JPH08218036A - Coating composition - Google Patents

Abstract

PURPOSE: To provide a coating composition composed of a pigment incorporated with a specific organic pigment derivative, etc., and an acid-setting coating varnish, having excellent pigment dispersibility, non-agglomerating tendency, non-crystallizability, fluidity, etc., and forming a coating film having high clarity, gloss and hardness. CONSTITUTION: This coating composition is composed of (A) a pigment composition produced by incorporating (i) 100 pts.wt. of an organic or inorganic pigment preferably having excellent light-resistance, weather resistance and dissolution resistance with (ii) 0.5-100 pts.wt. of an organic pigment derivative, an anthraquinone derivative or an acridone derivative of formula, Q-[X-NR1 -Y-R2 ]n . [Q is an organic pigment residue, an anthraquinone residue or an acridone residue; X is SO2 , CO, CH2 or CH2 NHCOCH2 ; R1 is H, an alkyl or Y-R2 ; Y is a propylene oxide (co)polymer having an average molecular weight of 400-10,000; R3 is H or a 1-4C alkyl; (n) is 1-3] and (B) an acid-setting coating varnish composed of a hydroxyl-containing resin, a highly alkyl-etherified melamine resin, an acid catalyst and a solvent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to non-aggregating, non-crystalline,
The present invention relates to a coating composition having excellent fluidity and the like, having a clear color tone and high gloss, and having 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, in various fields for dispersing pigments, various pigment dispersants such as pigment derivatives have been used, and organic dye derivatives having a basic substituent (hereinafter,
Abbreviated as basic organic dye derivative. ) Or a basic group-containing resin-type pigment dispersant obtained by binding a basic substance with a polyester, an acrylic polymer or the like is extremely effective in general paints.

However, in the acid-curable coating composition, the acid catalyst interacts with the basic pigment derivative or the basic group-containing resin type pigment dispersant, so that the pigment cannot be effectively dispersed and the catalytic activity is further increased. It has been found that the problem of deterioration of curing occurs due to a decrease in the viscosity.

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.

As a result of earnest research in view of the above problems, the present inventors have found that in an acid-curable coating composition, a specific organic dye derivative in a pigment composition contained in the acid-curable coating composition, By adding an anthraquinone derivative or an acridone derivative, pigment dispersibility, non-aggregation property, non-crystallinity,
It was discovered that a coating composition having excellent fluidity and the like, 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.

[0008]

That is, the present invention provides a face
It is represented by the following general formula (1) with respect to 100 parts by weight of the material.
Organic dye derivative, anthraquinone derivative or acrid
A pigment composition to which 0.5 to 100 parts by weight of a vinyl derivative is added,
A coating composition comprising an acid-curable coating varnish. General formula (1) Q- [X-NR₁-Y-R₂]_n (However, in the general formula, Q is an organic dye residue and anthraquinone residue.
Group or acridone residue, X is -SO₂-, -CO-,
-CH₂-Or-CH₂NHCOCH₂-, R ₁Is water
Elementary atom, alkyl group or -Y-R₂-, Y is the average molecule
Propylene oxide polymer in an amount of 400 to 10,000
Is a copolymer of ethylene oxide and propylene oxide
Department, R₂Is a hydrogen atom or lower alkyl having 1 to 4 carbon atoms
And n represents an integer of 1 to 3. ) Further, the acid-curable coating varnish used in the present invention is
Group-containing resin (a), highly alkyl etherified melamine resin
(B), acid catalyst (c), solvent (d)
It

The present invention will be described in detail below. As the pigment in the present invention, various resistances when used in a coating material, for example, light resistance, weather resistance, those having good dissolution resistance and the like are desirable, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, At least one organic pigment selected from perylene pigments, perinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, benzimidazolone pigments, etc. or carbon black, acid value titanium, yellow lead, cadmium yellow It is possible to use at least one inorganic pigment selected from cadmium red, rouge, iron black, zinc white, navy blue, ultramarine and the like.

Organic dye derivative, anthra in the present invention
The quinone derivative or acridone derivative has the following general formula
It is represented by (1). General formula (1) Q- [X-NR₁-Y-R₂]_n (However, in the general formula, Q is an organic dye residue and anthraquinone residue.
Group or acridone residue, X is -SO₂-, -CO-,
-CH₂-Or-CH₂NHCOCH₂-, R ₁Is water
Elementary atom, alkyl group or -Y-R₂-, Y is the average molecule
Propylene oxide polymer in an amount of 400 to 10,000
Is a copolymer of ethylene oxide and propylene oxide
Department, R₂Is a hydrogen atom or lower alkyl having 1 to 4 carbon atoms
And n represents an integer of 1 to 3. )

As the organic dye residue Q in the general formula (1), anthraquinone dye, acridone dye, azo dye, phthalocyanine dye, quinacridone dye,
Examples include dioxazine dyes, anthrapyrimidine dyes, ansanthrone dyes, indanthrone dyes, flavanthrone dyes, pyranthrone dyes, perylene dyes, perinone dyes, and thioindigo dyes.

