JP3514272B2 - Method for producing graft copolymer and paint using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a graft copolymer useful for paints and the like, and a paint containing the graft copolymer.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand in the coating industry for coatings that are maintenance-free, that is, have high weather resistance, from the viewpoint of saving resources and energy. In order to obtain a highly weather resistant paint, a highly weather resistant resin is required together with a highly weather resistant pigment. In recent years, solvent-soluble fluorine-containing copolymers containing fluoroolefin, hydroxyalkyl vinyl ether, alkyl vinyl ether and cyclohexyl vinyl ether as essential components have been used. Compared with conventional resins containing tetrafluoroethylene as a main component, they are soluble in a solvent and have good coating workability. Therefore, they are used as resins for coating materials that can be cured at room temperature. Although this has better weather resistance than conventional acrylic resins, it has a problem that it is inferior in pigment dispersibility, initial gloss, and the like.

In order to improve such a problem, a graft copolymer is obtained by introducing a reactive carbon-carbon double bond into a hydroxyl group-containing fluoropolymer and polymerizing an ethylenically unsaturated monomer in the presence thereof. For manufacturing (Japanese Patent Publication No. 59-469)
64 publication) or a method of producing a graft copolymer by reacting a hydroxyl group-containing fluoropolymer with an isocyanato group-containing unsaturated compound to introduce an unsaturated group and then polymerizing an ethylenically unsaturated monomer. Kaihei 6-199937) and the like are known. These methods are effective in improving the pigment dispersibility and initial gloss, but copolymerize a monomer having a carboxyl group to further improve the pigment dispersibility, or add an unsaturated carboxylic group to the hydroxyl group-containing fluoropolymer. When an acid is reacted, there is a problem that the pot life of the paint is shortened and the workability of coating is extremely deteriorated when it is cured at room temperature using an isocyanate curing agent.

[0004]

The present invention is to solve the above problems and is excellent in weather resistance and pigment dispersibility.
And graft copolymers suitable excellent paint coating workability
And a paint using the same .

[0005]

The present invention provides a compound of the general formula (I) in the presence of a fluorine-containing resin (A) having a reactive double bond via a urethane bond.

[Chemical 2] (However, in the formula, R ¹ , R ² and R ³ represent hydrogen or a lower alkyl group, and m represents an integer of 1 to 10.) and an ethylenically unsaturated monomer (B) and a carboxyl group. preparation of the graft copolymer, which comprises polymerizing a monomer mixture comprising ethylenically unsaturated monomer (C) having relates paint containing graft copolymer obtained by this manufacturing method.

The fluorine-containing resin (A) is produced, for example, by reacting a fluorine-containing copolymer having a hydroxyl group, a polyvalent isocyanate compound having two or more isocyanato groups, and an ethylenically unsaturated monomer having a hydroxyl group. can do. In this method, a polyisocyanate compound and an ethylenically unsaturated monomer having a hydroxyl group are reacted to produce an isocyanato group-containing polymerizable adduct having a urethane bond, and then a fluorine-containing copolymer having a hydroxyl group is prepared. It is preferable to react. Here, as the polyvalent isocyanate compound, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, diphenylmethane diisocyanate,
2,2,4-trimethylhexamethylene diisocyanate, cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), biuret of hexamethylene diisocyanate, trimer of isophorone diisocyanate containing isocyanurate ring, etc. 2 There is no particular limitation as long as it is a compound having one or more isocyanato groups. Preferred are diisocyanate compounds having isocyanato groups having different reactivity such as 2,2,4-trimethylhexamethylene diisocyanate and tolylene diisocyanate.

As the ethylenically unsaturated monomer having a hydroxyl group, one having one hydroxyl group is preferable, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and -2-acrylic acid. Acrylic acid hydroxyalkyl ester such as hydroxyl butyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylic acid-2
-Methacrylic acid hydroxylalkyl ester such as hydroxylbutyl, N-methylolacrylamide, N-
Examples include methylol methacrylamide. The above-mentioned polyvalent isocyanate compound and the ethylenically unsaturated monomer having a hydroxyl group are blended so that the former isocyanato group / the latter hydroxyl group are in an equivalent ratio of 1.0 / 0.5 to 1.0 / 0.7. Then
It is preferable to react. Here, unreacted ethylenically unsaturated monomer having a hydroxyl group may remain.

The reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C., and a urethane reaction catalyst such as dibutyltin dilaurate may be used in the reaction. Also,
In the reaction, a polymerization inhibitor such as bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane or hydroquinone may be present. The reaction is preferably carried out in a suitable organic solvent. Examples of the organic solvent include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and cellosolve acetate. Thus, an isocyanate-containing polymerizable adduct having a urethane bond is obtained.

The fluorine-containing resin (A) can be obtained by reacting a fluorine-containing copolymer having a hydroxyl group with the above isocyanate-containing polymerizable adduct having a urethane bond. The reaction temperature is generally 20 to 150 ° C., preferably 40.
It is -100 degreeC, and it is preferable to carry out in inert gas atmosphere or airflow, such as nitrogen gas. Reaction time is 30 minutes to 5
0 hours is preferred. During the reaction, the urethane reaction catalyst, the polymerization inhibitor, etc. may be present. The reaction is preferably carried out in the above organic solvent. In addition, this reaction is
The reactive double bond is preferably 0.001 to 0.025 mol per 100 g of the obtained fluorine-containing resin.

The fluorine-containing resin (A) can be obtained by reacting a fluorine-containing copolymer having a hydroxyl group with an ethylenically unsaturated monomer having an isocyanato group.
The reaction is carried out in the same manner as above. As the ethylenically unsaturated monomer having an isocyanato group, isocyanatomethyl acrylate, isocyanatoethyl acrylate, isocyanatoalkyl acrylate such as isocyanatobutyl acrylate, isocyanatomethyl methacrylate, isocyanatoethyl methacrylate, isocyanatobutyl methacrylate, etc. Isocyanatoalkyl methacrylate, etc.

The hydroxyl group-containing fluorine-containing copolymer used in the fluorine-containing resin (A) preferably has a hydroxyl value of 0.57 to 250, more preferably 3 to 120. If the hydroxyl value is less than 0.57, the introduction of double bonds tends to be insufficient, while if it exceeds 250, turbidity occurs when dissolved in a solvent, and the water resistance of the coating film tends to decrease. There is a tendency. Further, this copolymer preferably has a fluorine content of 1 to 60% by weight from the viewpoint of pigment dispersibility and the like.

Examples of the fluorine-containing copolymer having a hydroxyl group include copolymers obtained from a monomer mixture containing fluoroolefin, hydroxylalkyl vinyl ether, and alkyl vinyl ether and / or cycloalkyl vinyl ether. Examples of fluoroolefins include fluoroethylene such as monofluoroethylene, difluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, and 1,1-bis (trifluoromethyl) ethylene. Examples of the hydroxyl alkyl vinyl ether include hydroxyl ethyl vinyl ether, hydroxyl propyl vinyl ether, hydroxyl butyl vinyl ether, hydroxyl pentyl vinyl ether, hydroxyl hexyl vinyl ether and the like, and those in which hydrogen of these alkyl groups or vinyl groups is replaced with fluorine.
Examples of alkyl vinyl ethers and cycloalkyl vinyl ethers include cyclohexyl vinyl ether and the like.

Among the hydroxyalkyl vinyl ethers, examples of the hydroxyalkyl vinyl ether in which hydrogen of the alkyl group or vinyl group is substituted with fluorine include, for example,

[Chemical 3] Etc. Fluorine-containing copolymer having a hydroxyl group, as other components, ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl acetate,
Unsaturated acids such as n-vinyl butyrate, methyl methacrylate, maleic acid, fumaric acid, acrylic acid and methacrylic acid, carboxyalkyl vinyl ethers such as carboxyethyl vinyl ether and carboxypropyl vinyl ether, fluorine-substituted compounds thereof, and carboxyalkyloxyalkyl vinyl ethers. An ethylenically unsaturated monomer having a carboxyl group such as the fluorine-substituted compound may be contained as a copolymerization component.

