JP3117511B2 - Paint composition and coating method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an paint sets Narubutsu, more particularly, to significantly improve the scratch resistance, weather resistance, excellent chemical resistance, it relates to coating sets Narubutsu .

[0002]

2. Description of the Related Art As a top coat for an automobile body or the like, the finished appearance (gloss and smoothness) of a coating film, weather resistance, chemical resistance,
The mechanical properties, adhesion to the undercoat, adhesion during recoating, etc. are generally required performance, but in recent years, with the growing need for coating color design, dark and clear colors such as dark blue, black, and red Since the proportion of the coating color has increased, there has been a problem that the finished appearance is deteriorated due to scratches on the coating film surface. Abrasion The in automobile body, the fabric used in car washing brush, or car wash machine refers to a flaw caused by the collision, such as blown sand soar hair Bataki by <br/> payment wiping scratches, further traveling, this The durability against scratches and the resistance to scratches are performances required for a coating film from immediately after coating to after natural exposure.

Conventionally, as a thermosetting resin composition for paints having excellent weather resistance and improved low-temperature flexibility, a lactone-modified fluorinated copolymer obtained by graft-adding a lactone compound to a fluorinated copolymer and a curing agent (JP-A-59-96177).

[0004] Coatings obtained from this resin composition have a high degree of flexibility and are excellent in weather resistance.
Since the denaturation reaction is carried out at a temperature of several degrees Celsius, the polymer solution is colored, and the storage stability of the lactone-modified fluorocopolymer is poor.

[0005] In order to improve this problem, a fluorine-containing copolymer obtained by copolymerizing a vinyl ether grafted with a lactone compound has been proposed (Japanese Patent Laid-Open No. Heisei 1).
-16815).

[0006] The resin composition has excellent storage stability, when the coating film, to together as having low temperature flexibility, to absorb the external force scratches, have very good effect on scratch resistance. However, this resin composition has water resistance, chemical resistance, has a problem in weather resistance.

Further, as a composition excellent in the scratch resistance of plastics, there has been proposed a coating composition containing a silane compound and a fluorine-containing copolymer using ω-hydroxyalkyl vinyl ether as essential components (USP 3, 42
9,845). This composition has a short alkyl chain length of ω-hydroxyalkyl vinyl ether (n = 2 to 6).
The fluorinated copolymer alone does not exhibit sufficient anti-scratching properties, and since it is a binary alternating copolymer of fluoroolefin and ω-hydroxyalkyl vinyl ether, the hydroxyl value increases and it can be dissolved only in highly polar solvents such as alcohol. There was a problem that not.

That is, in the two-coat one-bake coating method in which the undercoat base paint and the topcoat paint are applied repeatedly and both the coatings are simultaneously cured, the undercoating is performed to secure the separation property of both the coatings and to improve the appearance of the coating. since the top coat using a polar solvent quick-drying the coating base is generally used non-polar solvent which does not dissolve the undercoat base was a big problem in coatability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems of the prior art and to provide a top coat for an automobile body or the like with excellent scratch resistance, weather resistance, and chemical resistance. An object of the present invention is to provide a paint composition having general paint film properties such as water resistance, water resistance and sharpness, and paint properties such as coloring property and storage stability.

[0010]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems. A) CH ₂ = CRO (CH ₂ ) _n OH (R is H or C
H ₃ , n is an integer of 7 to 18) containing 5 to 50 mol% of units based on a hydroxyl group-containing long-chain alkyl vinyl ether and 30 to 70 mol% of units based on fluoroolefin, and having a glass transition. the temperature is -30 to + 50
° C, hydroxyl value is 50-160mgKOH / g, acid value is 0
~ 30mgKOH / g, number average molecular weight 4,000 ~ 4
Fluorine-containing copolymer is 0,000, b) a curing agent having a functional group reactive with a hydroxyl group, containing as essential components, the total of a) component and b) component,
a) component is 50 to 95 wt%, b) component is to provide a coating composition characterized Oh Rukoto in a proportion of 5 to 50 wt%.

In the fluorine-containing copolymer a) used in the composition of the present invention, a hydroxyl group-containing long-chain alkyl vinyl ether monomer is used as an essential component from the viewpoint of scratch resistance.

