JPH05320561A - Aqueous dispersion of pigment - Google Patents

Abstract

PURPOSE:To provide the subject dispersion composed of an organic pigment, a specific pigment dispersing agent and a water-based resin, having high fluidity and storage stability and giving a coating film having excellent gloss and coloring power when used as a water-based paint. CONSTITUTION:The objective dispersion is composed of (A) an organic pigment, (B) 0.1-30wt.% (based on the component A) of an organic colorant derivative, an anthraquinone derivative or an acridone derivative expressed by formula (P is organic colorant residue, anthraquinone residue or acridone residue; X is bivalent linking group composed of 2-15 atoms selected from S, C, etc.; R1 is H, 1-18C alkyl, etc.; R2 is 1-4C alkyl; Y is random copolymer of ethylene oxide and propylene oxide having an average molecular weight of 400-10,000; (n) is 1-3) and (C) a water-based resin. The compound of formula is generally produced by introducing a substituent such as SO2 group into an organic colorant, anthraquinone or acridone and reacting with bis(polyoxyalkylene)amine in a reaction solvent such as water.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous pigment dispersion having excellent film gloss and tinting strength, fluidity and storage stability.

[0002]

2. Description of the Related Art In recent years, water demands for paints and inks have been increasing due to increasing needs such as resource protection, environmental protection, and improvement of work stability. Similar to the oil-based paint, the required quality of the water-based paint is fluidity, storage stability, gloss of the film, sharpness, tinting strength and the like. However, most of the organic pigments have extremely poor suitability in terms of pigment dispersibility and the like with respect to the aqueous vehicle, so that a satisfactory quality cannot be obtained by an ordinary dispersion method. Therefore, the use of various additives, such as aqueous dispersion resins and surfactants, has been studied in the past, but no grades have been obtained that satisfy all of the above suitability. That is, the gloss of the film immediately after dispersion by the use of a certain aqueous dispersion resin,
Although the sharpness and the coloring power are improved, there are practically fatal drawbacks such as deterioration of fluidity, thickening or gelation over time, and bad influence on physical properties of the film.

[0003]

SUMMARY OF THE INVENTION The present inventor has proposed a method for solving the above-mentioned drawbacks by adding 0.1 to 0.1% to an organic pigment.
The inventors have found that 30% by weight of an organic dye derivative represented by the following general formula (1), an anthraquinone derivative or an acridone derivative is effective as a pigment dispersant, and completed the present invention.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to an organic pigment and the following general formula (1) of 0.1 to 30% by weight based on the organic pigment.
An aqueous pigment dispersion comprising an organic dye derivative, an anthraquinone derivative or an acridone derivative represented by and an aqueous resin. Formula (1) P- [X-NR ₁ -Y-R _{2] n} (where general formula P is an organic pigment residue, anthraquinone residue, or acridone residue, X is S, C, N, O, A divalent linking group consisting of a chemically rational combination composed of 2 to 15 atoms selected from H, R ₁ is H or an alkyl group having 1 to 18 carbon atoms, or Y—R ₂ , R ₂ Is a lower alkyl group having 1 to 4 carbon atoms, and Y is an average molecular weight of 400 to 1
Random copolymer part of ethylene oxide and propylene oxide of 0000, n represents a number of 1 to 3. )

Organic pigments used in the present invention include phthalocyanine pigments, insoluble azo pigments, azo lake pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments,
Examples include diketopyrrolopyrrole pigments, anthrapyridine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perinone pigments, perylene pigments, and thioindigo pigments.

As the organic dye of the general formula (1), phthalocyanine type, insoluble azo type, azo lake type, anthraquinone type, quinacridone type, dioxazine type, diketopyrrolopyrrole type, anthrapyridine type, ansanthrone type, indanthrone type System, flavanthrone system, perinone system, perylene system, thioindigo system, etc. X is S,
A divalent linking group consisting of a chemically rational combination composed of 2 to 15 atoms selected from C, N, O, and H, for example, —SO ₂ —, —CO—, —CH ₂ -,-
CH ₂ NHCOCH ₂ — and the like.

Y is a random copolymer part of ethylene oxide and propylene oxide having an average molecular weight of 400 to 10,000, and the ratio of ethylene oxide and propylene oxide is arbitrary, but the ratio of ethylene oxide is 60 to 9
9 mol% is preferable.

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 preferably 0.1 to 30% by weight.
If the amount is less than 0.1% by weight, the gloss, vividness, tinting strength, etc. of the film of the resulting aqueous pigment dispersion are not improved, and the amount is 30% by weight.
If it is used in a larger amount, the performance of the coating is adversely affected. The organic dye derivative of the general formula (1) of the present invention has an effect on most commercially available organic pigments as described above, but the organic dye derivative of the general formula (1) has a hue similar to that of the pigment used. It is industrially advantageous because the change in hue is small.