In the fluorine-containing copolymer having a hydroxyl group, the fluoroolefin is preferably contained as a constituent in an amount of 40 to 60 mol%, and the hydroxyalkyl vinyl ether is used so that the hydroxyl value of the copolymer becomes 0.57 to 250. It is preferably contained, and more preferably contained in the range of 3 to 120. Here, when the content of fluoroolefin is less than 40 mol%, the effect of improving the weather resistance tends to decrease, and when it exceeds 60 mol%, the production tends to become difficult. Further, the hydroxyl value is 0.
If it is less than 57, the introduction of double bonds tends to be insufficient, and if it exceeds 250, the solubility in organic solvents tends to be limited because the amount of hydroxyalkyl vinyl ether used increases. From the viewpoint of solubility in organic solvents, it is preferable that the hydroxyalkyl vinyl ether is 15 mol% or less as a constituent in the copolymer.

The cycloalkyl vinyl ether and the alkyl vinyl ether are preferably used in an amount of 5 to 60 mol% in total in the fluorine-containing copolymer. If the amount of cycloalkyl vinyl ether and alkyl vinyl ether is less than 5 mol%, the above copolymer tends to be difficult to dissolve in an organic solvent, and if it exceeds 60 mol%, the amount of fluoroolefin or hydroxyalkyl vinyl ether used decreases. Effects such as weather resistance tend to decrease. Further, it is more preferable in terms of characteristics that the cycloalkyl vinyl ether and the alkyl vinyl ether are used in an amount of 5 to 45 mol% in the copolymer. The above-mentioned other components are contained in the copolymer in an amount of 3
It is preferably used at 0 mol% or less. Among the other components, the ethylenically unsaturated monomer having a carboxyl group has a copolymer acid value of 0 to 20, and more preferably 1.0 to 1
It is preferably contained so as to be 0. Here, if the acid value exceeds 20, the solubility in an organic solvent tends to be limited.

Fluorine-containing resin (A) obtained as described above
Contains 0.001 to 1001 of reactive double bond per 100 g.
It is preferable to adjust to have 0.025 mol,
More preferably, it is prepared so as to have 0.002 to 0.015 mol. If it is less than 0.001 mol, graft polymerization tends to be difficult when polymerizing the monomer mixture, and if it exceeds 0.025 mol, gelation tends to occur easily when polymerizing. The reactive double bond needs to be present in the fluorine-containing resin (A) through a urethane bond. As a result, the graft copolymer obtained in the present invention has excellent transparency and pigment dispersibility.

The weight average molecular weight of the fluorine-containing resin (A) is preferably 1,000 to 200,000, more preferably 10,000 to 100,000. When this molecular weight is less than 1,000, the weather resistance and chemical resistance tend to be reduced, and when it exceeds 200,000, gelation tends to occur when the monomer mixture is polymerized. The weight average molecular weight in the present invention is a value measured by a gel permeation chromatography method and obtained using a standard polystyrene calibration curve.

The ethylenically unsaturated monomer (B) represented by the general formula (I) contains an amino group in the molecule. Examples of the monomer represented by the general formula (I) include aminoethyl acrylate, N-methylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N,
N-diethylaminoethyl acrylate, N, N-methyl
Le ethylamino ethyl acrylate, N, N- dipropyl aminoethyl acrylate, aminopropyl acrylate, N- methylamino propyl acrylate, N, N
-Dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-methylethylaminopropyl acrylate, N, N-dipropylaminopropyl acrylate, aminohexyl acrylate, N-methylaminohexyl acrylate, N, N-
Dimethylaminohexyl acrylate, N, N-diethylaminohexyl acrylate, N, N-methylethylaminohexyl acrylate, N, N-dipropylaminohexyl acrylate, aminohexyl acrylate, N-methylaminohexyl acrylate, N, N-
Amino group-containing acrylates such as dimethylaminohexyl acrylate, N, N-diethylaminohexyl acrylate, N, N-methylethylaminohexyl acrylate, N, N-dipropylaminohexyl acrylate, aminoethyl methacrylate, N-methylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-methylethylaminoethyl methacrylate, N, N-dipropylaminoethyl methacrylate, aminopropyl methacrylate, N-methylaminopropyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, N, N-methylethylaminopropyl methacrylate, N, -Dipropylaminopropyl methacrylate, aminohexyl methacrylate, N-methylaminohexyl methacrylate, N, N-dimethylaminohexyl methacrylate, N, N-diethylaminohexyl methacrylate, N, N-methylethylaminohexyl methacrylate, N, N-di Propylaminohexyl methacrylate, aminohexyl methacrylate, N-methylaminohexyl methacrylate, N, N
Examples thereof include amino group-containing methacrylates such as dimethylaminohexyl methacrylate, N, N-diethylaminohexyl methacrylate, N, N-methylethylaminohexyl methacrylate and N, N-dipropylaminohexyl methacrylate.

