JPH08209043A - Coating material composition - Google Patents

Abstract

PURPOSE: To obtain a coating material composition which gives a coating film excellent in color tone, brightness, hardness, resistance to weather, resistance to solvents and also excellent in dispersibility, non-coagulation, and non- crystallization properties and fluidity even by using low molecular weight resins. CONSTITUTION: This coating material composition is composed of (A) an acid curable paint varnish and (B) a pigment composition composed of 100wt.pts of pigment, 0.5-30wt.pts of an organic dyestuff of the general formula described below or its aluminum salt and 0.5-100wt.pts of a resin type dispersing agent having a weight average molecular weight of 1000-100000, an amine value of 10-200mgKOH/g containing basic group. General formula Q-(A-:SO3 H)n (Q: an organic dyestuff residue. A: CONHY1 , SO2 NH-Y1 , -CH2 NH-Y1 -; Y1 : a 1-20C (substituted) alkylene or a (substituted) alkenylene or a (substituted) arylene; (n) an integer of 1-4).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a coating composition which is excellent in non-aggregation property, non-crystallinity, fluidity, etc., has a clear color tone and high gloss, and has a sufficient coating film hardness. More specifically, it relates to paints for automobiles.

[0002]

2. Description of the Related Art Acid-curing paints that contain an acid catalyst in the paint and cure when heated form a coating film with excellent weather resistance,
It is not easily affected by acid rain, which has become a social problem in recent years, and is drawing attention as a paint for automobiles. However, since the acid-curable coating material contains an organic solvent, it causes air pollution and the like. As a countermeasure against this, the development of high-solid type paint that reduces the organic solvent contained in the paint is underway.

In high solid acid-curable coatings,
With the increase in paint viscosity due to the reduction of organic solvent content,
There is a problem that the paintability deteriorates. Therefore, it has been attempted to prevent the viscosity from increasing and to improve the coating property by reducing the molecular weight of the resin constituting the paint or completely etherifying the amino resin.

However, when a resin having a relatively low molecular weight is used, it is difficult to sufficiently disperse the pigment as described later.

On the other hand, when the amino resin is completely etherified, the reactivity of the coating material is deteriorated accordingly, and there is a problem that the curing is slower than that of the conventional acid-curable coating material. For this reason, it is necessary to add a large amount of an acid catalyst or use a strong acid catalyst to accelerate the curing of the coating material. However, the acid-curable coating composition containing a large amount of acid catalyst or a strong acid catalyst has a new problem that the dispersion stability of the pigment is deteriorated. Therefore, the development of effective pigment dispersants and pigment compositions has been desired.

Conventionally, various pigment dispersants such as pigment derivatives have been used in various fields in which pigments are dispersed, and pigment derivatives having a basic substituent (hereinafter abbreviated as basic pigment derivative) and the like. The basic group-containing resin-type pigment dispersant obtained by combining a basic substance with a polyester, an acrylic polymer or the like is extremely effective in general paints. However, in acid-curable coatings, the acid catalyst interacts with these basic pigment derivatives and basic group-containing resin-type pigment dispersants, making it impossible to effectively disperse the pigment and further reducing the catalytic activity. It was found that problems such as curing inhibition occur.

As the organic dye derivative having an acidic functional group (hereinafter, abbreviated as acidic organic dye derivative), an aluminum salt of a pigment derivative having a carboxyl group disclosed in JP-B-64-5070 is used. Can be mentioned. However, even if the acidic organic dye derivative was used, almost no effect was observed with respect to the improvement of the pigment dispersibility in the acid-curable coating material.

Further, as an acidic organic dye derivative, a pigment derivative having a sulfone group is disclosed in JP-A-5-98200. However, the pigment derivative having a sulfone group exerted an excellent dispersing effect on a base resin having a relatively high molecular weight, but the thixotropy did not increase so much even if it was a high solid type, and coatability was not impaired. The effect was insufficient for such a low molecular weight resin having a weight average molecular weight of about 10,000 or less.