By copolymerizing the monomer, a side chain having a relatively long chain and high flexibility and having a cross-linking site at a terminal is introduced into the fluorine-containing copolymer. A cured coating obtained by curing such a fluorine-containing copolymer having a side chain forms an elastic coating having excellent self-healing properties. As a result, the coating film does not lead to destruction and absorbs as an elastic deformation to the external force of the scratch, and when the external force disappears, the deformation is promptly recovered, and the scratch is not applied or the degree of the scratch is small and inconspicuous.

[0013] In the fluorine-containing copolymer of the present invention, tetrafluoroethylene as fluoroolefins, but chlorotrifluoroethylene is preferably chosen, Ru can be used in combination. The copolymerization ratio is 30 to 7
It needs to be 0 mol%. If it is less than 30 mol%, sufficient weather resistance cannot be obtained, and if it exceeds 70 mol%, the solubility in a coating solvent becomes insufficient.

[0014] The following hydroxyl group-containing long-chain alkyl vinyl ether monomer is necessary that the methylene chain length is from 7 to 18. When the methylene chain length is 6 or less, a sufficient elastic coating film having an effect on the scratch resistance cannot be obtained, and when it is 19 or more, the solubility of the fluorine-containing copolymer in an aromatic solvent is impaired.

Further, the fluorine-containing copolymer in the present invention comprises:
The two other co-polymerizable vinyl monomer components but it may also be copolymerized. Such a copolymerizable vinyl monomer is not subject to any restrictions as long as it is copolymerizable with a fluoroolefin and a hydroxyl group-containing long-chain alkyl vinyl ether monomer. , Vinyl ether simple substance
In particular, ethyl vinyl ether, n-butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether and the like are preferably employed. further,
As these monomers , some or all of the molecules,
Those that have been fluorinated also Ru can be adopted. Also, these single
The body may have a functional group other than a hydroxyl group such as an epoxy group and a carboxy group.

The fluorinated copolymer of the present invention has a hydroxyl value of 50 to 160 mgKOH / g. If the hydroxyl value is too low, a sufficient crosslink density cannot be obtained as a cured coating film, and the mechanical strength, solvent resistance, and the like of the coating film are unsatisfactory. Those having an excessively high hydroxyl value are not preferred because solubility in a solvent is reduced. Those having a hydroxyl value too high, because only dissolve in a portion of the polar solvent such as alcohol, can not be used as a topcoat Ri paint in two-coat one-bake coating method as described below.

The hydroxyl value is adjusted by adjusting the copolymerization ratio of the fluoroolefin and the hydroxyl group-containing long-chain alkyl vinyl ether. In addition to the above two components, it is possible to lower the hydroxyl value by copolymerizing comonomers including each Ki vinyl ether compound described above. Further, it is possible to increase the hydroxyl value by copolymerizing each Ki other hydroxyl-containing monomers of hydroxy butyl vinyl ether.

The fluorinated copolymer of the present invention has an acid value of 0 to 30 mgKOH / g. Fluorine-containing copolymers having an acid value are preferred because of their improved dispersibility of the pigment and having a catalytic action to promote the reaction with the curing agent. However, those having an excessively high acid value are not preferred because the solubility in a solvent is reduced as in the case of the above-described hydroxyl group having a high acid value.

[0019] The acid number, for example, Ru can <br/> Rukoto to be granted by introducing a carboxylic acid group by the method described in Japanese Patent Publication 61-49323.

Further, the fluorocopolymer of the present invention, the glass transition temperature (you hereinafter abbreviated as T _g) is -30 to + 50 ° C.
It is. T If _g is too low scratch resistance for film hardness is reduced is deteriorated. In addition, stain resistance may be reduced, and tack may be easily generated. On the other hand, if the _Tg is too high, the flexibility, adhesion, and chipping resistance of the coating film decrease, which is not preferable.

The fluorine-containing copolymer of the present invention has a number average molecular weight of 4,000 to 40,000.
If the number average molecular weight is too small, a coating having sufficient strength cannot be obtained, which is not preferable. On the other hand, too large ones are not preferred because not only the viscosity of the solution becomes high and the coatability is lowered, but also the sharpness of the coating film is lowered.

[0022] Additional such copolymers, also the presence of the polymerization medium to monomer mixture of predetermined proportions or polymerization initiator under non coexistence effect brought by copolymerization reaction a polymerization initiator source, such as ionizing radiation Ru can be produced by tightening carried out.

