JPH02135252A - Curable fluororesin paint - Google Patents

Abstract

PURPOSE:To provide a curable fluororesin paint containing a thermoplastic acrylic resin as an essential component, having light-resistance, weather- resistance, etc., of the base resin and excellent flexibility and color stability and suitable as a paint for PCM, etc. CONSTITUTION:The objective composition can be produced by compounding (A) 20-70wt.% (in terms of solid paint component) of an OH-containing fluororesin having a number-average molecular weight of 1,000-300,000 and produced by copolymerizing polymerizable vinyl monomers consisting of a fluorine-containing vinyl monomer (e.g., vinyl fluoride), a copolymerizable vinyl monomer having hydroxyl group (e.g., hydroxyalkyl vinyl ether) and other copolymerizable vinyl monomer with (B) 2-50wt.% (based on the component A) of a curing agent (e.g., aminoplast) and (C) 5-50wt.% (based on the component A) of a thermoplastic acrylic resin having a number-average molecular weight of 15,000-300,000 and produced by the copolymerization of polymerizable monomers containing 2-4C alkyl ester of (meth)acrylic acid and a copolymerizable monomer having carboxyl (anhydride) group.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a curable fluororesin paint, and more specifically, the present invention relates to a curable fluororesin paint, and more specifically, by containing a medium-pressure thermoplastic acrylic resin as one of the essential components of the paint component, Good color reproducibility,
The present invention also relates to an air-dry curable or thermosetting fluororesin paint that provides a coating film with excellent flexibility.

[Conventional technology]

Fluororesin paints have traditionally been widely used in architectural applications due to their characteristics such as excellent stain resistance and chemical resistance as well as high weather resistance against outdoor exposure. The most commonly used paints are paints whose main component is a fluoroolefin thermoplastic resin (hereinafter referred to as thermoplastic fluororesin) such as vinyl fluoride sugar or vinylidene fluoride resin.

However, this type of paint requires baking at a temperature higher than the melting point of the thermoplastic fluororesin after painting.
It could not be widely used as an architectural paint.

In order to solve these problems, Japanese Patent Application Laid-Open No. 57-341
No. 07, JP-A-59-102962, JP-A-62-174213, etc. describe paints containing thermosetting fluororesins in which functional groups are introduced into fluororesins. By using a paint that combines a thermosetting fluororesin and an appropriate curing agent, it is possible to obtain a cured coating film at room temperature or at a relatively low baking temperature of up to 200°C, and the high-temperature baking process is not necessary. It has become possible to paint objects that were previously impossible to paint.

[Problem to be solved by the invention]

However, such thermosetting fluororesins generally have a problem in that the dispersion stability of pigments is significantly inferior, and the dispersion stability varies depending on the type of pigment, which causes the color tone to fluctuate depending on the coating conditions. Ta. Furthermore, thermosetting fluororesins that form films through crosslinking and curing reactions have a disadvantage in that they are significantly inferior in flexibility to thermoplastic fluororesins.

The problems to be solved by the present invention are weather resistance, chemical resistance,
It is an object of the present invention to provide a curable fluororesin paint that prevents color tone from fading due to coating conditions without impairing solvent resistance and has flexibility comparable to thermoplastic fluororesin paints.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a curable fluororesin paint containing (1) a fluororesin having a hydroxyl group, (2) a curing agent, and (3) a thermoplastic acrylic resin (hereinafter, the fluororesin of the present invention). paint).

The fluororesin having a hydroxyl group used in the present invention is, for example, a fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, another copolymerizable vinyl monomer, a color polymerizable vinyl monomer, a radical polymerization initiator, etc. It can be produced by polymerization using known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization.

Examples of the fluorine-containing vinyl monomer include vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene,
Hexafluorots fluoropyrene, ()4-)fluoroalkyl trifluorovinyl ether ((flL, (]4-
) The number of carbon atoms in the fluoroalkyl group is an integer of 1 to 18. ) etc.

The amount of the fluorine-containing vinyl monomer used is preferably in the range of 10 to 90% by weight, and 20 to 85% by weight of the polymerizable vinyl monomer.
Particular pressure is preferably within the range of weight.

Examples of copolymerizable vinyl monomers having a hydroxyl group include (c) hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, and hydroxybutyl vinyl ether; Examples include alkyl (meth)acrylates.