[0009]

DISCLOSURE OF THE INVENTION As a result of earnest research in view of the above problems, the present inventors have found that in an acid-curable coating composition,
By adding a specific amount of a specific organic dye derivative having an acidic functional group and a basic group-containing resin type pigment dispersant in the pigment composition contained in the acid-curable coating material in a specific amount, the weight average molecular weight is Excellent in pigment dispersibility, non-aggregation, non-crystallinity and fluidity even for low molecular weight resins of about 10,000 or less
The inventors have found that a coating composition having a clear color tone and high gloss as a coating film and having sufficient coating film hardness can be obtained, and completed the present invention.

[0010]

That is, the first or second invention is that the organic dye derivative represented by the following general formula (1) or the aluminum salt of the organic dye derivative is added to 100 parts by weight of the pigment. 0.5 to 30 parts by weight, weight average molecular weight 1000 to 100000, amine value 10 to 200 mg
KOH / g basic group-containing resin type pigment dispersant 0.5 to 10
A coating composition comprising a pigment composition containing 0 part by weight and an acid-curable coating varnish.

General formula (1) Q- (A-SO ₃ H) _{n In the} formula, Q represents an organic dye residue. _{A: -CONH-Y 1 -,} - SO 2 NH-Y 1 -, - C
H ₂ NH-Y ₁ -Y ₁ : an alkylene group having 1 to 20 carbon atoms, which may have a substituent, an alkenylene group which may have a substituent, or a substituent. Arylene group which may be. n: represents an integer of 1 to 4.

Alternatively, in the third invention, the acid-curable coating varnish comprises the resin (a) having a hydroxyl group, the highly alkyletherified melamine resin (b), the acid catalyst (c) and the solvent (d). A coating composition according to the invention or a second invention,
Further, the fourth invention is the coating composition according to the third invention, wherein the hydroxyl group-containing resin (a) has a weight average molecular weight of 10,000 or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
As the pigment in the present invention, various resistance when used in a coating material, for example, light resistance, weather resistance, solvent resistance and the like are desirable, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Perylene-perinone pigment, dioxazine pigment, diketopyrrolopyrrole pigment, anthraquinone pigment, at least one organic pigment or carbon black selected from benzimidazolone pigment, titanium oxide, yellow lead, cadmium yellow, cadmium red, At least one kind of inorganic pigment selected from red iron oxide, iron black, zinc white, navy blue, ultramarine, etc. can be used.

The present invention includes an organic dye derivative represented by the following general formula (1) or an aluminum salt of this organic dye derivative. Formula (1) Q- (A-SO 3 H) n wherein Q: represents an organic dye residue. _{A: -CONH-Y 1 -,} - SO 2 NH-Y 1 -, - C
H ₂ NH-Y ₁ -Y ₁ : an alkylene group having 1 to 20 carbon atoms, which may have a substituent, an alkenylene group which may have a substituent, or a substituent. Arylene group which may be. n: represents an integer of 1 to 4.

Examples of the organic dye residue represented by Q in the general formula (1) include anthraquinone dyes, azo dyes,
Phthalocyanine dyes, quinacridone dyes, dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, indanthrone dyes, flavanthrone dyes, pyranthrone dyes, perylene dyes, perinone dyes, thioindigo dyes. To be

The organic dye derivative represented by the general formula (1) can be prepared by converting an organic dye into -SO ₂ Cl, -COCl,
Introducing a substituent such as —CH ₂ Cl, —CH ₂ NHCOCH ₂ Cl, water, alcohol, acetone or N, N—
It can be obtained by reacting a compound having a sulfone group with a group capable of reacting with these substituents in a reaction solvent such as dimethylformamide in the presence of an alkali catalyst in some cases.