[0023] In this case, as the polymerization initiator, polymerization format or
Other depending on the polymerization medium, or water-soluble it can use an oil-soluble appropriate. Specifically, examples of the water-soluble initiator include a redox initiator comprising a persulfate such as potassium persulfate, hydrogen peroxide or a combination thereof with a reducing agent such as sodium hydrogen sulfite or sodium thiosulfate. Agent,
Further, an inorganic initiator such as a system in which a small amount of iron, ferrous salt, silver nitrate and the like coexist, or a dibasic acid oxide such as disuccinic peroxide, diglutaric peroxide, or monosuccinic peroxide, or azobisisobutyl Organic initiators such as amidine dihydrochloride are exemplified.

Examples of the oil-soluble initiator include peroxyester-type peroxides such as t-butylperoxyisobutyrate and t-butylperoxyacetate, and dialkylperoxydicarbonates such as diisopropylperoxydicarbonate. Benzoyl peroxide,
Azobisisobutyronitrile and the like are exemplified.

The amount of the polymerization initiator, the type, depending on the copolymerization reaction conditions, Ru can be appropriately changed, but usually with respect to monomer total amount to be copolymerized, 0.005 wt%,
In particular, about 0.05 to 0.5% by weight is employed.

In the above-mentioned copolymerization reaction, the type of reaction is not particularly limited, and bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and the like can be employed. from easiness of separation, alcohols such as emulsion polymerization or t- butanol in an aqueous medium, esters, saturated halogenated hydrocarbons containing one or more fluorine atoms, aromatic hydrocarbons such as xylene Solution polymerization using a compound such as a solvent is preferably employed. When the copolymerization reaction is carried out in an aqueous medium, it is preferable to add a basic buffer so that the pH value of the solution during the polymerization does not fall below 4, preferably 6. The addition of a basic substance is also effective in the case of solution polymerization. Further, the method of the present invention can be carried out by a batch system, a semi-continuous system, a continuous system or the like.
You.

In such a copolymerization reaction, the copolymerization reaction temperature can be appropriately selected within the range of -30 ° C. to + 150 ° C. depending on the polymerization initiation source, the type of the polymerization medium, and the like. 0 ° C. to +10 when performing the polymerization reaction
0 ° C., preferably about 10 ° C. to 90 ° C. may be employed.
The reaction pressure is Ru can be appropriately selected, typically from 1 to 10
It is desirable to adopt 0 kg / cm ² , especially about ² to 50 kg / cm ² . The Ru can also occupy perform copolymerization reaction in the presence of a suitable chain transfer agent.

The composition of the present invention contains a curing agent b) having a functional group which reacts with a hydroxyl group. As such a curing agent, it is important to use a polyfunctional compound having reactivity with a hydroxyl group contained as a curing site in the copolymer.

As such a curing agent, first, a melamine curing agent as used in a usual thermosetting acrylic paint,
Examples thereof include a heat curing type such as a urea resin curing agent, a polybasic acid curing agent, and an isocyanate curing agent such as a block polyvalent isocyanate. Melamine curing agents include butylated melamine, methylated melamine, epoxy-modified melamine ,
Partially or fully alkylated etherified melamine resins <br/> like are exemplified, can be used any of various modification degree of 0-6 depending on the application, the self-condensation degree can also be selected as appropriate. As urea resin curing agents , methylated urea resin , butylated urea
Resins and the like are exemplified. Examples of the polybasic acid curing agent, a long chain aliphatic dicarboxylic acids, <br/> also aromatic polycarboxylic acids and anhydrides thereof and the like are useful. As the block polyvalent isocyanate, a block compound of a polyvalent isocyanate described below is suitable. In use of the melamine curing agent or a urea resin <br/> curing agent, it is also possible to accelerate the curing by the addition of an acid catalyst.

[0030] As the curing agent in the present invention, Ru can be used further ones such room temperature curing type isocyanate curing agent such as polyvalent isocyanates. As polyvalent isocyanates, non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, and adducts thereof are particularly useful. When to perform cold cured using isocyanates may Ru can also be accelerated curing by addition of a curing catalyst such as dibutyltin dilaurate <br/> over preparative.

Further, Ru can also employed curing agent comprising a compound having an epoxy group as a curing agent. As such a curing agent, an epoxy compound having an average of two or more epoxy groups in one molecule and having an epoxy equivalent of 100 to 2,000 is preferable. Further, the epoxy group is preferably a so-called alicyclic epoxy group such as dicyclopentadiene dioxide because of its excellent reactivity with a hydroxyl group. Such an epoxy compound is disclosed in JP-A-2-73825.
And the like.

