JPH02300253A - Curable fluorinated resin coating material - Google Patents

Abstract

PURPOSE:To provide an ordinary temp.-curable or thermosetting fluorinated resin coating material providing a coating film with a satin pattern by incorporating a curing agent and a fine silica powder surface-treated with a silicone oil in a hydroxylated fluorinated resin. CONSTITUTION:A curable fluorinated resin coating material is provided by incorporating 20-70wt.% fluorinated resin with hydroxyl groups (A) (wherein the average MW is 1,000-300,000, pref. 5,000-200,000; the hydroxyl value is 30-70mgKOH/g; e.g. 'Fluonate K700' a product of Dainippon Ink Chem. Industries, Inc.) based on the solid content of the coating material, 2-50wt.% curing agent (e.g. an aminoplast, a polyisocyanate, etc.) based on the component A and 10-50wt.% silica powder surface-treated with a silicone oil (C) (the particle diameter is 5-300mum pref. 10-100mum for obtaining a uniform satin pattern) based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable fluororesin paint, and more specifically, the present invention relates to a curable fluororesin paint, and more specifically, the paint component contains fine silica powder that has been surface-treated with silicone oil, and has a mold base pattern. The present invention relates to a room-temperature-curable or thermosetting fluororesin paint that provides a coating film.

[Conventional technology]

Fluororesin paints have recently come to be used not only as building materials but also in a wide range of fields such as furniture, fixtures, and vehicles, taking advantage of their excellent weather resistance, corrosion resistance, chemical resistance, fΩ water resistance, etc. In addition, with the diversification of market needs for, for example, gold used in furniture, decorative boards, etc., in addition to smooth coating films using conventional general-purpose feeds, we are also adding designs such as patterns on molded surfaces. There is a demand for paints that can make the colors stand out.

[Problem to be solved by the invention]

Currently, in addition to smooth paint films using general-purpose pigments, there are also paints that give patterns to the object being coated, such as metallic pattern paint films using aluminum flake powder as a pigment, silica powder, and glass fiber paints. , or a low-gloss patterned coating film using Teflon particles as bait, but none of them can express the high level of design typified by the molded pattern.

The problem to be solved by the present invention is to use a curable fluorocarbon that can form a coating film with a design characteristic, typified by a mold pattern, without impairing weather resistance, corrosion resistance, chemical resistance, or water repellency. Our goal is to provide resin paints.

[Means to solve the problem]

In order to solve the above-mentioned problems, the present invention provides a curable fluorine resin containing (a) a fluororesin having a hydroxyl group, (b) a curing agent, and (c) a fine silica powder surface-treated with silicone oil. The company provides resin paints. At this time, it is also preferable that the particle size of the silica fine powder surface-treated with silicone oil is in the range of 5 to 300 μm, and the fluororesin having a hydroxyl group is a fluorine-containing vinyl monomer, a copolymerizable vinyl monomer having a hydroxyl group, and other copolymerizable vinyl monomers. It is a copolymer obtained by copolymerizing a polymerizable vinyl monomer consisting of a polymerizable vinyl monomer, and the amount of copolymerizable vinyl monomer having a hydroxyl group used is such that the hydroxyl value of the fluororesin having a hydroxyl group is 30 in terms of solid content. ~7
It is also preferable that the amount is in the range of 0 KOH/g.
In addition, the curing agent is aminoplast, polyisocyanate,
It is also preferably at least one selected from the group consisting of blocked polyisocyanates, polybasic acids, polybasic acid anhydrides, polyepoxy compounds, and silane cambling agents containing epoxy groups or isocyanate groups.

Next, the present invention will be explained in detail.

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, and a polymerizable vinyl monomer containing other copolymerizable vinyl monomers are subjected to bulk polymerization, solution polymerization, and emulsion polymerization using a radical polymerization initiator. It can be produced by polymerization using a polymerization method such as

Examples of fluorine-containing vinyl monomers include hinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, promotrifluoroethylene, chlorotrifluoroethylene, pentafluoropropylene,
Hexafluoropropylene, (bar)fluoroalkyl trifluorovinyl ether (however, the number of carbon atoms in the (bar)fluoroalkyl group is an integer from 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.
A range of % by weight is particularly preferred.

Examples of the copolymerizable vinyl monomer having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, and hydroxybutyl vinyl ether; ) acrylate, etc.

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.
~70 nvKo)! An amount in the range of /g is preferred.