For the organic dye derivative of the present invention, it is practically advantageous to select one having a chemical structure having the same or similar skeleton as the pigment. That is, it is preferable that not only the effect on non-aggregation property, non-crystallinity, fluidity, etc. is great but also the change in hue is small as compared with the case of using the pigment alone. Further, colorless or slightly colored derivatives such as anthraquinone series are advantageous in that they have little change in hue even when added to various pigments and are excellent in versatility.

As Y ₁ in the general formula (1), a phenylene group, an ethylene group or the like is desirable.

The organic dye derivative of the present invention is advantageous in production when it is used as an aluminum salt. That is,
An organic dye derivative having a sulfone group is usually produced by introducing a sulfone group, and then adding it to a large amount of water and filtering it, but it has a disadvantage that it takes a long time to filter because of its high affinity for water. . The use of an aluminum salt as the sulfone group has a low affinity for water, and thus has the advantage of facilitating filtration and shortening the filtration time.

The basic group-containing resin type pigment dispersant used in the present invention is disclosed in JP-A-60-166318 and JP-A-61.
It is a high molecular weight copolymer having a basic substance and a polyester compound or an acrylic polymer, which are disclosed in JP-A-174939 and JP-A-46-7294, and has a weight average molecular weight of 1,000 to 100,000 and an amine value of 10 ~ 200 mg KOH / g.

When the weight average molecular weight of the basic group-containing resin type pigment dispersant is less than 1000, sufficient steric hindrance cannot be obtained,
The dispersing effect is lowered, and even if the weight average molecular weight is larger than 100,000, the aggregation action may occur, which is not preferable. Further, when the amine value of the pigment dispersant is less than 10 mgKOH / g, the interaction with the above organic dye derivative or the aluminum salt of this organic dye derivative is not sufficient, and even if the organic dye derivative is adsorbed on the pigment surface, the dispersion effect is obtained. Can't get
On the other hand, when the amine value of the pigment dispersant exceeds 200 mgKOH / g, the steric hindrance layer becomes smaller than that in the affinity portion for the pigment component, and a sufficient dispersing effect cannot be obtained, which is not preferable.

Such a basic group-containing resin type pigment dispersant may be commercially available, and examples thereof include Solsperse 24000 (manufactured by Zeneca Corporation), Disperbyk-160, Disperbyk-161 and Di.
Examples thereof include sperbyk-162 and Disperbyk-163 (manufactured by BYK Chemie).

The pigment composition and coating composition of the present invention are
The above-mentioned organic dye derivative or an aluminum salt of this organic dye derivative and a basic group-containing resin type pigment dispersant are used in combination. The amount of the organic dye derivative or the aluminum salt of the organic dye derivative added is 0.5 to 30 parts by weight with respect to 100 parts by weight of the pigment, and the amount of the basic group-containing resin-type pigment dispersant added is 100 parts by weight of the pigment. For 0.5 to 1
It is 00 parts by weight. If the addition amount of the organic dye derivative or the aluminum salt of the organic dye derivative and the addition amount of the basic group-containing resin type pigment dispersant are both less than 0.5 parts by weight, the pigment dispersing effect is small, which is not preferable. Further, even if the amount of the organic dye derivative or the aluminum salt of the organic dye derivative used is more than 30 parts by weight, the effect of the amount used cannot be obtained, and the amount of the basic group-containing resin type pigment dispersant is more than 100 parts by weight. If it is used, not only the effect is not obtained but also the curability is lowered.

The method for producing the coating composition of the present invention is carried out by adding a pigment and an organic dye derivative or an aluminum salt of the organic dye derivative and a resinous pigment dispersant containing a basic group to a varnish for an acid-curable coating, and then using a ball mill or It can be manufactured by dispersing with a disperser such as a sand mill and adding an additive such as an anti-sagging agent if necessary. The pigment and the organic dye derivative or the aluminum salt of the organic dye derivative are preferably mixed in advance as a paste or a slurry.

Further, in a pigment such as copper phthalocyanine, quinacridone or dioxazine which requires a pigmentation step such as solvent salt milling, an organic dye derivative can be mixed during the pigmentation step.