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, anthraquinone or acridone is converted into --SO ₂ Cl, --COCl or --CH ₂ C.
1, a substituent such as —CH ₂ NHCOCH ₂ Cl is introduced,
In general, a method of reacting with mono- or bis- (polyoxyalkylene) amine in a reaction solvent such as water, alcohol, acetone or N, N'-dimethylformamide in the presence of an alkali catalyst to remove the solvent is generally used. However, in the case of azo pigments, mono- or bis- (polyoxyalkylene) is previously added to the diazo component or the coupler component.
It is industrially advantageous to react the amine and then perform coupling.

The water-based resin of the present invention is an acrylic copolymer system, a styrene-acrylic acid copolymer system, a styrene-maleic acid copolymer system, an alkyd-based, epoxy-based, polyester-based, urethane-based water-dispersed resin or water-soluble resin. Although there are resins, water-dispersible resins or water-soluble resins based on acrylic copolymers are particularly preferable.

The acrylic copolymer resin is 50-80% by weight of (meth) acrylic acid alkyl ester, acrylic acid,
5 to 30% by weight of a carboxylic acid-containing monomer such as methacrylic acid, maleic acid and itaconic acid and other monomers 0
Molecular weight of 5,000 to 30,000 obtained by emulsion polymerization or solution polymerization of 20% by weight in a water-soluble solvent.
A resin having an acid value of 0 and an acid value of 1 to 200. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth).
Isopropyl acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Examples include n-hexyl acrylate and lauryl (meth) acrylate. Examples of the above-mentioned other monomers include 2-hydroxyethyl (meth) acrylate, and (meth) acrylic acid 2
-Hydroxypropyl, acrylamide, N-methylol acrylamide, diacetone acrylamide, glycidyl (meth) acrylate, styrene, vinyltoluene, vinyl acetate, acrylonitrile, vinyl alcohol, ethylene and the like.

The above water-dispersible resin can be produced by dropping the mixture of the above monomers into an aqueous medium to which an emulsifier is added and emulsion-polymerizing the mixture. High molecular weight dispersants may be used in place of or in combination with the emulsifier. Further, the water-dispersible resin of the present invention may be dispersed in an aqueous dispersion by neutralizing the carboxylic acid incorporated in the resin by adding amine or ammonia. For example,
A water-dispersible resin can be obtained by neutralizing an acrylic copolymer resin having a free carboxylic acid polymerized in a hydrophilic organic solvent with an organic amine and adding water.
The water-soluble resin can be obtained by neutralizing an acrylic copolymer resin having a free carboxylic acid polymerized from the monomer in a hydrophilic organic solvent with an organic amine and adding water.

The aqueous medium of the aqueous resin used in the present invention may be only water, but in some cases, an alcohol solvent such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, or ethylene. Water-miscible organic solvents such as glycols or mono- or dialkyl ethers of diethylene glycol can be admixed up to 50% by weight in the aqueous medium.

In the method for producing the aqueous pigment dispersion of the present invention, it is most convenient to mix the organic pigment and the organic dye derivative of the general formula (1), the anthraquinone derivative or the acridone derivative into the aqueous resin dispersion or solution. .. Alternatively, an organic pigment is suspended in water or an organic solvent, and a solution or suspension of the organic dye derivative, anthraquinone derivative or acridone derivative of the general formula (1) in water or the organic solvent is mixed to remove the water or the organic solvent. After that, it can be incorporated into a dispersion or solution of the aqueous resin. In addition, the organic dye derivative, anthraquinone derivative or acridone derivative of the general formula (1) is added during coupling in the case of azo pigments or during the pigmentation process such as salt milling method or sulfuric acid dissolution method in the case of phthalocyanine pigments, quinacridone pigments and dioxazine pigments. The pigment composition obtained by mixing may be blended with a dispersion or solution of an aqueous resin. In order to disperse the pigment or the pigment composition in the aqueous resin dispersion or solution, it is preferable to use a disperser such as a dissolver, a high speed mixer, a homomixer, a sand mill or an attritor.

The aqueous pigment dispersions of the invention can be used as aqueous printing inks or coatings and as concentrated dispersions thereof.