Of these, preferred are N,
Mention may be made of N-dimethylaminoethyl acrylate and N, N-dimethylaminoethyl methacrylate. When the graft copolymer is produced, the amount of the component (B) used is
0 for the total amount of (A), (B), (C) and (D).
01 to 10% by weight is preferable, 0.1 to 5% by weight is more preferable, and 0.1 to 3% by weight is particularly preferable. 0.01
If it is less than 10% by weight, the effect of extending the pot life tends to decrease, and if it exceeds 10% by weight, the water resistance of the coating film tends to decrease.

Examples of the ethylenically unsaturated monomer (C) having a carboxyl group include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid monoalkyl ester. The amount of the component (C) used is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the total amount of the components (A), (B), (C) and (D). , 0.1 to 3% by weight is particularly preferable.
If it is less than 0.01% by weight, the pigment dispersibility tends to decrease, and if it exceeds 10% by weight, the pot life of the coating material tends to be short and the coating tends to be difficult.

Other ethylenically unsaturated monomers (D)
Is an optional component and is used as necessary. As the component (D), methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylic acid Acrylic alkyl esters such as lauryl, stearyl acrylate, cetyl acrylate, dodecyl acrylate, and similar methacrylic acid alkyl esters,
Styrene or vinyltoluene, α-methylstyrene, substituted styrene such as chlorostyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl acetate, maleic acid dialkyl ester and the like can be used,
2-hydroxyethyl acrylate, acrylic acid 2
-Hydroxypropyl, acrylic acid hydroxyalkyl esters such as 2-hydroxybutyl acrylate, similar hydroxyalkyl esters of methacrylic acid, monoacrylic acid esters or monomethacrylic acid esters of polyhydric alcohols such as glycerin and trimethylolpropane, N
-A polymerizable monomer having a hydroxyl group such as methylol acrylamide, N-methylol methacrylamide or an alkyl ether compound thereof can be used. Also,
If necessary, an unsaturated amide such as acrylamide or methacrylamide, or a polymerizable monomer having an oxirane group such as glycidyl methacrylate or glycidyl acrylate can be used. The component (D) is (A),
0 to 8 relative to the total amount of components (B), (C) and (D)
The content of 9.98% by weight is preferable because other components can be used in the above-mentioned preferable range. If the amount of the polymerizable monomer having an unsaturated amide and / or oxirane group is too large, the water resistance of the coating film may be lowered, or the reaction solvent may be limited, so that (A), (B ),
It is preferably used in an amount of 30% by weight or less based on the total amount of the components (C) and (D).

The graft copolymer of the present invention comprises the above (A)
It can be obtained by mixing the components (B) and (C) and, if necessary, the component (D) in the presence of the components and polymerizing. Here, the component (A) is preferably 10 to 90% by weight, more preferably 30 to 80% by weight, the total of the components (B), (C) and (D) (hereinafter referred to as “(BCD) component”). (Omitted)
Is preferably 90 to 10% by weight, more preferably 20 to
Add 70% by weight. Here, the ratio of the component (A) and the component (BCD) is (A) component / (BCD) component (weight ratio),
If it is less than 10/90, the weather resistance and chemical resistance of the coating film will tend to deteriorate, and if it exceeds 90/10, the initial gloss, dispersibility of the pigment, drying property, compatibility with other resins, etc. Tends to decrease.

The polymerization of the component (BCD) in the presence of the component (A) can be carried out by adding toluene, xylene, methyl isobutyl ketone, butyl acetate, ethyl acetate, cellosolve acetate, butyl cellosolve, 1-butanol, 2-butanol, if necessary. , 1-propanol, 2-propanol and the like organic solvents can be used as the reaction solvent. As a polymerization catalyst, benzoyl peroxide, lauroyl peroxide, bis-
3,5,5-trimethylhexanol peroxide, t
-Butyl cumyl peroxide, di-t-butyl peroxide, 1,1-di-t-butyl peroxy-3,3,5
-Trimethylcyclohexane, t-butylperoxy-
2-ethylhexanoate, t- butyl peroxy benzoate, di -t- butyl peroxy - trimethyl adipate, cumene hydroperoxide, organic peroxide compound, such as t-butyl hydroperoxide, azobisisobutyronitrile, There are azo compounds such as dimethyl azodiisobutyrate, and one or more of these can be used. The amount used is preferably 0.1 to 10% by weight, more preferably 0% by weight based on the total monomers. 2 to 4% by weight, and the reaction condition can be carried out by heating at 50 to 200 ° C. for 1 to 10 hours. The polymerization catalyst is appropriately selected in order to obtain a polymerization temperature, a desired molecular weight and a desired molecular weight distribution, and to complete the polymerization, that is, to reduce the residual monomer.

