JPH086065B2 - Resin composition for paint - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for coatings, which has long-term weather resistance, durability, corrosion resistance, and is excellent in coating appearance such as high gloss.

[0002]

2. Description of the Related Art In recent years, in the field of metal coating such as automobiles, curtain walls, and pre-coated metals, it has become necessary to extend the life of coating films, and therefore fluororesin coating materials have been receiving attention. As a conventional fluororesin paint, a dispersion type fluororesin paint in which polyvinylidene fluoride resin powder is dispersed in a solvent or a solution containing a solvent and a liquid resin is predominant. Although the coating has excellent weather resistance, durability, and corrosion resistance, the polyvinylidene fluoride resin powder has a high melting point and requires high temperature baking to form a uniform melt phase in the liquid resin for dispersion. The film had a fatal problem of poor adhesion, repaintability during repair, and poor gloss.

Therefore, a fluororesin for paints that solves such problems has been developed and a patent application has been filed (Japanese Patent Laid-Open No. 57-34107). The fluororesin is a hydroxyl group-containing fluorocopolymer having fluoroolefin, cyclohexyl vinyl ether, etc. as constituent components, and is soluble in ordinary organic solvents at room temperature and has a hydroxyl group, so that it is baked at room temperature or low temperature. However, it is possible to form a coating film, and the obtained coating film is excellent in not only weather resistance and durability but also corrosion resistance, chemical resistance, adhesion, repaintability during repair, etc. . However, paints using the above-mentioned fluorine-containing copolymer having a hydroxyl group have selectivity in the dispersibility of pigments, and therefore, defects such as color separation and floating may occur depending on the pigments, and the resulting coatings The film has a drawback that it has a small elongation and that the gloss and sharpness of the coating film are slightly inferior to those of acrylic resin-based paints, aminoalkyd resin-based paints and the like. Due to such drawbacks, the above-mentioned paints cannot be said to have sufficient commercial value in the paint field in which the initial appearance and aesthetics of the coating film are important, and therefore excellent weather resistance and durability are recognized. Early improvement was also requested.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have reached the present invention as a result of intensive studies in order to solve the above-mentioned drawbacks in view of the above-mentioned circumstances, and therefore, the present invention is intended for long-term use. It is an object of the present invention to provide a coating composition having weather resistance, durability, corrosion resistance, and excellent in coating appearance such as high gloss.

[0005]

Means for Solving the Problems That is, the present invention provides a fluorine-containing copolymer having a hydroxyl group in which a fluorine atom is bonded to the main chain obtained by using a fluoroolefin as an essential component, and acrylic acid and / or as a copolymerization component. An acrylic copolymer having a hydroxyl value of 5 to 150, which is a copolymer of an ethylenically unsaturated monomer containing 10 to 80% by weight of an alkyl ester of methacrylic acid having 2 to 4 carbon atoms (provided that the acrylic component is an acrylic copolymer). Acid and / or methacrylic acid are not used so that the content of the alkyl ester having 10 or more carbon atoms is at least 20% by weight or more), and a resin composition for coating material comprising an aminoplast compound. Is. The coating resin composition of the present invention has good pigment dispersibility, and the obtained coating film is excellent in weather resistance, durability, corrosion resistance, chemical resistance, adhesion, repaintability during repair, and the like. A specific acrylic copolymer is used, and its compatibility with the fluorine-containing copolymer having hydroxyl groups is improved, so the transparency of the clear coating or the gloss of the enamel coating is significantly improved. are doing. Hereinafter, the present invention will be described in detail.

The fluorine-containing copolymer having a hydroxyl group used in the present invention is a fluorine-containing copolymer having a hydroxyl group, in which a fluorine atom is bonded to the main chain obtained from a fluoroolefin as an essential component, and preferably, The above-mentioned JP-A-57
Fluorine-containing copolymers described in JP-A-34107 are mentioned. That is, the fluorocopolymer has fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as constituent components, and each has a proportion of 30 to 70% by weight, 5 to 60% by weight and 3 to
The content is 50% by weight and 3 to 20% by weight. A fluorine-containing copolymer having a weight average molecular weight of about 20,000 to about 100,000 is suitable. If the content of the fluoroolefin is too low, the weather resistance is lowered, and if it is too high, the production is difficult. Further, if the cyclohexyl vinyl ether content is too low, the hardness when formed into a coating film decreases, and if the alkyl vinyl ether content is too low, the flexibility decreases.

