JPH04178471A - Pigment composition and coating composition produced by using the same - Google Patents

Abstract

PURPOSE:To provide a pigment composition composed of a pigment, an Al salt of an organic pigment (derivative) containing sulfonic acid group and an Al salt of an aromatic carboxylic acid and exhibiting excellent agglomeration resistance, crystallization resistance and fluidity when used in an acid-curable coating material. CONSTITUTION:The objective composition is composed of 100 pts.wt. of a pigment, 0.5-30 pts.wt. of an aluminum salt of an organic pigment (derivative) containing sulfonic acid group and 0.5-40 pts.wt. of an aluminum salt of a 7-16C aromatic carboxylic acid.

Description

[Detailed description of the invention] [Objective of the invention] (Industrial application field) The present invention exhibits excellent non-aggregation, non-crystallinity, and fluidity when used in paints, especially acid-curing paints. The present invention relates to a pigment composition and a coating composition.

(Prior Art) In general, pigments dispersed in paints are required to exist in the form of very fine particles in order to obtain clear color tone and high coloring power. However, it is known that fine pigment particles are unstable and cause a number of problems, such as having a significant impact on the coating manufacturing process and the value of the resulting product.

For example, paints containing pigments made of fine particles tend to have a high viscosity, which not only makes it difficult to remove and transport the product from a dispersion machine, but even worse, it gels during storage and becomes unusable. Sometimes. Furthermore, when different types of pigments are mixed and used, phenomena such as color separation and sedimentation due to aggregation may cause color unevenness in the coating film and a decrease in tinting power. Furthermore, regarding the surface of the paint film, the gloss decreases,
This may result in poor condition such as poor leveling.

Further, although it is not directly related to the dispersibility of the pigment, some organic pigments experience a phenomenon that is accompanied by a change in the crystalline state of the pigment. That is, the pigment crystal particles, which are energetically unstable in the paint, change their size and shape and shift to a stable state, resulting in significant changes in hue and decrease in tinting power in the paint film.
The product value may be damaged due to the generation of coarse particles.

In order to solve the various problems mentioned above, many proposals have been made, mainly using copper phthalocyanine and quinacridone pigments. The content can be broadly divided into the following two categories based on technical methods.

The first law is USP No. 3370971 and USP 29
As seen in Japanese Patent No. 65511, pigment particles are coated with colorless compounds such as silicon oxide, aluminum oxide and tertiary butylbenzoic acid.

The second method is Japanese Patent Publication No. 41-2466 and USP 27
As typified by Japanese Patent No. 61865, this is a method of mixing a compound obtained by using an organic pigment as a base skeleton and introducing substituents such as a sulfone group, a sulfonamide group, an aminomethyl group, and a phthalimidomethyl group into the side chain.

Compared to the first method, the second method improves the non-aggregation of pigments in the paint.
Is this a very advantageous method judging from the large effects on amorphousness, fluidity, etc., and the ease of manufacturing the pigment composition, or is the practical problem still not completely resolved? be. In particular, there are many problems with acid-curing paints, and it is desired to develop effective pigment dispersants and pigment compositions.

For example, pigment compositions containing derivatives of organic pigments with basic substituents, which are extremely effective in general paints, may interact with acid catalysts in acid-curing paints, causing the problems described above. There are many.

Furthermore, as an organic pigment derivative having an acidic functional group, a pigment composition containing an aluminum salt of a phthalocyanine derivative having a carboxyl group, an aluminum salt of an aromatic carboxylic acid, and tl- is known from Japanese Patent Publication No. 64-5070. However, almost no improvement was observed when this pigment composition was used in acid-curing paints.

(Problems to be Solved by the Invention) The present invention improves the various problems described above, and exhibits excellent non-aggregation, non-crystallinity, and fluidity when used in paints, especially acid-curing paints. The present invention provides a pigment composition comprising the pigment composition and an acid-curable paint.

[Structure of the invention]

(Means for Solving the Problems) The present invention comprises 100 Jtjt parts of a pigment, 0.5 to 30 parts by weight of an organic dye or organic dye derivative having a sulfonic acid group, and 0 parts by weight of an aromatic carboxylic acid having 7 to 16 carbon atoms. The present invention relates to a pigment composition comprising .5 to 40 parts by weight of an aluminum salt and an acid-curable coating composition containing the pigment composition as an essential component.