[0016]

EXAMPLES Production Example 1 A mixture of 2000 parts of water, 698 parts of N-polyoxyalkyleneamine (however, the average number of moles of polymerization is 40 moles of ethylene oxide and 10 moles of propylene oxide) and 318 parts of sodium carbonate was added to copper phthalocyanine sulfonyl chloride. An aqueous wet cake containing 145 parts (containing an average of 1.5 chlorosulfonyl groups per molecule) was added and kept at 80 ° C. for 1 hour. The released blue resin layer was isolated by a liquid separation operation to obtain a paste containing 834 parts of the compound (a).

Production Example 2 2,000 parts of dimethylformamide, 185 parts of N-polyoxyalkyleneamine (however, the average number of moles of polymerization is 8 moles of ethylene oxide and 2 moles of propylene oxide),
1 part of a mixture of 135 parts of chloromethyl copper phthalocyanine (containing an average of 2 chloromethyl groups per molecule)
Hold at 00 ° C. for 3 hours. Then, the mixture was filtered and washed with water to obtain a paste containing 312 parts of compound (b).

Production Example 3 A suspension of 263 parts of N-polyoxyalkylene-4-acetoacetylaminobenzenesulfonylamide (however, the average number of moles of polymerization is 20 moles of ethylene oxide and 5 moles of propylene oxide) and 1000 parts of water, A diazonium solution obtained by diazotizing 4,4'-dichlorobenzidine by a conventional method was coupled by a conventional method, filtered and washed with water to obtain a paste containing 291 parts of compound (c).

Production Example 4 54 parts of anthraquinone-2-carbonyl chloride, N,
N'-bis- (polyoxyalkylene) amine (however,
The average number of moles of polymerization is 200 moles of ethylene oxide and 20 moles of propylene oxide) 1984 parts and acetone 20
00 parts were mixed and stirred at 55 ° C. for 1 hour. Then water 5
Compound (d) 203 was added by adding 000 parts, filtering and washing with water.
A paste containing 0 parts was obtained.

Production Examples 5 to 15 Compounds (e) to (o) shown in Table 1 according to Production Examples 1 to 4
Was synthesized.

[0021]

[Table 1]

Example 1 CIPigment Blue 15: 1 Wet cake containing 20 parts water
A solution prepared by dispersing 4 parts of the compound (a) in 50 parts of water was added to and mixed with 200 parts of the mixture. Then, it was filtered, washed with water, dried and pulverized to obtain 23 parts of a pigment composition. When the obtained pigment composition was made into a paint and spread by the following method, excellent film gloss was obtained.

(Painting and color development method) 10 parts of pigment composition, 12.5 parts of acrylic resin solution (solid content 20%) having a weight average molecular weight of 25,000 and an acid value of 60, 20 parts of deionized water, and 150 parts of 3 mmφ alumina beads. Was placed in a 225 ml glass container and dispersed with a paint conditioner for 3 hours. Acrylic resin above
37.5 parts and methylated melamine resin (trade name Cymel 303
(Mitsui Cyanamid) 4.3 parts were added and mixed to obtain a water-based paint. The resulting waterborne paint was developed on a PET film with a 4 mil film applicator and baked at 140 ° C for 30 minutes. The gloss was measured at 20 ° gloss with a digital variable angle gloss meter.

Examples 2 to 21 Compounds (a) to (o) were mixed with various pigments in the same manner as in Example 1, and the mixture was made into a paint and color-developed, and similarly excellent film gloss was obtained. The results are shown in Tables 2 and 3.

Comparative Example When the pigments used in Examples 1 to 21 were made into a paint without adding the compounds (a) to (o) and the color was developed, the pigments were brighter than those to which the compounds (a) to (o) were added. Was inferior. The results are shown in Tables 2 and 3.

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

INDUSTRIAL APPLICABILITY The aqueous pigment dispersion of the present invention, when used as an aqueous paint, has excellent film gloss and sharpness without impairing the fluidity of the paint.

Claims (1)

[Claims] 1. An organic pigment, and 0.1 to 30 with respect to the organic pigment.
Wt% of an organic dye derivative represented by the following general formula (1),
An aqueous pigment dispersion comprising an anthraquinone derivative or acridone derivative and an aqueous resin. Formula (1) P- [X-NR ₁ -Y-R _{2] n} (where general formula P is an organic pigment residue, anthraquinone residue, or acridone residue, X is S, C, N, O, A divalent linking group consisting of a chemically rational combination composed of 2 to 15 atoms selected from H, R ₁ is H or an alkyl group having 1 to 18 carbon atoms, or —Y—R ₂ , R ₂ is a lower alkyl group having 1 to 4 carbon atoms, Y is an average molecular weight of 400 to
A random copolymer part of 10000 ethylene oxide and propylene oxide, n represents a number of 1 to 3. )