The amount of the copolymerizable vinyl monomer having a hydroxyl group to be used is such that the hydroxyl value of the fluororesin having a hydroxyl group is 30 in terms of solid content.
A child with a range of ~90 m9KOH/g is preferred.

Other copolymerizable vinyl monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl piperate, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl persate, vinyl laurate, and stearate. Vinyl esters of linear or segmented aliphatic carboxylic acids such as vinyl; alicyclic carboxylic acid vinyl esters such as cyclohexane carboxylic acid vinyl ester; benzoic acid vinyl ester, p-t-butylbenzoic acid vinyl ester , aromatic carboxylic acid vinyl esters such as salicylic acid vinyl ester; vinyl monomers having epoxy groups such as glycidyl vinyl ether and glycidyl methacrylate; acrylic acid, methacrylic acid,
Vinyl monomers containing carboxyl groups such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itanate, monovinyl adipate, monovinyl sebacate; dimethyl Vinyl monomers containing amino groups, such as aminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N,N-dimethylaminopropyl (meth)acrylamide, and dimethylaminoethyl (meth)acrylate; no ro r
Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, β-hydroxyethyl (meth)acrylate (meth)acrylic acid esters such as; (meth)acrylonitrile, (meth)acrylamide, N-methylol (
Examples include meth)acrylamide and the like.

The number average molecular weight of the fluororesin having hydroxyl groups is 1.00
The range is preferably 0 to 300,000, s, ooo to 2
A range of 00.000 is particularly preferred.

Typical commercially available fluororesins with hydroxyl groups include:
For example, ``700J to Fluonate'' manufactured by Dainippon Ink and Chemicals, 701J to ``Fluonate'' manufactured by Dainippon Ink and Chemicals, [[
Lumifron LP'1OOJ, rki 70n LF
200J, "Lumiflon LF400J," Lumiflon L
F601. J, “Lumiflon LF700J etc.

The amount of the fluororesin having a hydroxyl group to be used is preferably in the range of 20 to 70% by weight of the solid content of the fluororesin paint of the present invention.

Examples of the curing agent used in the present invention include aminoplast, polyincyanate, block polyisocyanate, polybasic acid, polybasic acid anhydride, polyepoxy compound,
Examples include epoxy group- or incyanate group-containing silane coupling agents.

Aminoplasts can be obtained by, for example, reacting an amino group-containing compound such as melamine, urea, acetoguanamine, benzoguanamine, spiroguanamine, etc. with an aldehyde P group-containing compound such as formaldehyde, acetaldehyde, or glyoxol by a known and conventional method. and etherified products obtained by reacting these condensates with alcohols. In particular, from the viewpoint of compatibility with the fluororesin, it is desirable to use methyl etherified methylolmelamine.

A typical commercial product of the methyl etherified methylol melamine is "Su/I" manufactured by Dainippon Ink & Chemicals.
Examples include "P-Beccamin L105", "Cymel 303" and "Cymel 37o" manufactured by Mitsui Toatsu Chemical Co., Ltd., and "Nikaratsuku MW24XJ" manufactured by Sanwa Chemical Co., Ltd.

Examples of polyincyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylene diisocyanate and inphorone diisocyanate; tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate. Examples include organic diisocyanates such as aromatic diisocyanates, adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight/IJ ester resins, water, etc., polymers of organic diisocyanates, incyanate/biuret bodies, etc. .

As a typical commercial product of the polyisocyanate, for example, "Burnock DN-" manufactured by Dainippon Ink and Chemicals
950J, [Burnock DN-981J, [Takene] D14ONJ manufactured by Ota Pharmaceutical Co., Ltd., r Takenate D1
70J, "Coronate HL" manufactured by Nippon I Urethane Kogyo ■
J, “Coronate gaJ, etc.”

Examples of the blocked polyisocyanate include those obtained by reacting the above polyisocyanate with a known blocking agent.

Examples of polybasic acids include acrylic resins or polyester resins having two or more calgexyl groups in the molecule, pyromellitic acid, trimellitic acid, and the like.

Examples of polybasic acid anhydrides include acrylic resins having two or more acid anhydride groups in the molecule, trimellitic anhydride, pyromellitic anhydride, and the like.

Examples of polyepoxy compounds include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, and sorbitol;
Examples include acrylic resins having two or more epoxy groups in the molecule.

The amount of curing agent used is 2 to 5 of the fluororesin having hydroxyl groups.
A range of oxxts is preferred.

When using aminoplast, polyisocyanate or blocked polyisocyanate as a curing agent, a curing catalyst can be blended into the fluororesin coating material of the present invention.