In the present invention, pigments have various resistance properties when used in paints,
For example, pigments with no practical problems in terms of light resistance, weather resistance, and solvent resistance, such as soluble and insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene/perinone. Organic pigments such as dioxazine pigments, diketopyrrolobyroll pigments, vat dye pigments, and basic dye pigments, as well as carbon black, titanium oxide, yellow lead, cadmium yellow, cadmium red, Bengara, Inorganic pigments such as iron black, zinc white, navy blue, and ultramarine can be used.

In the present invention, organic dyes include, for example, azo, phthalocyanine, anthraquinone, quinacridone, dioxazine, anthrapyrimidine, anthanthrone, indanthrone, flavanthrone, perinone, perylene, and thioindigo. . Here, in the case of an organic dye containing a sulfone group and having a structure insolubilized by a metal element such as calcium or barium, the present invention can be easily achieved by changing the metal to aluminum. Further, in the case of an organic dye not containing a sulfonic group, an aluminum salt can be formed after introducing a sulfonic group using sulfuric acid, oleum, diluted sulfuric acid, etc. according to a conventional method. It is practically advantageous to select the organic dye of the present invention having a chemical structure that is the same or similar to that of the pigment. In other words, not only are they often effective in improving non-aggregation, non-crystallinity, and fluidity, but also
This is preferable because there is less change in hue compared to the case of using a pigment alone. The amount of the aluminum salt of the organic dye or organic dye derivative having a sulfonic group of the present invention is 0.5 to 3 parts by weight of the organic dye or organic dye derivative per 100 parts by weight of the pigment.
0 parts by weight is preferred.

If it is less than 0.5 parts by weight, the effect will be small, and if it is more than 30 parts by weight, the effect will not be obtained.

In the present invention, the aromatic carboxylic acid having 7 to 16 carbon atoms is
For example, benzoic acid, nitrobenzoic acid, chlorobenzoic acid,
Aminobenzoic acid, tertiary butylbenzoic acid, salicylic acid,
These include aminosalicylic acid, phthalic acid, naphthalene-2-carboxylic acid, 2-hydroxy-3-naphthoic acid, and anthraquinone-2-carboxylic acid. Note that if an aliphatic carboxylic acid is used instead of an aromatic carboxylic acid, the effects of the present invention cannot be obtained at all. Further, the amount of the aluminum salt of aromatic carboxylic acid used in the present invention is preferably 0.5 to 40 parts by weight as aromatic carboxylic acid per 100 parts by weight of the pigment. If it is less than 0.5 parts by weight, the effect will be small, and if it is more than 40 parts by weight, the effect will not be obtained.

The method for producing the pigment composition of the present invention may be carried out by mixing each component of the pigment, an aluminum salt of an organic dye having a sulfonic group or an organic dye derivative, and an aluminum salt of an aromatic carboxylic acid in a dry powder state, or by mixing the components in a dry powder state, or by mixing the components in a dry powder state or a paste. It is preferable to mix in the form of a slurry or a slurry. In addition, a slurry in which a pigment, a sodium salt of an organic dye having a sulfonic group or an organic dye derivative, and a sodium salt of an aromatic carboxylic acid are well dispersed is prepared, and the slurry is mixed with aluminum chloride,
Even more favorable effects can be obtained when a pigment composition is prepared by adding a water-soluble aluminum compound such as aluminum sulfate. Furthermore, for pigments that require a pigmentation process such as solvent salt milling, such as copper phthalocyanine, quinacridone, and dioxazine, they can be mixed during the pigmentation process.

The acid-curing coating composition of the present invention is produced by dispersing the pigment composition in an acid-curing coating varnish using a dispersing machine such as a ball mill or sand mill, and adding additives such as anti-sagging agents as necessary. can do. A representative example of acid-curable paint varnish is a varnish prepared by adding a solvent and an acidic compound to a resin composition containing a hydroxyl group-containing resin as a base resin and an aminoaldehyde resin as a crosslinking agent. Hydroxyl group-containing resins include, for example, polyester polyol resins, alkyd polyol resins, acrylic polyol resins, epoxy polyol resins, urethane polyol resins, and silicone polyol resins, and aminoaldehyde resins include, for example, hexamethyl etherified methylol melamine, hexabutyl ether methylolmelamine, methylbutyl etherified methylolmelamine, and methyletherified methylolmelamine. The acidic compounds include, for example, carboxylic acid compounds, phosphoric acid compounds, sulfonic acid compounds, and mineral acids, and sulfonic acid compounds, particularly aromatic sulfonic acid compounds, are usually used.