Further, it is particularly important that the content of the hydroxyalkyl vinyl ether is within the above range in order to improve the curability without impairing various useful properties as a paint base. That is, if the hydroxyalkyl vinyl ether content is too high, not only the solubility of the copolymer in an organic solvent is reduced, but also the flexibility of the coating film is reduced, and conversely if it is too low, the durability of the coating film, Adhesion decreases. In the fluorinated copolymer, the fluoroolefin is preferably a perhaloolefin, particularly chlorotrifluoroethylene or tetrafluoroethylene. Further, as the alkyl vinyl ether, one containing a linear or branched alkyl group having 2 to 8 carbon atoms, particularly one having 2 to 4 carbon atoms in the alkyl group is preferable.

The fluorine-containing copolymer may contain a comonomer other than the above-mentioned four kinds of constituent components within a range not exceeding 40% by weight. Typical examples of such comonomer include ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, methyl methacrylate, butyl acetate and the like. The fluorine-containing copolymer can be produced by causing a copolymerization reaction by causing a polymerization initiator to act on a monomer mixture in a predetermined ratio in the presence of a polymerization medium. Further, the acrylic copolymer used in the present invention is an α, β- having a C 2-4 alkyl ester of acrylic acid and / or methacrylic acid and a hydroxyl group.
It is a copolymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer as an essential component. Those having a weight average molecular weight of about 10,000 to about 120,000 are preferable. The alkyl ester of acrylic acid and / or methacrylic acid having 2 to 4 carbon atoms is an essential component for being uniformly compatible with the fluorine-containing copolymer, and the content thereof is 10 to 80% by weight.

If the content is too low, the compatibility decreases,
As a result, the transparency of the clear coating film and the gloss of the enamel coating film in which the pigment is dispersed are reduced, which is not preferable. On the other hand, if the content is too high, the hardness of the coating film tends to decrease and the weather resistance tends to decrease, which is not preferable. The content of the α, β-ethylenically unsaturated monomer having a hydroxyl group is such that the copolymer has a hydroxyl value of 5 to 150, particularly preferably 1
The amount is 0 to 120. If the hydroxyl value is lower than the above range, the curability of the coating film is deteriorated, and the hardness, stain resistance, etc. are also deteriorated, which is not preferable. On the contrary, when the hydroxyl value is higher than the above range, the flexibility of the coating film is deteriorated and the post-processability and the like are deteriorated, which is not preferable. The acrylic acid and /
Alternatively, as the alkyl ester of methacrylic acid having 2 to 4 carbon atoms, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, acrylic acid n
-Butyl, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate and the like.

Typical examples of the α, β-ethylenically unsaturated monomer having a hydroxyl group include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and the like. In addition, the acrylic copolymer has the above 2
In addition to various types of monomers, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic anhydride, and other acid monomers, methyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, and other acrylic monomers It is obtained by copolymerizing acid and / or methacrylic acid esters, and other one or more kinds of comonomer which is an ethylenically unsaturated monomer such as styrene, α-methylstyrene and vinylpyridine. An alkyl ester of acrylic acid or methacrylic acid having 10 or more carbon atoms can also be used as a copolymer component, but its content is less than 20% by weight of the acrylic copolymer.

In the above acrylic copolymer, a polymerization initiator is allowed to act on a monomer mixture of ethylenically unsaturated monomers in a predetermined ratio in the presence of a polymerization solvent such as xylene, toluene, ethyl acetate or butyl acetate. It can be produced by carrying out a copolymerization reaction by a conventional method. The polyol component used in the present invention is composed of the fluorine-containing copolymer and the acrylic copolymer, and the mixing ratio (weight basis) of both is (95: 5 to 10:90), particularly preferably (9
0:10 to 20:80). When the amount of the fluorinated copolymer is more than the above range, color separation due to the pigment selectivity is likely to occur, and the gloss and flexibility of the obtained coating film are deteriorated. The weather resistance, durability, corrosion resistance, chemical resistance, etc., which are the characteristics of the polymer, tend to decrease.