The hydroxyl group-containing resin (a) used in the present invention serves as a base resin, and contains at least two hydroxyl groups in one molecule which are reaction sites with the highly alkyletherified melamine resin (b). Examples of the resin include polyester polyol resin, alkyd polyol resin, acrylic polyol resin, epoxy polyol resin, epoxy ester polyol resin, and the like, and acrylic polyol resin and alkyd polyol resin are preferable.

The present invention uses the organic dye derivative or the aluminum salt of the organic dye derivative in combination with the basic group-containing resin type pigment dispersant in a specific amount so as to disperse the pigment over a wide range from low molecular weight to high molecular weight. Therefore, the molecular weight of the hydroxyl group-containing resin (a) used is not particularly limited. Conventional dispersants have a weight average molecular weight of 10
The dispersibility of the pigment could hardly be improved in a system of about 10,000 or less, but in the present invention, the dispersibility of the pigment and the like can be improved even in the system of the hydroxyl group-containing resin (a) having a weight average molecular weight of 10,000 or less.

Polyester polyols include ethylene glycol, polyethylene glycol, neopentyl glycol, 1,6-hexanediol, pentanediol,
Butylene glycol, 1,5-pentanediol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, and other polyhydric alcohols having 2 to 6 hydroxyl groups in one molecule, phthalic acid, isophthalic acid, terephthalic acid, and maleic acid. Acid, methyl terephthalate,
Use a polybasic acid having 2 to 4 carboxyl groups in one molecule such as tetrahydrophthalic acid, trimellitic acid, pyromellitic acid and their anhydrides and, if necessary, a monobasic acid or a monohydric alcohol. It is obtained by an esterification reaction.

The alkyd polyol resin is the polyhydric alcohol, the polybasic acid and castor oil, linseed oil, safflower oil, soybean oil, corn oil, cottonseed oil, hempseed oil, rice bran oil, coconut oil, olive oil, palm oil. And the like, or fatty acids such as heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and isostearic acid.

Acrylic polyol resins include (meth) acrylic acid hydroxyl esters such as hydroxyethyl (meth) acrylate and hydroxylpropyl (meth) acrylate or ε-caprolactone and γ-valerolactone of the above (meth) acrylic acid hydroxyl ester. With a hydroxyl group-containing vinyl monomer obtained by homopolymerizing a hydroxyl group-containing vinyl monomer such as a lactone adduct,
Alkyl (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate
Carboxylic acid-containing monomers such as acrylate, acrylic acid, methacrylic acid, and itaconic acid, styrene-based monomers such as styrene and α-methylstyrene, and vinyl-based monomers such as acrylonitrile, methacrylonitrile, and vinyl acetate. It is obtained by polymerization.

As the epoxy polyol resin, a hydroxyl group-containing epoxy resin, for example, manufactured by Yuka Shell Epoxy Co., Ltd., trade name Epicoat 828, 1001, 1004,
There is 1007 etc.

As the epoxy ester polyol resin, there is one obtained by reacting the above epoxy polyol resin with the above-mentioned monobasic acid or polybasic acid.

As the hydroxyl group-containing resin (a) of the present invention,
An isocyanate compound such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or a modified polyol resin obtained by modifying the above polyol resin with a silicone resin can be used.

The highly alkyl etherified melamine resin (b) used in the present invention forms a carbonium ion in the presence of an acid catalyst to serve as a cross-linking agent, and the amino group is completely or 50% or more alkyl etherified. Melamine resin. Here, the amount of the alkyl ether group is 100% when all the hydrogen atoms of the amino group in the melamine resin are replaced with alkanol and then all the terminal OH groups are replaced with an alkoxy group, and the actually added alkyl is The average ratio of ether groups is expressed in%. The degree of alkyl etherification of the melamine resin must be 50% or more, and the degree of alkyl etherification is 5%.
If it is less than 0%, the acid resistance of the coating film decreases. Examples of the highly alkyl etherified melamine resin are those in which H of a methylol group added to an amino group is substituted with an alkyl group, and the alkyl group includes a methyl group, an ethyl group, n
-Butyl group, isobutyl group and the like can be mentioned.