Other copolymerizable vinyl monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprate, vinyl caprylate, vinyl versatate, vinyl laurate, and vinyl stearate. Vinyl esters of linear or classified aliphatic carboxylic acids such as; alicyclic carboxylic acid vinyl esters such as dichlorohexane carboxylic acid vinyl ester; benzoic acid vinyl ester, pt-butylbenzoic acid vinyl ester, vinyl salicylate Aromatic carboxylic acid vinyl esters such as esters; vinyl septamers having epoxy groups such as glycidyl vinyl ether and glycidyl methacrylate; acrylic acid, methacrylic acid,
Carboxyl group-containing vinyl monomers such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itaconate, monovinyl adipate, monovinyl sebacate; Dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N,N-dimethylaminopropyl (meth)
Vinyl monomers containing amino groups such as acrylamide and dimethylaminoethyl (meth)acrylate; halogen-containing vinyl monomers excluding fluorine such as vinyl chloride and vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene, and vinyltoluene. ; (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, β-hydroxyethyl (meth)acrylate; (meth)acrylonitrile, (meth) Examples include acrylamide, N-methylol (meth)acrylamide, and the like.

The number average molecular weight of the fluororesin having hydroxyl groups is 1,0
The range is preferably from 00 to 300,000, and 5,000
A range of ˜200.000 is particularly preferred.

Typical commercially available fluororesins with hydroxyl groups include:
For example, Fluonate 700J and Fluonate 701J manufactured by Dainippon Ink and Chemicals, Lumiflon LF100J and Lumiflon LF200J manufactured by Asahi Glass.
, ``Lumiflon LF400J, ``Lumiflon LF601
J, "Lumiflon LF700", etc.

The amount of the fluororesin having a hydroxyl group 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, polyisocyanate, block polyisocyanate, polybasic acid, polybasic acid anhydride, polyepoxy compound,
Examples include epoxy group- or isocyanate group-containing silane coupling agents.

Examples of aminoblasts include condensates obtained by reacting amino group-containing compounds such as melamine, phosphorus, acetoguanamine, benzoguanamine, and spiroguanamine with aldehyde group-containing compounds such as formaldehyde, acetaldehyde, and glyoxal; , and etherified products obtained by reacting these condensates with alcohols6. In particular, from the viewpoint of compatibility with fluororesins, it is desirable to use methyl etherified methylolmelamine.

Typical commercially available products of the methyl etherified methylol melamine include "Super Beckamine L105J" manufactured by Dainippon Ink and Chemicals, "Cymel 303" and "Cymel 370" manufactured by Mitsui Toatsu Chemical, and Three Phase Chemical ■. Manufactured by [
Examples include Nikarasoku MW24XJ.

Examples of the polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylene diisocyanate and isophorone diisocyanate; Examples include organic diisocyanates such as aromatic diisocyanates, adducts of these organic diisocyanates with polyhydric alcohols, low-molecular polyester resins, water, etc., polymers of organic diisocyanates, and isocyanate biuret forms.

As a typical commercial product of the polyisocyanate, for example, "Burnock DN-" manufactured by Dainippon Ink and Chemicals
950J, [Parnock DN-980], [Takenate D14ONJ, "Takenate D17" manufactured by Takeda Pharmaceutical Company Ltd.
0J, "Koro 2-to HLJ" manufactured by Nippon Polyurethane Industry @
, rCoronate EH", 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 carboxyl 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 0% by weight is preferred.

When using aminoplast, polyisocyanate or block polyisocyanate as a curing agent, a curing catalyst can be blended.

When the curing agent is an aminoplast, examples of the curing catalyst include ly-)luenesulfonic acid, phosphoric acid, monoalkyl ester of phosphoric acid, dialkyl ester of phosphoric acid,
Examples include dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, and organic amine-blocked products of these compounds.

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

The fluororesin paint of the present invention is a two-component paint that cures at room temperature when a compound having free isocyanate groups is used as a curing agent, and a thermosetting two-component paint when other isocyanate groups are blocked. -Can be used as a molding paint.

The particle size of the silica fine powder surface-treated with silicone oil used in the present invention is in the range of 5 to 300 .mu.m, and in particular, 10 to 100 .mu.m steel is preferred in order to obtain a uniform mold pattern. One method of surface treatment is to mix porous silica fine powder into silicone oil and stir it with a stirrer.

The film thickness of the coating film using fluororesin paint is usually 20 to 70 mm.
If the silica fine powder is smaller than 10 μm, it will tend to be buried in the coating film and it will be difficult to obtain a patterned pattern.If it is larger than 100 μm, the fluororesin paint It tends to be difficult to uniformly disperse the fine silica powder in the paint, and the fine silica powder tends to protrude on the surface of the paint film, causing cracks in the paint film, and the fine silica powder tends to fall off from the paint film. be.