When the curing agent is an aminoplast, examples of the curing medium include p-toluenesulfonic acid, phosphoric acid, monoalkyl ester of phosphoric acid, sialkyl ester of phosphoric acid,
Examples include dinonylnaphthalene sulfonic acid, dodecylbenzenesulfonic acid, and organic amine blocked products of these compounds.

Examples of the curing catalyst when the curing agent is a polyisocyanate or a block polyisocyanate include diptyltin noacetate, diptyltin dioctate, diptyltin silaurylate, triethylamine, dimethylaminoethanol, and the like.

The fluoropolymer solvent of the present invention can be used as a two-component paint that hardens at room temperature when a compound having a free incyanate group is used as a curing agent, and as a thermosetting deep paint in other cases. .

As the thermoplastic acrylic resin used in the present invention, a polymer obtained by copolymerizing a polymerizable vinyl monomer containing an acrylic ester and/or a methacrylic ester as a main component by a conventional method can be used.
Copolymerizing a polymerizable vinyl monomer containing (1) an alkyl ester of acrylic acid and/or methacrylic acid having 2 to 4 carbon atoms and (2) a copolymerizable vinyl monomer having a carboxyl group or anhydrous carboxyl group. A copolymer obtained by

Examples of alkyl esters having 2 to 4 carbon atoms of acrylic acid and methacrylic acid include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, ethyl methacrylate, n
Examples include -propyl methacrylate, isopropyl methacrylate, and -butyl acrylate.

The content of the alkyl ester of acrylic acid and methacrylic acid having 2 to 4 carbon atoms in the polymerizable vinyl monomer is preferably in the range of 10 to 99.5% by weight. If the amount is less than 10x, the compatibility with the fluororesin having a hydroxyl group tends to decrease, which is not preferable.

Examples of the copolymerizable vinyl monomer having a carboxyl group or carboxyl anhydride group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid,
itaconic anhydride, 7-F# acid, monoethyl maleate,
Examples include monobutyl maleate, monobutyl itaconate, monovinyl adipate, monovinyl sepacate, and the like.

The content of the copolymerizable vinyl monomer having a carboxyl group or anhydrous carboxyl group in the polymerizable vinyl monomer is such that the acid value of the thermoplastic acrylic resin solid content is 1.0 to 11.
An amount in the range of 0 is preferable.

If the acid value is less than 10, it is not preferred because it tends to make it difficult to obtain a sufficient pigment dispersion effect.

If the acid value is greater than 11.0, chemical resistance such as alkali resistance tends to decrease, and thickening and gluing tend to occur when a hardening agent is mixed, which is not preferable.

As polymerizable vinyl monomers constituting the thermoplastic acrylic resin, (1) alkyl esters of acrylic acid and methacrylic acid having 2 to 4 carbon atoms, and (2) monomers having a carboxyl group or carzaxyl anhydride group. Other than the polymerizable vinyl heptamer, other copolymerizable vinyl monomers used in producing the fluororesin having a hydroxyl group can also be used.

The number average molecular weight of the thermoplastic acrylic resin is 15,00
A range of 0 to 300,000 is preferred.

Typical commercially available thermoplastic acrylic resins used in the present invention include, for example, "Acridic A166J" manufactured by Dainippon Ink and Chemicals, "Dyanal BR-106J" manufactured by Mitsubishi Rayon, and "Dyanal BR-106J" manufactured by Rohm and Haas Company, USA. Examples include ``Paraloid B66JJ'' and ``Karautroid B67'' and ``Nogaruroid F-10J.''

The amount of thermoplastic acrylic resin used is preferably in the range of 5 to 50% by weight of the fluororesin having hydroxyl groups. If the weight is less than 5 weight, it tends to be difficult to obtain sufficient pigment dispersibility and flexibility, and if it is more than 50 weight, weather resistance, solvent resistance, chemical resistance, etc. tend to decrease. I don't like it because it is.

In order to obtain the fluororesin paint of the present invention, an organic solvent is added to the above-mentioned thermoplastic acrylic resin or a mixture of a thermoplastic acrylic resin and a fluororesin having a hydroxyl group, and a known inorganic or organic pigment is added to the mixture. First, it is dispersed and stirred using a Gale mill, a sand mill, a roll mill, a homodisno, or any other known and commonly used method, and then, if necessary, a fluororesin having a hydroxyl group, a solvent, a curing agent, a curing accelerating catalyst,
What is necessary is just to add an ultraviolet absorber, an antioxidant, and other various additives and stir. The nonvolatile content concentration is preferably 10 to 80% by weight, particularly preferably 20 to 60% by weight, based on the total amount of the coating composition.