As a curing agent, a silane compound is used .
That the curing agent also Ru can be adopted. Such silane compounds include:
A silane compound having a functional group selected from an average of two or more alkoxysilyl groups, silanol groups and acyloxysilyl groups in one molecule is preferably employed. Such silane compounds, silane coupling agents, silane-based curing agent, a silicone-based curing agent, alkoxysilanes are commercially available under names such Shiran'a <br/> Rukoki sheet mode.

As the curing agent, one of the above curing agents may be used alone, or a plurality of curing agents may be used in combination.

The composition of the present invention can be used as a solution type coating by dissolving it in a coating solvent. Here, as the solvent, it can use without any particular limitation those which are used for ordinary coating. When used as a top coating composition of 2-coat 1-bake coating method is preferably a solubility parameter selects 9 following a single or mixed solvent. In this case, it is necessary that the fluorinated copolymer be dissolved in a solvent having a solubility parameter of 9 or less. In addition, as the undercoat paint at this time , a solution paint using a solvent having a solubility parameter of more than 9 is preferable. This combination is preferable because the finished appearance is excellent. The solvents of the undercoat paint and the topcoat paint are reversed (that is,
Solvent parameter of undercoat paint is 9 or less
And the solvent of the top coat paint
Is greater than 9) or the same (ie, under
Dissolve both the solvent for the coat paint and the solvent for the top coat paint.
The solvency parameter is 9 or less, or
-Solvent for top coat paint and solvent for coat paint together
If the solubility parameter is greater than 9) .
When the topcoat paint is applied, the undercoat paint is re-dissolved and the finished appearance is remarkably deteriorated, which is not preferable.

Solvents having a solubility parameter of 9 or less include toluene, xylene, pentane, hexane, heptane, nonane, cyclohexane, Solvesso # 100 (manufactured by Exxon), Solvesso # 150 (manufactured by Exxon),
Swazol # 1000 (manufactured by Maruzen Petrochemical Co., Ltd.), Swazol # 1500 (manufactured by Maruzen Petrochemical Co., Ltd.), swazol # 18
00 (made by Maruzen Petrochemical Co., Ltd.).

Solvents having a solubility parameter larger than 9 include methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diacetone alcohol, methyl cellosolve, cellosolve, and butyl cellosolve. , Cellosolve acetate, ethyl acetate, butyl acetate,
Examples include isobutyl acetate, benzene, methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone.

It is also preferable to apply the coating composition of the present invention over a water-dilutable aqueous basecoat paint in a two-coat, one-bake coating method since a good finished appearance can be obtained.

In preparing the coating composition of the present invention,
Various devices used for ordinary coating, such as a ball mill, a paint shaker, a sand mill, a jet mill, a three-roll mill and a kneader, can be used. At this time, pigments, dispersion stabilizers, viscosity regulators, leveling agents, gelling inhibitors, ultraviolet absorbers, light stabilizers, and other synthetic resins can be added as long as the purpose is not impaired.

[0039] When using the coating composition of the present invention as a so-called baking coating of heat-curing, upon the formulation, melamine, urea resin, polybasic acids Moshiku its anhydrides, blocked polyvalent isocyanates And the like are mixed at the same time and used as a one-pack type paint.

On the other hand, when used as a room temperature-curable coating using non-blocked polyvalent isocyanates, the curing agent component is separately prepared to form a two-pack coating. In this case, the pot life of about 1 to 10 hours is adjusted by adjusting the type and amount of the isocyanate and the catalyst, the copolymer concentration, and the content of the unit based on hydroxyalkyl vinyl ether in the copolymer. Have, several hours ~
It can be a paint that cures at room temperature in a few days and gives a coating film having good physical properties.

The coating composition used in the present invention contains the above components a) and b) as main components, and the composition ratio of these components is 5% based on the total weight of components a) and b).
0 to 95% by weight, preferably 60 to 85% by weight, and component b) is 5 to 50% by weight, preferably 15 to 40% by weight.
If component a) is less than 50% by weight, the coating does not show sufficient self-healing properties against external forces of scratches,
If the content is more than 10% by weight, the solvent resistance and stain resistance of the cured coating film are undesirably reduced.

When the amount of component (b) is less than 5% by weight, the coating film is not sufficiently cured and an elastically deformed coating film having an effect on scratch resistance is not sufficiently formed. The film is too hard and brittle to reduce the scratch resistance, which is not preferable.