Such a melamine resin is usually obtained by subjecting a melamine resin to an addition reaction or an addition condensation reaction with an aldehyde such as formaldehyde or paraformaldehyde, and etherifying with a monohydric alcohol having 1 to 4 carbon atoms. To be These alkyl etherified melamine resins are those synthesized by a usual method, and those having a number average molecular weight of 2000 or less are preferably used. When the number average molecular weight exceeds 2,000, it becomes difficult to make the coating high solid.

Since the highly alkyletherified melamine resin (b) of the present invention has a small self-condensation property, it is necessary to add an acid catalyst (c) in order to activate it to generate a carbonium ion. Examples of the acid catalyst (c) include sulfonic acid compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, alkylbenzenesulfonic acid, and alkylnaphthalenesulfonic acid, metaphosphoric acid, orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, phosphoric acid, trimetaline. Acids, triphosphoric acid, tetrametaphosphoric acid, phosphorous acid, monobutylphosphoric acid, monoethylhexylphosphoric acid, phosphoric acid compounds such as monolaurylphosphoric acid, carboxylic acid compounds such as formic acid, oxalic acid, acetic acid, lactic acid, sulfuric acid, hydrochloric acid, etc. There are mineral acids and mineral acid salts such as ammonium chloride. Among them, sulfonic acid compounds such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid are particularly preferable. Further, these acid catalysts may be blocked by amine.

The compounding amount of the hydroxyl group-containing resin (a) and the highly alkyl etherified melamine resin (b) is 90/10 to 30/70 in terms of hydroxyl group containing resin / highly alkyl etherified melamine resin.

The amount of the acid catalyst (c) blended is 0.3 to 5% by weight of the solid content of all resins. When the amount of the acid catalyst (c) is less than 0.3% by weight, the above-mentioned active hydrogen substitution reaction does not proceed well and the coating film is insufficiently cured. on the other hand,
If it exceeds 5% by weight, a hard and brittle coating film is obtained.

As the solvent (d) for dissolving the resin, Solvesso 100 (Exxon Chemical Co., Ltd.), toluene,
Hydroxyl solvent such as xylene, ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate,
Examples thereof include ester solvents such as butyl acetate, ether solvents such as dioxane and ethylene glycol diethyl ether, alcohol solvents such as butanol and propanol. These solvents can be used alone or in an appropriate mixture.

The weight ratio (solid content) of the pigment composition and the acid-curable coating varnish is preferably 3/97 to 50/50, more preferably 5/95 to 30/70. When the compounding ratio of the pigment composition is less than 3, the coloring power of the coating composition is reduced,
If it exceeds 50, it becomes difficult to disperse the pigment, and the quality of the coating tends to be deteriorated.

[0041]

The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Production Example 1 A mixture of 10% aqueous acetic acid solution (200 parts), p-aminobenzenesulfonic acid (36 parts) and anthraquinone-2-carbonyl chloride (20 parts) was reacted at 60 ° C. for 2 hours. Then, the organic dye derivative (1) (14 parts) was obtained by filtering, washing with water, drying and pulverizing.

[0043]

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Production Example 2 Water (200 parts), aminoethanesulfonic acid (16 parts),
Anthraquinone-2-sulfonyl chloride (20 parts),
A mixture of sodium carbonate (7 parts) was reacted at 60 ° C for 2 hours. Then, the organic dye derivative (2) (13 parts) was obtained by filtering, washing with water, drying and pulverizing.

[0045]

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Production Example 3 Water (200 parts), p-aminobenzenesulfonic acid (38
Part), 2-chloromethylanthraquinone (20 parts) and sodium carbonate (7 parts) were reacted at 60 ° C. for 2 hours. Then, the organic dye derivative (3) (13 parts) was obtained by filtering, washing with water, drying and pulverizing.