Next, in the present invention, an aminoplast compound is used as a curing agent component for the polyol component.
This aminoplast compound is a condensation product of an amino compound such as melamine, urea, benzoguanamine, and acetoguanamine and an aldehyde compound, or a compound obtained by etherifying the condensation product with an alcohol such as butanol. By mixing in a ratio, a bake-curable one-pack type coating material is obtained. Mixing ratio (weight basis) of polyol component consisting of fluorine-containing copolymer and acrylic copolymer and aminoplast compound curing agent component
Is (95: 5 to 60:40), particularly preferably (90:
10 to 70:30), and it becomes possible to exhibit the original resin characteristics in this range.

If the amount of the aminoplast compound is more than the above range, the reaction between the aminoplast compounds tends to occur, and the flexibility and chemical resistance of the coating film are deteriorated. Conversely, if the amount is too small, satisfactory curability is obtained. Since the crosslinking density is low, the solvent resistance, stain resistance, etc. tend to decrease. In the present invention, it is also possible to use a partially blocked isocyanate compound together with the aminoplast compound as the curing agent component. When a blocked isocyanate compound is used in combination, chemical resistance, especially acid resistance is improved. The resin composition for paints of the present invention comprises the above-mentioned polyol component and a curing agent component, and can be used as a paint by adding various pigments, organic solvents, additives and the like as required.

As the pigment, the pigments usually used for paints can be used as they are. Specifically, colored inorganic pigments such as titanium oxide, zinc white, iron oxide, and lead, colored organic pigments such as phthalocyanine blue and penzidine yellow, quartz powder, alumina oxide, extender pigments such as precipitated barium sulfate, and stainless powder. Typical examples are metal powders such as zinc powder, aluminum powder, bronze powder, and mica powder. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone;
Typical examples are alcoholic solvents such as methanol, ethanol, butanol and the like. As additives, surface modifiers, dispersants, ultraviolet absorbers, thickeners,
Additives that are generally known as additives for paints such as reaction adjusting catalysts can be mentioned.

The paint thus obtained can be applied not only to various kinds of metal materials such as steel plates, stainless steel plates and aluminum plates but also to inorganic materials such as mortar, concrete and glass, plastics and wood. As a painting method, air spray, airless spray, electrostatic spray,
Conventional methods such as shower coating, dip coating, brush coating, and roll coating can be used as they are. The curing conditions are 130 to 150 ° C. and 20 to 3
Various conditions such as low temperature baking for 0 minutes, high temperature short time baking for 200 to 230 ° C. and 30 to 200 seconds can be adopted. As described above, the coating resin composition of the present invention has long-term weather resistance,
Durability, corrosion resistance, chemical resistance, flexibility, gloss,
It has a feature that a coating film having excellent appearance such as sharpness can be obtained.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to examples. In the examples, "part" and "%" are based on weight. The following were used as the fluorine-containing copolymer and acrylic copolymer used in the examples and comparative examples. (I) Fluorine-containing copolymer (1) Fluorine-containing copolymer (A) Chlorotrifluoroethylene 55.2%, cyclohexyl vinyl ether 20.0%, ethyl vinyl ether 15.0%
A 60% xylol solution of a fluorine-containing copolymer (hydroxyl value 28.3, Tg 45 ° C.) was prepared from the above monomer and 9.8% of hydroxybutyl vinyl ether according to the method described in JP-A-57-34107. (This is called fluorinated copolymer (A))

(2) Fluorine-containing copolymer (B) A monomer containing 47% of tetrafluoroethylene, 30% of cyclohexyl vinyl ether, 8% of ethyl vinyl ether and 15% of hydroxybutyl vinyl ether is similarly polymerized to give a fluorine-containing copolymer. Polymer (hydroxyl value 43.4, Tg
A 60% xylol solution at 35 ° C.) was prepared. (This is referred to as a fluorinated copolymer (B)) (II) Acrylic copolymers (i) to (x) 32.3 parts of xylol in a reaction vessel equipped with a stirrer and a cooler.
After charging 32.3 parts of butyl acetate and heating to 80 ° C., 100 parts of the monomer mixture shown in Table 1 and 1.5 parts of azobisisobutyronitrile were added dropwise over about 2 hours to carry out a stirring reaction. Further, 0.5 part of azobisisobutyronitrile was added, the temperature was raised to 85 ° C., and the mixture was stirred and reacted for 4 hours to prepare an acrylic copolymer having a nonvolatile content of 60% and a weight average molecular weight of 1.8 to 45,000. .