The coating systems of the coating composition of the present invention, immediately when the one-coat solid in the base plate was allowed forming the intermediate coating film undercoat or optionally, if the two-coat one-bake clear was enameled Wet-on-wet paint on top.

The coating method is d A fog scheme, rotary atomizing method,
Airless method, electrostatic coating, immersion coating, etc.

The curing conditions after coating are as follows. Curing at room temperature to 250 ° C. for 1 to 60 minutes depending on the object to be coated, the type of curing agent to be used, etc. A film is obtained.

[0046]

The present invention will be described in more detail with reference to the following examples. Parts and% in the examples are parts by weight and% by weight unless otherwise specified . Synthesis Reitoku Publication of fluorocopolymer 6
Monomers shown in Table 21 to according to the method described in 0-21686
After copolymerization according to the body composition, JP-B-61-4932
Modification was performed according to the method described in No. 3 to obtain fluorinated copolymers A-1 to A-9 shown in Tables 1 and 2 .

[0047]

[Table 1]

[0048]

[Table 2]

Example 1 A-1 in Table 1 was used as a fluorine-containing copolymer, and 54 parts of xylene and 50 parts of butylated melamine (Uban 20SE60, manufactured by Mitsui Toatsu Co. ) were used for 100 parts of A-1. , N-
Butyl alcohol 10 parts, UV absorber (Tinuvin # 9
00, Ciba Geigy) 30 parts of a 10% xylene solution,
10 of light stabilizer (Tinuvin # 144, Ciba-Geigy)
% Xylene solution, 14 parts, surface conditioner (BYK300, B
0.5 part of YK Chemie) was stirred and mixed to prepare composition B-1.

The above composition was diluted using Solvesso # 100 with a Ford cup # 4 to a viscosity of 25 seconds / 20 ° C. to obtain a clear coat paint C-1 .

Examples 2 to 5 Other than using A-2 to A-5 in Table 1 for the fluorinated copolymer.
Prepared compositions (B-2 to B-5) in the same manner as in Example 1.
MadeThen, clear coat paints C-2 to C-5 are obtained.
Was.

Example 6 A-6 shown in Table 2 was used as a fluorine-containing copolymer. Based on 100 parts of A-6 , 21 parts of an isocyanate-based curing agent (Coronate HX: manufactured by Nippon Polyurethane), xylene 54
Parts, curing catalyst (dibutyltin dilaurate) 0.003
Parts, 30 parts of a 10% xylene solution of an ultraviolet absorber, 14 parts of a 10% xylene solution of a light stabilizer (manufactured by Tinuvin # 144 Ciba-Geigy), and 0.5 part of a surface conditioner (BYK300, manufactured by BYK Chemie) are stirred and mixed. A composition (B-6) was prepared.

The above composition was diluted with Solvesso # 100 in a Ford cup # 4 to a viscosity of 25 seconds / 20 ° C. to obtain a clear coat paint C-6 .

Comparative Examples 1 to 3 Compositions (B-7 to B-9) were prepared in the same manner as in Example 1 except that A-7 to A-9 in Table 2 were used for the fluorinated copolymer. Thus, clear coat paints C-7 to C-8 were obtained . Comparison
Composition B-9 of Example 3 was applied without dissolving to Solvesso # 100.
It was impossible to wear.

Production example of base coat paint 10 parts of styrene, 25 parts of methyl methacrylate, 35 parts of ethyl acrylate, 15 parts of n-butyl methacrylate and 2 parts of acrylic acid were mixed in xylene using azobisisobutyronitrile as a polymerization initiator. Polymerization was performed to obtain an acrylic resin solution D-1 having a resin content of 48%. Using this acrylic resin solution, a solvent-type base coat E- 1 was prepared with the following composition. Acrylic resin solution (D-1) 200 parts of Cymel 303 ¹⁾ 20 p-toluenesulfonic acid solution 4.0 Carbon Black FW # 200 ²⁾ 2.0 Note 1) Mitsui Saianamitsu de Ltd. Melamine resin 2) Degussa Carbon black

Next, this base coat E-1 was mixed with toluene 4
0 part, 40 parts of ethyl acetate and 20 parts of cellosolve acetate with a viscosity of 13.5 seconds (Ford Cup #
(4/20 ° C.).

Preparation of Test Plate and Its Evaluation A cationic electrodeposition paint for automobiles was applied on a 0.8 mm-thick dull steel plate which had been subjected to zinc phosphate chemical conversion treatment.
Bake for 0 minutes. Next, apply an intermediate paint for automobiles,
After baking at 40 ° C for 30 minutes, it is ground with # 600 sandpaper, dried, degreased with white gasoline,
The material was used for testing.