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 type and acridone type are advantageous in that they have little change in hue even when added to various pigments and are excellent in versatility.

Y is a propylene oxide polymer having an average molecular weight of 400 to 10,000 or a copolymer part of ethylene oxide and propylene oxide. The ratio of ethylene oxide and propylene oxide is arbitrary, but from the viewpoint of water resistance, the ratio of propylene oxide is preferably 50% or more.

The ratio of the organic dye derivative of formula (1), the anthraquinone derivative or the acridone derivative in the present invention to the pigment is 0.5 to 100 parts by weight of the pigment.
100 parts by weight is preferred. If the amount is less than 0.5 parts by weight, the effect of dispersing the pigment is small, which is not preferable. Further, even if it is used in an amount of more than 100 parts by weight, the effect of the used amount cannot be obtained and the coating film performance is adversely affected.

The method for producing the organic dye derivative, the anthraquinone derivative or the acridone derivative of the general formula (1) in the present invention is a conventional method in which the organic dye is -SO ₂ Cl, -C.
OCl, -CH ₂ Cl, by introducing a substituent such as -CH ₂ NHCOCH ₂ Cl, water, alcohol, acetone or,
A method of reacting with mono- or bis- (polyoxyalkylene) amine in the presence of an alkali catalyst in a reaction solvent such as N, N-dimethylformamide and the like to remove the solvent is generally used. It is industrially advantageous to react the diazo component or the coupler component with a mono- or bis- (polyoxyalkylene) amine and then to couple them.

The method for producing the coating composition of the present invention is a dispersion machine such as a ball mill or a sand mill in which a pigment and an organic dye derivative of the general formula (1), an anthraquinone derivative or an acridone derivative are added to a varnish for an acid-curable coating material. Dispersed with
If necessary, an additive such as an anti-sagging agent may be added for production. The pigment and the organic dye derivative of the general formula (1), the anthraquinone derivative, or the acridone derivative are preferably mixed in advance as a paste or a slurry. In the case of a pigment such as copper phthalocyanine, quinacridone or dioxazine that requires a pigmentation step such as solvent salt milling, the organic dye derivative, anthraquinone derivative or acridone derivative of the general formula (1) is mixed during the pigmentation step. You can also

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 reactive sites with the highly alkyl etherified melamine resin (b). Examples of the resin include polyester polyol resin, alkyd polyol resin, acrylic polyol resin, epoxy polyol resin, and epoxy ester polyol resin.

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, Maleic 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, acrylonitrile, methacrylonitrile, vinyl-based monomers such as vinyl acetate. It was obtained by copolymerization.

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.

Examples of the epoxy ester polyol resin include those 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 etherifying a melamine resin obtained by subjecting an aldehyde such as formaldehyde or paraformaldehyde to an addition reaction or an addition condensation reaction 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 alkyl etherified 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.

[0030]

EXAMPLES The present invention will be described below based on examples.
In the examples, "part" means "part by weight" and "%" means "% by weight"
Respectively.

Production Example 1 150 parts of chloromethyl copper phthalocyanine, 468 parts of N, N-bis- (polyoxypropylene) amine (however, the average degree of polymerization of propylene oxide is 15) and 2000 parts of methanol were mixed and mixed at 65 ° C. Hold for 4 hours. Then, the compound (A) was filtered and the methanol was distilled off under reduced pressure.
A paste containing 504 parts was obtained.

Production Example 2 Copper phthalocyanine sulfonyl chloride (containing an average of 1.5 chlorosulfonyl groups per molecule) 143
Parts, N-polyoxyalkylene amine (however, the average degree of polymerization of propylene oxide is 40, the average degree of polymerization of ethylene oxide is 5) 800 parts, pyridine 160 parts, and methanol 2000 parts are mixed and held at 65 ° C. for 4 hours. To do. Then, the mixture was filtered and the methanol was distilled off under reduced pressure to obtain a paste containing 920 parts of compound (B).

Production Example 3 150 parts of copper phthalocyanine sulfonyl chloride (containing an average of 2 chlorosulfonyl groups per molecule),
240 parts of N-polyoxyalkylene amine (however, the average degree of polymerization of propylene oxide is 9, and the average degree of polymerization of ethylene oxide is 1) and 2,000 parts of methanol are mixed and kept at 65 ° C. for 4 hours. Then, the mixture was filtered and the methanol was distilled off under reduced pressure to obtain a paste containing 373 parts of compound (C).

Production Example 4 300 parts of N-polyoxyalkylene-4-acetoacetylaminobenzenesulfonylamide (wherein the average degree of polymerization of propylene oxide is 10 mol and the average degree of polymerization of ethylene oxide is 30) 300 parts, and 1000 parts water Suspension,
4,4-Dichlorobenzidine was coupled by a conventional method, filtered and washed with water to obtain a paste containing 320 parts of compound (D).

Production Example 5 82 parts of anthraquinone-2-carbonyl chloride, N-
600 parts of polyoxyalkylene amine (provided that the average degree of polymerization of propylene oxide is 40, the average degree of polymerization of ethylene oxide is 5), 160 parts of pyridine and 2000 parts of acetone are mixed and kept at 55 ° C. for 4 hours. Then, the mixture was filtered and acetone was distilled off under reduced pressure to give Compound (E) 67.
A paste containing 0 parts was obtained.