[0018]

[Table 1] (Unit: part) ──────────────────────────────────── Acrylic copolymer i ii iii iv v vi vii viii ix x ──────────────────────────────────── Ethyl acrylate 22 Methacryl Methyl acid 26.4 26.4 75 69 49 9 2.5 structure Isobutyl methacrylate 35 59.1 4 10 30 70 80 85 Synthetic 2-ethylhexyl methacrylate 39 Monocyclohexyl methacrylate 59.1 Amount 2.5 2.5 2.5 Acrylic acid Methacrylic acid 1 1 1 1 Human doxyethyl methacrylate 21 21 12 12 20 20 20 20 20 10 Styrene 40 22 ──────────────────────────────────── Hydroxy acid Base value (solid content) 90 90 51.6 51.6 86 86 86 86 86 43 ─────────────────────────────────── ── Tg ( ) 40 40 63.5 75 92 88 76 55 49 51 ────────────────────────────────────

[Examples 1 to 6 and Comparative Examples 1 to 3] Metallic paints shown in Table 2 were applied to xylol on an object to be coated on which a mild steel plate was coated with a cationic electrodeposition coating film and a polyester / melamine resin-based intermediate coating film. Viscosity for 17 seconds (Ford Cup # 4, 2
After adjusting to 0 ° C.), it was applied by air spray so that the dry film thickness was 20 μm. Then, after standing for 3 minutes, the top clear shown in Table 3 was adjusted to a viscosity of 22 seconds with a mixed solvent of toluol / xylol = 50/50, and then air-sprayed to obtain a dry film thickness of 25 μ. Then, after flashing off for 13 minutes, it was baked at 150 ° C. for 25 minutes. The appearance and gloss of the obtained coating film are shown in Table 4. As is apparent from Table 4, the examples using the resin composition of the present invention had a good coating film appearance and high gloss. On the other hand, Comparative Examples 1 to 3 using the acrylic copolymer (v) having a low content of an alkyl ester of acrylic acid and / or methacrylic acid having 2 to 4 carbon atoms have a clear coating appearance of milky white and low gloss. there were.

[0020]

[Table 2] (Unit: part) ──────────────────────────────────── Actual example comparison Example Metallic paint ──────────────────────── 1 2 3 4 5 6 1 2 3 ────────────── ───────────────────── Fluorine-containing copolymer (A) 30 30 30 30 30 Fluorine-containing copolymer (B) 30 30 30 30 Acrylic copolymer (Vi) 70 Acrylic copolymer (vii) 70 70 70 Acrylic copolymer (viii) 70 Acrylic copolymer (ix) 70 Acrylic copolymer (v) 70 70 70 Aluminum paste (NV: 65%) 10 10 10 10 10 10 10 10 10 Xylol 15 15 15 15 10 10 15 10 10 Aminoplast compound Note 1) 25 25 25 25 31 25 25 31 25 Block isocyanate compound Note 2) 5 5 Paratoluenesulfonic acid 0.2 0.2 0.2 0.2 0.2 Surface conditioner 0.3 0.3 0.3 0.3 0.3 0. 3 0.3 0.3 0.3 ──────────────────────────────────── Note 1) “Super Beckamine L-117 -60 "(trade name of Dainippon Ink and Chemicals, Inc.), NV 60% Note 2)" Coronate DC2725 "(trade name of Nippon Polyurethane Co., Ltd.), NV 80%, Varnish NCO equivalent 362

[0021]

[Table 3] (Unit: parts) ─────────────────────────────────── Actual example ratio Comparative example Top clear ─────────────────────── 1 2 3 4 5 6 1 2 3 ──────────────── ─────────────────── Fluorine-containing copolymer (A) 70 70 70 70 70 Fluorine-containing copolymer (B) 70 70 70 70 Acrylic copolymer (vi ) 30 Acrylic copolymer (vii) 30 30 30 Acrylic copolymer (viii) 30 Acrylic copolymer (ix) 30 Acrylic copolymer (v) 30 30 30 Aminolast compound Note 1) 25 25 25 25 25 20 25 25 20 Block isocyanate compound Note 2) 10 10 Solvent naphtha # 100 / n-Beta 20 20 20 20 20 20 20 20 20 20 Mixed solvent (90/10) UV absorber 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Surface conditioner 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0. 3 ───────────────────────────────────