[0047]

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Production Example 4 A mixture of 10% aqueous acetic acid solution (200 parts), p-aminobenzenesulfonic acid (16 parts) and copper phthalocyanine carbonyl chloride (20 parts) was reacted at 60 ° C. for 2 hours.
Then, the organic dye derivative (4) (12 parts) was obtained by filtering, washing with water, drying and pulverizing.

[0049]

[Chemical 4]

Production Example 5 A mixture of 10% aqueous acetic acid solution (200 parts), p-aminobenzenesulfonic acid (28 parts) and quinacridone-2-carbonyl chloride (20 parts) was reacted at 60 ° C. for 2 hours. Then, the organic dye derivative (5) (13 parts) was obtained by filtering, washing with water, drying and pulverizing.

[0051]

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Production Example 6 Organic dye derivative (1) (5 parts) of Production Example 1 was mixed with water (200 parts).
(0 part) was used to make a slurry, and sodium hydroxide was added to make the solution weakly alkaline. Then, after heating to 60 ° C., an aqueous solution of aluminum sulfate (2 parts) was added to form a sulfone compound as an aluminum salt, which was filtered, washed with water, dried and pulverized to obtain an organic dye derivative (9) (5 parts).

Examples 1 to 7 and Comparative Examples 1 to 6 As shown in Table 1, pigment (CIPigment Red 177), organic dye derivative, basic group-containing resin type pigment dispersant ("Solsperse 24000" manufactured by Zeneca Corporation). ), An acrylic resin (styrene / n-butyl acrylate / 2 ethylhexyl acrylate / 2 hydroxyethyl methacrylate / methacrylic acid copolymer, weight average molecular weight 8000) and Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.) are mixed and dispersed. , A completely alkoxy-type methylated melamine resin (manufactured by Mitsui Cytec Co., Ltd., "Cymel 303") and an acid catalyst (dodecylbenzenesulfonic acid ("Necure 5225", manufactured by King Co.)) were mixed to obtain an acid-curable coating material. The organic dye derivative (6) shown in Table 1 is an anthraquinone in which a sulfone group is directly substituted.

[0054]

[Chemical 6]

When the viscosity of each coating material was measured, as shown in Table 1, the coating composition of the present invention had smaller thixotropy (TI value) than the coating composition of the comparative example, and showed excellent fluidity. Indicated.

The above coating composition was applied to Ford Cup #
The viscosity was adjusted to 4 seconds and 20 seconds, and an intermediate coated plate (a steel plate coated with a primer coating in advance) was coated with air spray so that the thickness of the dry coating film was about 30 μm.
After leaving it to stand for 10 minutes, it was baked at 140 ° C. for 30 minutes.
As shown in Table 1, the coating composition of the present invention does not cause curing inhibition even when a basic group-containing resin-type pigment dispersant is used, exhibits good coating hardness, and exhibits excellent coating gloss. The inventive coating composition was superior to the comparative examples.

The non-aggregation property and the non-crystallinity were evaluated by the stability of color separation, which is a problem in practical use. The above coating composition is diluted with a titanium oxide base coating (titanium oxide dispersion paste, titanium oxide 50 phr dispersed with acrylic / melamine resin) so that the ratio of pigment to titanium oxide is 1/10. , Adjust light color paint. Then, after diluting with Solvesso 100 and adjusting the viscosity with Ford cup # 4 for 20 seconds, it was injected into a test tube and the change of the glass wall surface was observed. As a result, the coating composition according to the present invention was used. Color separation over time was less than that using the coating composition of Comparative Example.

[0058]

[Table 1]

Examples 8-11, Comparative Examples 8, 10, 12,
14, 16 Various pigments 11.4 shown in Table 2 in the same manner as in Example 1
Parts, 0.6 parts of various organic dye derivatives, and a basic group-containing resin-type pigment dispersant (“Sensperse 2400” manufactured by Zeneca Corporation).
0 ") 1.2 parts, 22.8 parts of the acrylic resin, 24 parts of the fully alkoxylated methylated melamine resin, acid catalyst 1
And 39 parts by weight of Solvesso 100 were mixed and dispersed to obtain an acid-curable coating material.