The fluororesin paint of the present invention can be applied by spray painting, brush painting,
A coating film can be formed on a substrate by a known and commonly used method such as roller coating or a roll coater.

Examples of the substrates to which the fluororesin paint of the present invention is applied include metal materials such as steel plates, galvanized iron sheets, and aluminum materials; ceramic materials such as foamed concrete plates and plaster layers; plastic materials such as FRP, etc. However, examples include those whose surfaces are coated with an organic coating (primer coating).

Before applying the fluororesin paint of the present invention, it is common practice to first apply a primer paint to the base material in order to improve corrosion resistance and adhesion to the base material. As the resin component of the primer paint, for example, alkyd resin,
Examples of alkyd resins include epoxy resins and acrylic resins, but in order to improve adhesion to the base material and improve corrosion resistance, alkyd resins include epoxy-modified alkyd resins, phenol-modified alkyd resins, and acrylic resins. It is preferable to use a modified alkyd resin. Moreover, when using an epoxy resin or an acrylic resin, it is preferable to use it together with a curing agent.

Examples of curing agents for epoxy resins used in primer paints include aminoplasts, polyisocyanates, block polyisocyanates, and polyamines.

Examples of curing agents for acrylic resins used in primer paints include aminoplasts, polyisocyanates, and block polyinocyanates.

Pigment components used in primer paints vary depending on the type of base material, but if the base material is iron or galvanized steel, pigments such as suzutan, lead cyanamide, zinc dichromate, and chromium can be used. Rust-inhibiting pigments such as chromate-based pigments such as strontium oxide are preferred.

The composition of the primer paint is 10 to 60% of the above resin by weight,
A range of 0 to 50% by weight of the pigment and 10 to 40% by weight of the solvent is preferred.

The primer paint is applied to the substrate with a brush, wool roller, spray roll coater, etc., and cured at a temperature of 20° C. to 200° C. for 40 seconds to 7 days.

The dry coating thickness is suitably in the range of 5 to 80 μm. Incidentally, in order to further improve the coating film performance, overcoating of the same or different types of primer paints is also carried out. In addition, especially when the base material is an aluminum material and the surface thereof has been subjected to chromic acid treatment with a total amount of chromium of 50 m97 m'' or more, the primer coating can be omitted.

The fluororesin paint of the present invention can be applied by spray painting, brushing,
A coating film can be formed on a substrate coated with a primer, if necessary, by a known and commonly used method such as roller coating or a roll coater.

The coating thickness after drying is preferably in the range of 10 to 200/7 m, particularly preferably in the range of 15 to 150 μm.

〔Example〕

Next, the present invention will be explained in more detail using Examples and Comparative Examples to clarify its effects, but the present invention is not limited to these Examples in any way. In addition, all parts and parts hereinafter are based on weight.

Synthesis Example (Synthesis of Thermoplastic Acrylic Resin) 300 parts of toluene and 500 parts of butyl acetate were charged into a four-way flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 115°C. To the warm mixture of each monomer composition listed in the table, 200 parts of toluene, t-butyl/4'-
Octoate) 20 parts and t-butylhachenzoate 3
After adding a further 5 parts of the mixture dropwise over 4 hours,
The thermoplastic acrylic resin solutions A-1 to A-4 listed in Table 1 were obtained by holding at 115° C. for about 6 to 16 hours. However, the number average molecular weights in Table 81 were measured by permeation chromatography.

In addition to the above-mentioned thermoplastic acrylic resin, we also have "Dyanal BR106J (Mitsubishi Rayon natural thermoplastic acrylic resin, number average molecular weight 60.000 acid value 3.5) 10
A-5 was prepared by dissolving 00 parts of the resin in a mixed solvent of 500 parts of toluene and 500 parts of gtylacetate.

Table 1 Example 1 (Preparation of fluororesin paint of the present invention 1 good, acrylic resin solution A-4l b, titanium oxide IC, Kagen black d, xylene 0.0 part 5.51 2.0# 9.01 e, "Fluoney) K700J 56.0
(Fluororesin 501 solution manufactured by Dainippon Ink & Chemicals)
f, diptyltin dilaurate 0.051 solution 1. OI
g, silicone antifoaming agent 0.1#h,
[Burnock DNQ80. J 6.1 (
Polyisocyanate 75 solution (made by Dainippon Iyd Engineering Industry ■) a = d was thoroughly lined with a mail mill, and then 1
A curable fluororesin paint was obtained by adding the mixture of ~g with stirring, and then adding and stirring h before coating.