[0022]

[Table 4] (Unit: parts) ──────────────────────────────────── Actual example ratio comparison Example ─────────────────────────── 1 2 3 4 5 6 1 2 3 ───────────── ─────────────────────── Clear coating Appearance Transparent Same as left Same as left Same as same left Same as left Milky white Same as left Same as left ────────────── ────────────────────── Hikarizawa 89 90 93 94 92 90 58 63 60 (60 ° specular reflectance) ─────────── ────────────────────────── Good Same as left Same as left Same as left Same as left Same as left Same as left Same left Same as left Metallic appearance No aluminum feel ───────── ────────────────────────────

[Examples 7 to 9 and Comparative Examples 4 to 7] The black paints shown in Table 5 were applied to the same objects as in Example 1 with a mixed solvent of cellosolve acetate / xylol acetate = 20/80 to obtain a viscosity. After adjusting to 22 seconds, dry film thickness 35 by electrostatic spray
It was applied so as to have a thickness of μ. Then leave for 10 minutes, then 160
It was baked at ℃ for 20 minutes. The appearance, hardness, blackness, initial gloss and gloss after the weather resistance test of the obtained coating film are as shown in the lower part of Table 5.

[0024]

[Table 5] (Unit: parts) ──────────────────────────────────── Actual example ratio comparison Example ─────────────────────── 7 8 9 4 5 6 7 ─────────────────── ───────────────── Fluorine-containing copolymer (A) 90 60 20 100 60 Black acrylic copolymer (ii) 10 40 80 100 Acrylic copolymer (i) Color Aminoplast compound Note 1) 30 30 30 30 30 40 100 Xylol 45 45 45 45 45 45 45 Coated carbon black 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Pigment dispersion aid 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Material p-toluenesulfonic acid 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Surface conditioning agent 0.6 0.6 0.6 0.6 0.6 0.6 0.6 ────────────────────────────────── ─── Appearance of coating film Good Same as left Same as left Same as left Same as left Good ──────────────────────────────────── Lead brush hardness H 2H 3H F 3H 2H 3H ── ────────────────────────────────── White black The blackness of the coating film is good Same as left Same as left Same as left Same as left Good Sumi appearance ──────────────────────────────────── Initial Mitsuzawa 91 94 96 76 96 44 98 ──────────────────────────────────── 500 hrs 90 92 95 75 93 41 98 Accelerated weatherability ── ──────────────────────────── 1000 hrs 88 88 91 74 90 39 91 Gloss after the test ───────── ───────────────────── Note 3) 2000 hrs 85 83 84 73 74 32 73 ──────────────── ───────────────────── Note 3) Gloss after accelerated weathering test by sunshine weatherometer (60 ° specular reflectance)

As is clear from Table 5, the examples using the resin composition of the present invention have a good coating appearance and high gloss,
The weather resistance was also excellent. On the other hand, Comparative Example 4 not using the acrylic copolymer had low gloss. Further, Comparative Examples 5 and 7 which did not use the fluorine-containing copolymer had poor weather resistance. Further, Comparative Example 6 in which an acrylic copolymer (i) not containing an alkyl ester of acrylic acid and / or methacrylic acid having 2 to 4 carbon atoms is used as the acrylic copolymer.
The coating film was glossy and had very low gloss, and choking occurred in the accelerated weather resistance test of 1500 hrs. It is considered that these causes are due to poor compatibility between the fluorinated copolymer and the acrylic copolymer (i). This is because Comparative Example 1 of the fluorinated copolymer alone and the acrylic copolymer ( i) It can also be estimated from the fact that the gloss is lower than that of Comparative Example 7 alone.

[Examples 10 to 11 and Comparative Examples 8 to 12]
The white paint shown in Table 6 was applied to a chromic acid-based chemical conversion treatment aluminum plate with a knife coater so that the dry film thickness was 25 μm, and baked at 230 ° C. for 1 minute. The gloss, weather resistance, rubbing resistance, bendability, impact resistance and solvent resistance of the obtained coating film are as shown in the lower part of Table 6.