Comparative Examples 7, 9, 11, 13, 15 In the same manner as in Comparative Example 1, various pigments 11.4 shown in Table 2 were used.
Parts, 0.6 parts of various organic dye derivatives, the acrylic resin 2
4 parts, the completely alkoxy type methylated melamine resin 24
Parts, 1 part of acid catalyst and 39 parts by weight of Solvesso 100,
By mixing and dispersing, an acid-curable coating material was obtained.

In Table 2, the content of the organic dye derivative is expressed as 5% based on the amount of (pigment + organic dye derivative), and the content of the basic group-containing resin type pigment dispersant is ( It was expressed as 10% based on the amount of pigment + organic dye derivative).

Further, the organic dye derivative (6) shown in Table 2,
(7) and (8) are obtained by directly substituting a sulfone group on an organic dye residue, (6) is an anthraquinone type, (7) is a phthalocyanine type, and (8) is a quinacridone type. .

[0063]

[Chemical 7]

[0064]

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The coating fluidity, coating gloss and coating hardness were evaluated in the same manner as in Examples 1-6 and Comparative Examples 1-6.
The results are shown in Table 2.

[0066]

[Table 2]

As shown in Table 2, the coating composition of the present invention is superior to the coating composition of Comparative Example in both coating fluidity and coating gloss, and the coating composition of the present invention is a resin containing a basic group. Curing inhibition does not occur even if a type pigment dispersant is used,
It showed good coating hardness.

[0068]

The acid-curable coating composition of the present invention is not only excellent in non-aggregation property, non-crystallinity and fluidity, but also excellent in gloss and hardness of the coating film, and also in weather resistance and solvent resistance. Better than when used alone.

Claims (4)

[Claims] 1. An organic dye derivative represented by the following general formula (1) is used in an amount of 0.5 to 30 parts by weight, a weight average molecular weight of 1,000 to 100,000, and an amine value of 10 to 200 mg KOH / g, relative to 100 parts by weight of a pigment. A coating composition comprising a pigment composition containing 0.5 to 100 parts by weight of a basic group-containing resin type pigment dispersant and an acid-curable coating varnish. Formula (1) Q- (A-SO 3 H) n wherein Q: represents an organic dye residue. _{A: -CONH-Y 1 -,} - SO 2 NH-Y 1 -, - C
H ₂ NH-Y ₁ -Y ₁ : an alkylene group having 1 to 20 carbon atoms, which may have a substituent, an alkenylene group which may have a substituent, or a substituent. Arylene group which may be. n: represents an integer of 1 to 4. 2. 100 parts by weight of the pigment, 0.5 to 30 parts by weight of an aluminum salt of an organic dye derivative represented by the following general formula (1), and a weight average molecular weight of 1000 to 100.
Coating composition comprising an acid-curable coating varnish and a pigment composition containing 0.5 to 100 parts by weight of a basic group-containing resin type pigment dispersant having an amine value of 10 to 200 mg KOH / g. Formula (1) Q- (A-SO 3 H) n wherein Q: represents an organic dye residue. _{A: -CONH-Y 1 -,} - SO 2 NH-Y 1 -, - C
H ₂ NH-Y ₁ -Y ₁ : an alkylene group having 1 to 20 carbon atoms, which may have a substituent, an alkenylene group which may have a substituent, or a substituent. Arylene group which may be. n: represents an integer of 1 to 4. 3. The acid-curable coating varnish comprises a hydroxyl group-containing resin (a), a highly alkyletherified melamine resin (b), an acid catalyst (c), and a solvent (d). Or the coating composition according to 2. 4. The coating composition according to claim 3, wherein the hydroxyl group-containing resin (a) has a weight average molecular weight of 10,000 or less.