Example 2 (Preparation 2 of fluororesin paint of the present invention) Example 1
A curable fluororesin paint was obtained in the same manner as in Example 1, except that acrylic resin solution A-4 was replaced with A-5.

Comparative Example 1 A curable fluororesin paint was obtained in the same manner as in Example 1, except that acrylic resin solution A-4 was replaced with A-1.

Comparative Example 2 A curable fluororesin paint was obtained in the same manner as in Example 1, except that acrylic resin solution A-4 was replaced with A-2.

Comparative Example 3 A curable fluorine resin paint was obtained in the same manner as in Example 1, except that acrylic resin solution A-4 was replaced with A-3.

Comparative Example 4 In Example 1, acrylic resin solution A-1 was heated for 33 s.
A curable fluororesin paint was obtained in the same manner as in Example 1, except that 33 parts of 700J and 38 parts of Partsmac DN980J were added to J Fluonate.

Comparative Example 5 In Example 1, acrylic resin solution A-1 was not used, and 66.0 parts of 700J was added to fluoronate.
A curable fluororesin paint was obtained in the same manner as in Example 1, except that 7.5 parts were changed from 6.4 parts of Burnock DN980J.

The base material for testing these paints was an aluminum plate (material JIS Al100, thickness 2.0 m/
m) was used.

The aluminum plate was immersed in a degreasing liquid (Fine Cleaner 315j, manufactured by Nippon Parkerizing Co., Ltd.) for 10 minutes and then dried.Then, the aluminum plate was degreased and soaked in a chemical conversion liquid (Denran, manufactured by Nippon Parkerizing Co., Ltd.). 713
After soaking in J) for 2 minutes, dry thoroughly. A chemical conversion-treated aluminum plate (total chromium content: 80η/m2) was coated with each of the room-temperature-curing fluororesin paints obtained in the Examples or Comparative Examples using air spray to a dry film thickness of 30 microns, and then left at room temperature. (20° C.) for 7 days to obtain coated test plates.

Test conditions (1) Weather resistance test After conducting an accelerated weather resistance test for 500 hours on the coating film of the above-mentioned test coated board using a device that complies with the ASTM (American Society for Testing and Materials) G23 test standard, the gloss retention rate was determined. and the color difference was determined.

(2) Light resistance test Toshiba's Shishiyaku Lande was used for the coating film of the above-mentioned test coated board.
After peeling off 15cIrL and irradiating it with ultraviolet rays for 1,000 hours, the gloss retention rate and color difference were determined.

[Gloss retention rate (GR)] In accordance with the JIS-5400 test standard, the 60' specular gloss was measured before and after the accelerated weathering test or ultraviolet irradiation test, and the value after the test was expressed as a percentage of the value before the test. It is expressed as

[Color difference (ΔE)]

Measured before and after accelerated weathering test or ultraviolet irradiation test under optical conditions in accordance with JIS-28722 test standards,
Color difference (ΔE) was determined using Hunter's color difference formula.

(3) Solvent Resistance Test The coated test plate described above was immersed in xylene at room temperature for 24 hours, and then dried with warm air. The obtained coating film after immersion was compared with the coating film before immersion.

(4) Alkali resistance test 5'I After dropping an aqueous NaOH solution onto the painted surface, it was covered with a watch glass and left for 24 hours. The painted surface was then washed with water and dried with warm air, and the condition of the resulting paint film was compared with the paint film before the test.

(5) Except for using the aluminum plate for the bending resistance test coated plate, JIS
It was carried out in accordance with K5400, and the results were shown at the minimum diameter of the mandrel that was covered by the coating and no peeling was observed.

The smaller this value is, the better the bending resistance is.

(6) Color Stability Test In addition to the coated plate prepared by spray painting, a coated plate coated with a percoater was prepared, and the difference in color tone between the two with the same paint was expressed as color difference (ΔE).

The smaller this value is, the better the stability of color tone is.

Table 2 shows the test results conducted according to the above test methods (1) to (6).

/ B≦2 As is clear from the test results shown in Table 2, the fluororesin paint of the present invention has the light resistance, weather resistance, and solvent resistance that were characteristic of conventional fluororesin paints.