[0027]

[Table 6] Unit: Parts) ──────────────────────────────────── Example Comparison Comparative Example ── ──────────────────── 10 11 8 9 10 11 12 ──────────────────────── ──────────── Fluorine-containing copolymer (A) 63 21 70 63 21 21 White acrylic copolymer (iii) 27 49 70 Acrylic copolymer (iv) 27 49 Color acrylic copolymer Combined (x) 49 Aminoplast compound Note 4) 10 30 30 30 10 30 30 Coated titanium White 40 40 40 40 40 40 40 40 Silver 30 30 25 25 30 30 30 Material Butyl acetate 30 30 25 25 30 30 30 Surface conditioning agent 0.3 0.3 0.3 0.3 0.3 0.3 0.3 ────────────────────────────────── ── Hikarizawa 88 89 72 92 51 56 90 Weather resistance Note 5) 〇 〇 〇 × × × 〇 Rubbing resistance Note 6) 〇 〇 〇 〇 〇 〇 〇 × Foldability Note 7) 〇 〇 × 〇 〇 〇 〇 〇 Impact resistance Note 8) 〇 〇 × 〇 〇 〇 〇 〇 Solvent resistance Note 9) 〇 〇 〇 〇 〇 〇 〇 × ─────── ────────────────────────────

Note 4) Isobutyl etherified melamine (N
V60%) ["U-Van 20SE-60" (trade name, manufactured by Mitsui Toatsu Chemicals, Inc.)] Note 5) Observation of the coating film state after 2000 hours using a sunshine weatherometer 〇: No abnormality ×: Abnormality such as chalking Note 6) Soak the xylol in the gauze, and use your fingers to strongly press 100
Reciprocating and observing the state of the coating film ◯: No appearance of the base material ×: Appearance of the base material Note 7) Bending and crimping 180 degrees and observing the coating film 〇: No abnormality ×: Cracking Note 8) DuPont impact tester 50 to a 1/2 inch diameter impulse
A 0 g weight is dropped from a height of 30 cm and the state of the coating film is observed. ◯: No abnormality x: Cracking Note 9) Cyclohexanone is spotted and the state of the coating film is observed after standing for 3 minutes. ◯: No abnormality x: Dissolution, blistering, etc. Abnormality of

As is clear from Table 6, the examples using the resin composition of the present invention had high gloss and excellent coating performance. On the other hand, Comparative Example 8 not using the acrylic copolymer,
It was inferior in bendability and impact resistance. Further, Comparative Example 9 in which the fluorine-containing copolymer was not used was inferior in weather resistance. Further, Comparative Examples 10 and 11 each using an acrylic copolymer (iv) not containing an alkyl ester of acrylic acid and / or methacrylic acid having 2 to 4 carbon atoms as the acrylic copolymer have very low gloss. there were. Moreover, the comparative example 12 which used the acrylic copolymer (x) which contains a C2-C4 alkyl ester of methacrylic acid as an acrylic copolymer excessively was inferior to rubbing resistance and solvent resistance.

Claims (4)

[Claims] 1. A fluorine-containing copolymer having a hydroxyl group in which a fluorine atom is bonded to a main chain obtained by using a fluoroolefin as an essential component, and acrylic acid and / or methacrylic acid having 2 to 4 carbon atoms as a copolymer component. 1 ester
An acrylic copolymer having a hydroxyl value of 5 to 150, which is a copolymer of ethylenically unsaturated monomers containing 0 to 80% by weight (provided that acrylic acid and / or methacrylic acid has 10 or more carbon atoms as a copolymerization component). It is not used so that the content of the alkyl ester is at least 20% by weight or more.), And a resin composition for coating material, which comprises an aminoplast compound. 2. The fluorocopolymer comprises 30 to 70% by weight of fluoroolefin and 5 of cyclohexyl vinyl ether.
~ 60 wt%, alkyl vinyl ether 3-50 wt%, hydroxyalkyl vinyl ether 3-20 wt%
The resin composition for coating according to claim 1, which is a copolymer comprising 0 to 40% by weight of another comonomer. 3. The coating resin composition according to claim 1, wherein the mixing ratio (weight basis) of the fluorine-containing copolymer and the acrylic copolymer is (95: 5 to 10:90). Stuff. 4. The resin composition for coating composition according to claim 1, wherein the mixing ratio (weight basis) of the polyol component and the aminoplast compound is (95: 5 to 60:40).