The graft copolymer obtained according to the present invention is used as a component of the coating material of the present invention. The graft copolymer obtained according to the present invention can be dissolved in an organic solvent to form a lacquer paint. Further, a curing agent known as a curing agent for acrylic resin coatings, for example, a melamine resin, an isocyanate prepolymer or the like can be appropriately combined to form a curing coating composition. Particularly, the graft copolymer of the present invention is preferable when it is combined with an isocyanate prepolymer because the pot life of the coating composition is extended. In that case, the hydroxyl value of the graft copolymer is a factor that influences the performance of the cured coating film. The hydroxyl value can be adjusted by the hydroxyl value of the component (A) and the amount thereof, and the amount of the polymerizable monomer having a hydroxyl group in the component (D).

When used as a coating material, inorganic pigments such as titanium white, cadmium yellow and carbon black, and organic pigments such as phthalocyanine type and azo type pigments can be added, if necessary. Further, if necessary, additives such as an antioxidant, a pigment dispersant and an ultraviolet absorber may be used. It is preferable that such a pigment is sufficiently kneaded with the graft copolymer before use. The coating material obtained as described above is particularly suitable for coating materials such as wood, metal, slate, roof tile, and automobiles that require weather resistance.
As the organic solvent used in the paint, those which can be used as the reaction solvent can be used. In this case, the resin solid content is appropriately selected depending on the application, but is preferably 20 to 50% by weight.

[0026]

EXAMPLES Next, the present invention will be described in detail with reference to examples. In the examples, "part" and "%" mean "part by weight" and "% by weight", respectively. Synthesis Example 1 2,2,4-trimethylhexamethylene diisocyanate 210 parts, methyl ethyl ketone 110.6 parts, dibutyltin dilaurate 0.166 parts and bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane (polymerization (Inhibitor) 0.332 part was charged into a flask equipped with a thermometer, a stirrer, a nitrogen gas blowing tube and a reflux condenser, heated to 60 ° C., and then 121.8 parts of 2-hydroxyethyl acrylate was added over 3 hours. After evenly dripping,
The reaction was carried out at the same temperature for 2 hours to synthesize a polymerizable adduct having an isocyanato group. The resulting solution has a heating residue of 70%.
And the isocyanato group content of this polymerizable adduct is 9
%Met.

Synthesis Example 2 Lumiflon L as a fluorine-containing copolymer having a hydroxyl group
F-400 (trade name, manufactured by Asahi Glass Co., Ltd., hydroxyl value 47,
Acid value 5, Fluorine content about 27%, Weight average molecular weight about 8
30,000 (gel permeation chromatography analysis: standard polystyrene equivalent), a copolymer obtained from monomers containing trifluoroethylene and hydroxyalkyl vinyl ether, and trifluoroethylene is about 5
0 mol% xylene solution (heating residue 50%,
Specific gravity 1.4 (g / cc), viscosity about 800cps (normal temperature)) 10
0 part, 0.67 part of a solution of the polymerizable adduct having an isocyanato group obtained in Synthesis Example 1 and 0.33 part of xylene were charged into a flask equipped with a thermometer, a stirrer and a reflux condenser,
The reactive double bond is reacted with the resin 10 by reacting at 80 ° C. for 1 hour.
A fluorine-containing resin solution (heating residue 50%) having 0.003 mol in 0 g was obtained. This resin solution had a hydroxyl value of 23.