It can be seen that the chemical resistance (alkali resistance) and the like are maintained as they are, while the flexibility represented by the bending resistance and the stability of color tone are significantly improved.

〔Effect of the invention〕

The fluororesin paint of the present invention is a curable fluororesin paint that can form a coating film with excellent flexibility and color stability without impairing light resistance, weather resistance, solvent resistance, chemical resistance, etc. It is a base resin paint. Therefore, when the fluororesin paint of the present invention is used, it is possible to form a coating film with excellent processability without changing the color tone, and is therefore useful as a paint for PCM, etc.

Agent Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. A curable fluororesin paint containing (1) a fluororesin having a hydroxyl group, (2) a curing agent, and (3) a thermoplastic acrylic resin. 2. A claim that the fluororesin having a hydroxyl group is a copolymer obtained by copolymerizing a polymerizable vinyl monomer consisting of a fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, and another copolymerizable vinyl monomer. The curable fluororesin paint according to item 1. 3. The fluorine-containing vinyl monomer is vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, and (per)fluoroalkylfluorovinylether. (However, the number of carbon atoms in the perfluoroalkyl group is an integer of 1 to 18.) The fluororesin paint according to claim 3, wherein the fluororesin paint is selected from the group consisting of: 4. Claim 2 or 3, wherein the amount of the fluorine-containing vinyl monomer used is in the range of 10 to 90% by weight of the polymerizable vinyl monomer.
Fluororesin paint listed. 5. The curable fluororesin coating material according to claim 2, wherein the copolymerizable vinyl monomer having a hydroxyl group is selected from the group consisting of hydroxyalkyl vinyl ether, hydroxyalkyl acrylate, and hydroxyalkyl methacrylate. 6. The curable fluorine according to claim 2 or 5, wherein the amount of the copolymerizable vinyl monomer having a hydroxyl group is such that the hydroxyl value of the fluororesin having a hydroxyl group is in the range of 30 to 90 mgKOH/g in terms of solid matter. resin paint. 7. The number average molecular weight of the fluororesin having hydroxyl groups is 1.0
The curable fluororesin paint according to claim 1, which has a molecular weight in the range of 00 to 300,000. 8. The curable fluororesin paint according to claim 1, wherein the amount of the fluororesin having a hydroxyl group used is in the range of 20 to 70% by weight of the solid content of the paint. 9. The curing agent according to claim 1, wherein the curing agent is selected from the group consisting of aminoplast, polyisocyanate, blocked polyisocyanate, polybasic acid, polybasic acid anhydride, polyepoxy compound, and epoxy group- or isocyanate group-containing silane coupling agent. Curable fluororesin paint. 10. The amount of curing agent used is 2 for fluororesin having hydroxyl groups.
The curable fluororesin paint according to claim 1, wherein the amount is in the range of 50% by weight. 11. Polymerization in which the thermoplastic acrylic resin contains (1) an alkyl ester of acrylic acid and/or methacrylic acid having 2 to 4 carbon atoms and (2) a copolymerizable vinyl monomer having a carboxyl group or anhydrous carboxyl group. The curable fluororesin paint according to claim 1, which is a copolymer obtained by copolymerizing a vinyl monomer. 12. Number of carbon atoms in acrylic acid and methacrylic acid is 2
12. The curable fluororesin coating material according to claim 11, wherein the amount of the alkyl ester of 4 to 4 is in the range of 10 to 99.5% by weight of the polymerizable vinyl monomer. 13. The copolymerizable vinyl monomer having a carboxyl group or carboxyl anhydride group is (meth)acrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, itaconic acid Monobutyl, monovinyl adipate,
Claim 1 selected from the group consisting of monovinyl sebacate.
The curable fluororesin coating described in 1. 14. The curable composition according to claim 11 or 13, wherein the amount of the copolymerizable vinyl monomer having a carboxyl group or anhydrous carboxyl group is such that the acid value of the solid content of the thermoplastic acrylic resin is in the range of 1 to 11. Fluororesin paint. 15. The number average molecular weight of the thermoplastic acrylic resin is 15.0
The curable fluororesin paint according to claim 1, which has a molecular weight in the range of 00 to 300,000. 16. The curable fluororesin paint according to claim 1, wherein the amount of thermoplastic acrylic resin used is in the range of 5 to 50% by weight of the hydroxyl group-containing fluororesin.