersed for 10 minutes.
The beads were removed by filtration to obtain a coating composition.

Comparative Example 2 51.2 g of SF2 solution, Di
spybyk165 0.6g, taipaek 24.3
g, trimethyl orthoformate and steel beads were placed in a container and dispersed with a paint conditioner for 2 hours. Thereafter, 21.9 g of an OF2 solution and 1.0 g of trimethyl orthoformate were added to the obtained pigment dispersion, and dispersed for 20 minutes. Then, the beads were removed by filtration to obtain a coating composition. (Comparative Example 3) A coating composition was obtained in the same manner as in Comparative Example 1, except that a product obtained by mixing OF1 and SF1 in advance so that the weight ratio became 3/7 was used instead of SF1. .

(Comparative Example 4) A coating composition was prepared in the same manner as in Comparative Example 2, except that a mixture of OF2 and SF2 was used so that the weight ratio became 3/7 in place of SF2. I got

(Test Example 1) Examples 1 to 3 and Comparative Example 1
The following tests were performed on the coating composition obtained in Nos. 1 to 4, and the results are shown in Table 3. -Storage stability After the above-mentioned coating composition was stored in a bottle with a sealed stopper at 50 ° C for one month, the appearance of the liquid was observed. Gloss 1 g of dibutyltin dilaurate is added to 10.0 g of the coating composition.
1.5 g of a weight% solution, NUC Silicon A187 [Nippon Unicar Co., Ltd. epoxy group-containing silane coupling agent]
1.0 g of a 10% by weight solution was added, and the mixture was applied to a glass plate with a doctor blade. After drying at room temperature for one week, the gloss value at 60 ° was measured. -Accelerated weather resistance The composition adjusted for the gloss measurement was applied to a galvanized steel sheet coated with an epoxy primer. After drying at room temperature for one week and measuring the gloss, a 3000-hour test was performed using a sunshine weather meter, and the gloss after the test was measured to calculate the gloss retention.

[0039]

[Table 3]

Example 4 5.0 g of the composition prepared in Example 1, 45.0 g of the composition prepared in Example 3, and 10% of BYK331 (a leveling agent of BYK Chemie).
A coating composition was prepared by mixing 0.2 g of a weight% xylene solution.

Example 5 5.0 g of the composition prepared in Example 2, 45.0 g of the composition prepared in Example 3, and 10% of BYK331 (a leveling agent of BYK Chemie).
A coating composition was prepared by mixing 0.2 g of a weight% xylene solution.

Comparative Example 5 5.0 g of the composition prepared in Comparative Example 1, 45.0 g of the composition prepared in Comparative Example 2, and 10% of BYK331 (a leveling agent of BYK Chemie).
A coating composition was prepared by mixing 0.2 g of a weight% xylene solution.

Comparative Example 6 5.0 g of the composition prepared in Comparative Example 3, 45.0 g of the composition prepared in Comparative Example 4, and 10% of BYK331 (a leveling agent of BYK Chemie).
A coating composition was prepared by mixing 0.2 g of a weight% xylene solution.

(Test Example 2) Examples 4 to 5 and Comparative Example 5
The following tests were performed using the coating compositions of Nos. 6 to 6. -Color separation Dilute the coating composition obtained above with xylene,
Spray coating was applied to a 15 cm tin plate, and the coating composition was flow-coated on half of the coated surface. After drying at room temperature for 3 days, the color difference between the spray-coated part and the flow-coated part was measured by the method described in JIS Z8730, and the ΔE value was calculated. Storage stability 50 ° C with the adjusted paint composition in a bottle and sealed
For one month, and its appearance was observed. -Color separation after storage stability Using the coating composition after the storage stability test, the composition was applied in the same manner as in the color separation section, and the color difference between the spray part and the flow coating part was measured to calculate ΔE.

[0045]

[Table 4]

[0046]

The coating composition obtained by the production method of the present invention has excellent storage stability, does not gel or precipitate pigment during storage, and has high weather resistance and stain resistance. In addition to having a coating, it gives a coating film with high gloss and no color separation or blemishes, and its use value as a paint is remarkably high.

Claims (4)

[Claims] 1. A method comprising mixing a pigment dispersion obtained by dispersing a pigment in an organic solvent solution of a hydroxyl group-containing fluorine-containing copolymer with an organic solvent solution of a hydrolyzable silyl group-containing fluorine-containing copolymer. A method for producing a coating composition characterized by the following. 2. A fluorinated copolymer having a hydroxyl group and a fluorinated copolymer having a hydrolyzable silyl group in a weight ratio of 10%.
The method for producing a coating composition according to claim 1, wherein the ratio is in the range of / 90 to 90/10. 3. A fluorine-containing copolymer having a hydroxyl group comprising a fluoroolefin, a vinyl ether and / or a vinyl ester and an olefinic monomer having a hydroxyl group as essential components, and having a number average molecular weight of 3,000 to 200,000 in terms of polystyrene by GPC. A method for producing the coating composition according to claim 1 or 2. 4. A fluorinated copolymer having a hydrolyzable silyl group contains a fluoroolefin, a (meth) acrylate ester and an olefinic monomer having a hydrolyzable silyl group as essential components, and is converted into polystyrene by GPC. The number average molecular weight is 3,000 to 500,000.
A method for producing the coating composition according to claim 3.