Silicone oil for surface treatment of silica fine powder is
A condensation polymer of a hydrolyzate of dimethyl mono or dichlorosilane, for example, dimethyl silicone oil is preferable, especially when dimethyl silicone oil with a high degree of polymerization is used, since it tends to cause patterns on the mold surface. preferable.

The amount of silica fine powder surface-treated with silicone oil used is 10 to 50% of the solid content of the fluororesin paint of the present invention.
Preferably between. If the amount of the silica fine powder used is less than 10% by weight, most of the silica fine powder will be buried in the coating film even though it is uniformly dispersed, resulting in a mold pattern. If the amount is more than 50% by weight, cracks will occur in the coating film, and the coating film itself will tend to be very weak.

Typical commercially available products surface-treated with silicone oil used in the present invention include, for example, [Torefil F-200J, "Torefill F-201J" manufactured by Toray Silicone ■.
, “Trefil F-202”, “Trefill F-203”
4. ``Trefil F-250J, ``Trefil F-40
0J etc. are mentioned.

In order to obtain the fluororesin paint of the present invention, the above-mentioned fluororesin having a hydroxyl group and, if necessary, a curing agent and a coloring agent are dispersed or dissolved in an organic solvent using a dispersion mixer such as a sand mill or a ball mill. Then, fine silica powder surface-treated with the above-mentioned silicone oil may be added and dispersed.If a two-component paint curable at room temperature is to be obtained, the curing agent may be dispersed or dissolved before coating. The nonvolatile concentration is
It is preferably in the range of 30 to 75% by weight based on the total amount of the paint,
A range of 35 to 70% by weight is particularly preferred.

Before applying the fluorine resin paint of the present invention, it is common practice to first apply a brimer paint to the base material in order to improve corrosion resistance and adhesion to the base material. Examples of the resin components of the brimer paint include 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, acrylic-modified alkyd resins, etc. Preferably, resin is used. 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 brimer paints include aminoplasts, polyisocyanates, block polyisocyanates, and polyamines.

Examples of the curing agent for the acrylic resin used in the brimer paint include aminoplast, polyisocyanate, block polyisocyanate, and the like.

Pigment components used in brimer paints vary depending on the type of base material, but if the base material is iron or galvanized steel, lead-based pigments such as red lead and cyanamide lead; zinc chromate and strontium chromate are used. Rust-preventive pigments such as chromate pigments are preferred.

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

The brimer paint is applied to a 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 microns.

Incidentally, in order to further improve the coating film performance, it is also practiced to overcoat the same or different types of brimer paints. Moreover, only when the base material is an aluminum material and the surface thereof has been subjected to chromic acid treatment with a total chromium content of 50 μ/d or more, the brimer coating can be intentionally omitted.

The fluororesin paint of the present invention can be applied by spray painting, brush painting,
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.

Curing of the coating film in the room temperature curable fluororesin paint of the present invention using a compound having a free isocyanate group is as follows:
1 to 7 days at room temperature or 1 to 6 minutes at 50 to 120℃
It can be cured for 0 minutes.

The curing of the coating film of the fluororesin paint of the present invention using other curing agents such as those with blocked isocyanate groups is as follows:
It can be cured at ~250°C for 5 seconds to 40 minutes.

The fluororesin paint of the present invention can be used as an exterior paint for buildings, roof tiles, pre-coated metal (PCM), enamel paint or clear paint for office equipment, surface protection paint for ceramic products, FRP, etc.

Next, the present invention will be explained with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples in any way. Note that hereinafter all parts and percentages are based on weight.

〔Example〕

Example 1 (Preparation of fluororesin paint of the present invention) (1) Fluonate 700 J 6
1.0 parts (50% solution of fluororesin having hydroxyl group manufactured by Dainippon Ink and Chemicals) (2) Titanium oxide 15.5 parts (
3) Xylene 4.0 parts (4) r I-Le Fill F-400J
10.0 parts (fine silica powder surface treated with dimethyl silicone oil manufactured by Toray Silicone) (5) Butyl acetate 2.0 parts (
6) Dibutyltinsilaurylate 0.05% solution 0.
Part 5 (7) “Parnock DN980J
7.0 parts (75% polyisocyanate solution manufactured by Dainippon Ink & Chemicals ■) (1) to (3) were thoroughly kneaded in a ball mill, and then (
A curable fluororesin paint was obtained by adding the mixture of 4) to (6) with sufficient stirring, and then adding and stirring (7) before coating.