Production Examples 6 to 10 Compounds (F) to (J) shown in Table 1 according to Production Examples 1 to 5
Was synthesized. In the column of the substituent of the organic dye derivative, anthraquinone derivative or acridone derivative in the table, -15PO- indicates that the average degree of polymerization of propylene oxide is 15, and -40PO / 5EP- is
The average degree of polymerization of propylene oxide is 40, and the average degree of polymerization of ethylene oxide is 5.

[0037]

[Table 1]

Examples 1 to 19 and Comparative Examples 1 to 9 As shown in Tables 2 and 3, pigments, compounds synthesized in Production Examples, acrylic resins (styrene / n-butyl acrylate / 2 ethylhexyl acrylate / 2 hydroxyethyl). Methacrylate copolymer, weight average molecular weight 8000)
And Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.) were mixed and dispersed, and then a complete alkoxy type methylated melamine resin (“Cymel 303” manufactured by Mitsui Cytec Co., Ltd.) and an acid catalyst (dodecylbenzene sulfonic acid (manufactured by King Co.) "Nature 5225") was blended to obtain an acid-curable coating material.

When the viscosity of each coating material was measured, as shown in Tables 2 and 3, the coating composition of the present invention was superior in the thixotropy (TI value) to the coating composition of the comparative example. It showed fluidity.

The above coating composition was applied to Ford Cup #
The viscosity was adjusted to 4 for 20 seconds, and an intermediate coated plate (a steel plate which had been preliminarily coated with a primer coating and water-polished) was coated with air spray so that the thickness of the dried coating film was about 30 μm. After leaving it for a minute, it was baked at 140 ° C. for 30 minutes.

As shown in Tables 2 and 3, the coating composition of the present invention exhibits good coating hardness, and the coating composition of the present invention is superior to the comparative examples in terms of coating gloss. It was

The non-aggregation property and the non-crystallinity were evaluated by the color-separation stability which is a problem in practical use.
The above coating composition is a base coating of titanium oxide (titanium oxide dispersion paste, titanium oxide is dispersed in an acrylic / melamine resin system to have a PHR of 50 PHR), and the ratio of pigment to titanium oxide is 1/10. So dilute and adjust the light paint. Then dilute with Solvesso 100,
After adjusting the viscosity with a Ford cup # 4 for 20 seconds and then injecting it into a test tube and observing the change in the glass wall surface, the coating composition of the present invention was compared with the coating composition of Comparative Example. There was less color separation over time than the one used.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

The acid-curable coating composition of the present invention is not only excellent in non-aggregating property, non-crystallinity and fluidity, but also has a gloss of the coating film.
It has excellent hardness and is practically inferior in weather resistance and solvent resistance as compared with the case of using the pigment alone.

[Procedure amendment]

[Submission date] February 24, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

The present invention will be described in detail below. As the pigment in the present invention, various resistances when used in a coating material, for example, light resistance, weather resistance, those having good dissolution resistance and the like are desirable, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, Perylene pigments, perinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, at least one organic pigment or carbon black selected from benzimidazolone pigments, titanium oxide, yellow lead, cadmium yellow, At least one inorganic pigment selected from cadmium red, red iron oxide, iron black, zinc white, navy blue, ultramarine and the like can be used.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

Examples 1 to 20 and Comparative Examples 1 to 9 As shown in Tables 2 and 3, pigments, compounds synthesized in Production Examples, acrylic resins (styrene / n-butyl acrylate / 2 ethylhexyl acrylate / 2 hydroxyethyl). Methacrylate copolymer, weight average molecular weight 8000)
And Solvesso 100 (manufactured by Exxon Chemical Co., Ltd.) were mixed and dispersed, and then a complete alkoxy type methylated melamine resin (“Cymel 303” manufactured by Mitsui Cytec Co., Ltd.) and an acid catalyst (dodecylbenzene sulfonic acid (manufactured by King Co.) "Nature 5225") was blended to obtain an acid-curable coating material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C09D 161/32 PHK C09D 161/32 PHK

Claims (2)

[Claims] 1. The following general formula is added to 100 parts by weight of the pigment.
Anthraquinone derivative, an organic dye derivative represented by (1)
Add 0.5 to 100 parts by weight of body or acridone derivative
Set consisting of a pigment composition and an acid-curable coating varnish
Adult. General formula (1) Q- [X-NR₁-Y-R₂]_n (However, in the general formula, Q is an organic dye residue and anthraquinone residue.
Group or acridone residue, X is -SO₂-, -CO-,
-CH₂-Or-CH₂NHCOCH₂-, R ₁Is water
Elementary atom, alkyl group or -Y-R₂, Y is the average molecular weight
400-10,000 propylene oxide polymer or
Copolymer part of ethylene oxide and propylene oxide,
R₂Is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms,
n represents an integer of 1 to 3. ) 2. 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). The coating composition described.