Synthesis Example 3 Lumiflon L as a fluorine-containing copolymer having a hydroxyl group
F-200 (trade name, manufactured by Asahi Glass Co., Ltd., fluorine content 28
%, Hydroxyl value 53, acid value 0, weight average molecular weight 40,00
0 (gel permeation chromatography analysis: standard polystyrene conversion), chlorotrifluoroethylene and hydroxyalkyl vinyl ether copolymer) in xylene (heating residue 60%, specific gravity 1.13 (g / cc),
A viscosity of about 2500 cps (normal temperature)) 83 parts, a solution of the polymerizable adduct having an isocyanato group obtained in Synthesis Example 1 (0.67 parts) and xylene 0.16 parts are reacted in the same manner as in Synthesis Example 2,
A fluorine-containing resin solution having a reactive double bond in an amount of 0.003 mol per 100 g of resin (heating residue adjusted to 50% with xylene) was obtained. This resin solution had a hydroxyl value of 26.

Examples 1 to 7 and Comparative Examples 1 to 3 The formulations shown in Tables 1 and 2 were charged in a flask equipped with a thermometer, a stirrer, a nitrogen gas blowing tube and a reflux condenser.
While stirring, the mixture was heated at 100 ° C. for 6 hours under a nitrogen stream, and then 0.5 part of benzoyl peroxide was added, and then 110 ° C.
By heating for 2 hours, a copolymer was obtained. Then, xylene was added to adjust to an appropriate heating residue. The heating residue, acid value and hydroxyl value of the resulting copolymer solution are shown in Tables 1 and 2.
Shown in.

[0030]

[Table 1]

[0031]

[Table 2]

Evaluation Solution of the copolymers obtained in Examples 1 to 7 and Comparative Examples 1 to 3 , xylene solution of the fluorine-containing copolymer having a hydroxyl group used in Synthesis Example 2 (referred to as Comparative Example 4 ), and Using the xylene solution of the fluorine-containing copolymer having a hydroxyl group used in Synthesis Example 3 (referred to as Comparative Example 5 ), an isocyanate-curable coating material was produced and tested. The hydroxyl groups of the copolymer and the isocyanato groups of Coronate EH (isocyanate prepolymer, manufactured by Nippon Polyurethane Co., Ltd.), which is a curing agent, were blended in equimolar amounts. Bonderite # 144-treated steel plate (manufactured by Nippon Test Panel Co., Ltd.) was applied with a bar coater # 60 so as to have a film thickness of 30 μm, and dried at room temperature for 1 week to evaluate the coating film performance. Further, a solution prepared by coating the solution of the copolymer synthesized in Example 2 without blending an isocyanate curing agent was used as Comparative Example 6 and was similarly tested. The results are shown in Tables 3 and 4.

Test Conditions (1) Appearance of Resin The graft copolymer was placed in a glass beaker with a solution state of 300 cc.
The state (transparency) of the resin solution at 23 ° C. was visually observed and evaluated according to the following criteria. ○: transparent ×: cloudy film state Each solution was applied on a glass plate by flow coating, set for 20 minutes, dried at 108 ° C for 3 hours, and the state (transparency) of the resin film at 23 ° C was visually observed. And observed according to the following criteria. ○: transparent ×: cloudy

(2) Initial Gloss The initial gloss (60 degree specular reflectance) of the test plate prepared was measured with a gloss meter. (3) Accelerated weather resistance The prepared test plate is a Q-UV accelerated weather resistance tester (US, Q
-Panel), at 50 ° C for 4 hours-condensation 5
After exposure to ultraviolet rays for a predetermined time shown in Table 3 under a cycle condition of 0 ° C. for 4 hours, the specular reflectance of 60 degrees was measured, and the gloss retention rate was calculated by the following formula.

[Equation 1] (4) Pigment dispersibility 100 parts of each solution (solid content) and 3 parts of carbon black are mixed, kneaded with a three-roll mill, and the particle size is 5 μm with a particle gauge.
It kneaded until it became the following. Subsequently, the prepared coating material was allowed to stand at room temperature for 7 days, and the separability (sedimentability) of the pigment was examined. The pigment dispersibility was evaluated according to the following criteria. ○: No separation △: Some separation was observed ×: Clear separation

(5) Chemical resistance (acid resistance) The prepared test plate was immersed in 5% sulfuric acid and left for 240 hours, and the appearance of the coating film (blister, matting) was visually observed. The chemical resistance was evaluated according to the following criteria. ○: No abnormality in coating film ×: Abnormality in coating film (6) Pot life test About 15 g of the coating material used for preparing the plate was sealed in a 30 cc glass bottle, and the time until the coating composition stopped flowing at room temperature was measured.