Example 2 (l) Lumiflon LP-200461, 0 parts (60% solution of fluororesin having hydroxyl group manufactured by Asahi Glass ■) (2) Titanium oxide 15.5 parts (
3) Xylene 4.0 parts (4
) r Tre Hunru F-4QOJ IQ
, 0 parts (fine silica powder impregnated with or partially reacted with dimethyl silicone oil manufactured by Toray Silicone) (5) Butyl acetate 2.0 parts (
6) Dibutyltinsilaurylate 0.05% solution 0.
Part 5 (7) “Coronate EHJ
7.0 parts (polyisocyanate manufactured by Nippon Polyurethane Industry ■) The above (11 to (7)) were treated in the same manner as in Example 1 to obtain a curable fluororesin paint.

Comparative Example 1 (High-gloss fluororesin paint using only a general-purpose sealant) In Example 1, a curable fluororesin paint was applied in the same manner as in Example 1, except that ``Toray Fil F-400J'' was not added. Obtained.

Comparative Example 2 (Silica-added low gloss fluororesin paint) Example 1
[In place of Tore Fill F-400J, "Thyroid #404J (anhydrous silica manufactured by Fuji Davison Chemical ■)"
A curable fluororesin paint was obtained in the same manner as in Example 1, except that 2.5 parts were used.

(Preparation of primer paint) After adding 18 parts of titanium oxide to 20 parts of Epiclon 1050-70XJ (70% epoxy resin solution manufactured by Dainippon Ink & Chemicals) and dispersing it,
A brimer paint was obtained by adding and stirring 11 parts of Q66J (polyamide resin manufactured by Dainippon Ink & Chemicals) and 6 parts of butyl cellosolve.

(Creation of painted board for test) Aluminum board CJIS Al 100
15j) for 10 minutes and then dried.

Next, the degreased aluminum plate was immersed in a chemical conversion treatment solution (Bonderant 713J, manufactured by Nippon Parkerizing Co., Ltd.) for 2 minutes, and then dried. Painted to a thickness of 5μm and 48cm thick at room temperature (20℃)
Let dry for an hour.

Each of the curable fluororesin paints obtained in each Example and each Comparative Example was applied to the aluminum plate coated with this primer using air spray so that the dry film thickness was 30μ.
After drying at 20° C. for 7 hours, coated test plates were obtained.

(Evaluation of test coated board) (1) Appearance The texture of the paint film was observed and the texture of the mold pattern was examined.

(2) Weather resistance test After conducting an accelerated weather resistance test for 500 hours on the coating film of the test coated board using an apparatus compliant with ASTM (American Society for Testing and Materials) G23 test standards, the gloss retention rate and color difference were evaluated. I asked for

(3) Light resistance test A Toshiba germicidal lamp was used on the coating film of the above test coated board.
After irradiating with ultraviolet rays for 1,000 hours from a distance of 150,
Gloss retention and color difference were determined.

[Gloss retention rate (OR)] In accordance with the JIS-K 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
This is what I did.

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

The test results conducted according to the above test method fil-(3) are shown in the table.

The coating film made of the fluororesin paint of the present invention embodies the texture of the stencil pattern, and its coating performance is superior to that of current paints with low gloss.
This shows that the coating performance far exceeds that of Comparative Example 2), and even that of the full-gloss product (Comparative Example 1).

〔Effect of the invention〕

The fluororesin paint of the present invention can form a decorative coating typified by Nashiji G4 without impairing weather resistance, corrosion resistance, chemical resistance, flexibility, etc. Thereby, it is possible to enhance the beauty of metal decorative boards used not only as building materials but also for furniture, etc., enhance the design of furniture, etc., and increase its practical value.

May 16, 1999

Claims (5)

[Claims] (1) (a) Fluororesin having a hydroxyl group, (b) a curing agent and (c) Fine silica powder surface treated with silicone oil A curable fluororesin paint characterized by containing. (2) The curable fluororesin paint according to claim 1, wherein the silica fine powder surface-treated with silicone oil has a particle size in the range of 5 to 300 μm. (3) 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. Item 1 or 2
Curable fluororesin paint as described. (4) The amount of the copolymerizable vinyl monomer having a hydroxyl group used is such that the hydroxyl value of the fluororesin having a hydroxyl group is in the range of 30 to 70 mgKOH/g in terms of solid content. Curable fluororesin paint. (5) The curing agent is aminoplast, polyisocyanate,
Claim 1 characterized in that it is at least one selected from the group consisting of blocked polyisocyanates, polybasic acids, polybasic acid anhydrides, polyepoxy compounds, and silane coupling agents containing epoxy groups or isocyanate groups.
The curable fluororesin coating according to any one of 4 to 4.