After adjusting the viscosity of the base coat paint E-1 to 13.5 seconds on this material, the air spray gun W-6 was used.
1 (manufactured by Iwata cup), was applied to a 18Myu m in dry film thickness, after standing 3 minutes at room temperature, the air spray gun W-61 the clear coating composition C-1 was adjusted to a viscosity 25 seconds using wet-on-wet coating to a thickness of 30.mu. m in dry film thickness, allowed to stand at room temperature for 10 minutes, and baked in a hot air drying oven 140 ° C. 30 min, to prepare a test plate.

Clear Coating Paint C-1 of Examples 1 to 6
-C-6 and clear coat paint C-7 of Comparative Examples 1-2
With respect to C-8 , scratch resistance and general coating film performance were evaluated, and the results are shown in Table 3 .

[0060]

[0061]

[Table 3]

Evaluation method Scratch resistance : An automobile having a test plate attached to a roof was
After the car was washed 20 times with the car washer, the state of the coated surface of the coated plate was observed . The evaluation criteria are as follows. ◎ Passed with almost no scratches by visual observation . ○ Slight scratches were found, but the degree was extremely slight . △ Scratch was noticeable and failed . × × Scratch was noticeable and failed .

[0063] Pencil Hardness: measuring the scratches hardness using a Mitsubishi Pencil Co., Ltd. Uni.

Moisture resistance : The test plate was placed in a thermo-hygrostat at 50 ° C. and 98% RH for 120 hours , and the state of the coated surface immediately after removal was evaluated.

Gasoline resistance : Regular gasoline ( Japan
Visually evaluate the appearance after 24 hours immersion at room temperature Sekiyusha Ltd.).

Acid resistance : 0.3 cc of 10% sulfuric acid was spotted on the coated surface, allowed to stand at 20 ° C. for 24 hours, washed with water, and the coated surface was observed.

Alkali resistance : 0.3 cc of a 10% aqueous sodium hydroxide solution was spotted on the coated surface, allowed to stand at 20 ° C. for 24 hours, washed with water, and the coated surface was observed.

[0068] Weather resistance : Expressed as the gloss retention of the coating film after exposure for 3,000 hours with a sunshine weather meter.

[0069]

Coating composition of the present invention exhibits, and has excellent scratch resistance, form hardness, water resistance, chemical resistance, the balance of such chemical resistance balanced high weather resistance coating Therefore, it is extremely useful for painting automobile bodies and home appliances.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 175/04 C09D 175/04 183/04 183/04 (56) References JP-A-61-87766 (JP, A) JP-A-61-87766 JP-A-2-300253 (JP, A) JP-A-3-24145 (JP, A) JP-A-3-146177 (JP, A) JP-A-4-149287 (JP, A) JP-A-4-317776 (JP JP-A-1-304161 (JP, A) JP-A-63-59373 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 127/12 B05D 1/36 B05D 7/24 302 C09D 161/28 C09D 163/00 C09D 175/04 C09D 183/04

Claims (3)

(57) [Claims] 1. A) CH ₂ ＣＲCRO (CH ₂ ) _n OH (R
Is H or CH ₃ , n is an integer of 7 to 18) 5 to 50 mol% of a unit based on a long-chain alkyl vinyl ether having a hydroxyl group, and 3 units based on a fluoroolefin.
0 to 70 mol%, and the glass transition temperature is-
30 to + 50 ° C., hydroxyl value is 50 to 160 mg KOH /
g, acid value contained as a curing agent, the essential component having the 0～30MgKOH / g, number fluorocopolymer average molecular weight of 4,000~40,000, b) functional group reactive with a hydroxyl group, 50% to 95% by weight of component a) and 5 to 5% of component b) based on the total of components a) and b)
0 paint composition characterized Oh Rukoto at a ratio of weight%. 2. Component (b) is a melamine curing agent or a urea resin hardener.
Agent, polyacid curing agent, isocyanate curing agent, epoxy
A curing agent consisting of a compound having a silane group, or a silane compound
The coating composition according to claim 1 , which is a curing agent composed of a product. 3. A recoated the A Ndako preparative paint and top coat paint, in two-coat one-bake coating method for curing both coating films at the same time after accordingly, as a top coat paint, in claim 1 or 2 A coating method using the composition for coating according to the above .