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

The use of the graft copolymer obtained by the production method according to claim 1 gives a coating excellent in resin appearance, pigment dispersibility and pot life. Using this coating, initial gloss and weather resistance are obtained. Also, a coating film having excellent chemical resistance can be obtained. The production method according to the second aspect has the effects of the production method according to the first aspect, and a graft copolymer having particularly excellent weather resistance can be obtained. The manufacturing method in claim 3 is the same as in claim 1.
The graft copolymer having the effect of the production method in (1) and particularly excellent weather resistance can be obtained. The manufacturing method according to claim 4 is
The effects of the manufacturing method according to claim 1 are exhibited, and particularly the balance of those effects is excellent. The production method according to the fifth aspect has the effect of the production method according to the first aspect, and a graft copolymer having excellent transparency and pigment dispersibility can be obtained. The production method according to the sixth aspect has the effects of the production method according to the first aspect, and in particular, a graft copolymer having excellent water resistance of the coating film and pigment dispersibility can be obtained . Paint in 請 Motomeko 7, the appearance of the resin is an excellent paint pigment dispersibility and pot life, initial gloss using this paint,
A coating film having excellent weather resistance and chemical resistance can be obtained. Claim 8
The coating material according to the present invention is a curable coating material that exhibits the effect of the coating material according to claim 7 . The coating composition according to claim 9 is the coating composition according to claim 8.
The effect of the paint in is exhibited, and the pot life is further extended.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08F 220: 06 C08F 220: 34 220: 34) (56) References JP-A-4-39313 (JP, A) JP-A-7 -113002 (JP, A) JP 62-295914 (JP, A) JP 6-199937 (JP, A) JP 62-25104 (JP, A) (58) Fields investigated (Int.Cl) . ^7, DB name) C08F 290/00 - 290/14 C08F 299/00 - 299/08 C08G 18/00 - 18/87 C09D 1/00 - 201/10

Claims (9)

(57) [Claims] 1. In the presence of a fluorine-containing resin (A) having a reactive double bond via a urethane bond, the compound represented by the general formula (I): (However, in the formula, R ¹ , R ² and R ³ represent hydrogen or a lower alkyl group, and m represents an integer of 1 to 10.) and an ethylenically unsaturated monomer (B) and a carboxyl group. A method for producing a graft copolymer, which comprises polymerizing a monomer mixture containing an ethylenically unsaturated monomer (C) having 2. A fluorine-containing resin (A) is obtained by reacting a fluorine-containing copolymer having a hydroxyl group, a polyvalent isocyanate compound having two or more isocyanato groups, and an ethylenically unsaturated monomer having a hydroxyl group. The method for producing a graft copolymer according to claim 1, wherein 3. The graft copolymer according to claim 1, wherein the fluorine-containing resin (A) is obtained by reacting a fluorine-containing copolymer having a hydroxyl group and an ethylenically unsaturated monomer having an isocyanato group. How to make a coalesce. 4. Fluorine-containing resin (A) 10 to 90% by weight
In the presence of 0.01 to 10% by weight of the ethylenically unsaturated monomer (B) represented by the general formula (I) and 0.01 to 10 ethylenically unsaturated monomer (C) having a carboxyl group.
% By weight and other ethylenically unsaturated monomer (D) 0 to
The method for producing a graft copolymer according to claim 1, 2 or 3, which comprises polymerizing a monomer mixture consisting of 89.98% by weight. 5. The amount of reactive double bonds of the fluorine-containing resin (A) is 0.001 to 0.0 per 100 g of the resin (A).
It is 25 mol, The manufacturing method of the graft copolymer of Claim 1, 2, 3 or 4. 6. A fluorine-containing copolymer having a hydroxyl group,
The method for producing a graft copolymer according to claim 2 or 3, wherein the hydroxyl value is 0.57 to 250 and the fluorine content is 1 to 60% by weight. 7. The graph according to claim 1.
Graft copolymer obtained by the method for producing a copolymer
Paint that contains. 8. A combination of curing agents.
7. The paint according to 7 . 9. The coating composition according to claim 8 , wherein the curing agent is an isocyanate prepolymer.