〔Effect of the invention〕

Although the mechanism by which the physical properties of paints obtained using the pigment composition of the present invention, especially acid-curable paints, are superior is not necessarily clear, organic pigments or organic pigment derivatives having sulfonic groups on the surface of pigment particles are not necessarily clear. It is presumed that this is due to the dispersion stabilizing effect of the pigment particles due to steric hindrance caused by the strong adsorption of the pigment particles and the adsorption of the aromatic carboxylic acid via the aluminum ions.

The acid-curable coating composition of the present invention has non-aggregating, non-crystalline,
Not only does it have excellent fluidity, but also the gloss and hardness of the coating film, and in terms of weather resistance and solvent resistance, it is practically no worse than when a pigment is used alone.

Furthermore, the pigment composition of the present invention can be applied not only to acid-curing paints, but also to general paints that do not contain acidic compounds as curing catalysts. It exhibits almost the same excellent effect as a mixture of derivatives. Furthermore, when used in printing inks such as offset inks and gravure inks, it exhibits excellent fluidity and produces printed matter with high coloring strength and gloss.

(Example) The present invention will be explained below with reference to Examples. In the examples, "part" means part by weight, and "%" means % by weight.

Example I C,l Pigment Blue 5: l (1
00 parts), aluminum copper phthalocyanine sulfonate (
(10 parts) and aluminum benzoate (15 parts) were mixed to obtain a pigment composition (a).

Example 2 C, 1, Pigment Blue 15: 1
(100 parts), sodium copper phthalocyanine sulfonate (5 parts) and sodium benzoate (8 parts) in water (1 part).
After heating to 60°C, an aqueous solution of aluminum sulfate (5 parts) was added, followed by filtration, washing with water, drying, and pulverization to obtain pigment composition (b).

Example 3 C,1,Pigment Red 5 (100 copies)
, C,1, Pigment Red 53 (10 parts) and sodium 4-butylbenzoate (15 parts) were dissolved in water (100 parts).
After heating to 60°C, an aqueous solution of aluminum chloride (7 parts) was added, followed by filtration, washing with water, drying, and pulverization to obtain pigment composition [c].

Examples 4 to 6 C,1,Pigment Violet 19 (9 parts) was dissolved in 98% sulfuric acid (100 parts) and held at 80°C for 1 hour to perform a sulfonation reaction. Water (1000 parts)
After dilution, the mixture was filtered and washed with diluted hydrochloric acid to obtain an organic dye derivative having a sulfonic group (10 parts). Next, the pigments shown in Examples 4 to 6 in Table 1, aromatic carbonic acid, and water (1000 parts) were added, followed by filtration, washing with water, drying, and pulverization to obtain pigment compositions (d) to (f). Ta.

Examples 7 to 17 The organic dyes shown in Examples 7 to 17 in Table 1 were used in Examples 4 to 6.
An organic dye derivative having a sulfone group was obtained by sulfonation in the same manner as above. Next, the pigments shown in Examples 7 to I7 in Table 1, aromatic carboxylic acids, and water (1000 parts) were added to form a slurry, and the slurry was adjusted to pH 10 and heated to 60°C. An aqueous solution of aluminum sulfate was added thereto, followed by filtration, washing with water, drying, and pulverization to obtain pigment compositions (d) to (q).

Examples 18-34 Pigment compositions (a)-- obtained in Examples 1-17 so that the pigment content is 10% in a varnish consisting of polyester polyol, methyl etherified methylol melamine, and dodecylbenzenesulfonic acid as an acidic compound (q) and for comparison, the viscosity of an acid-curing paint obtained by dispersing a pigment alone was measured. The results are shown in Table 2. In all cases, the pigment composition according to the present invention is superior to the comparative pigment alone. In addition, the clarity of the color tone of the painted object painted with this paint,
It was also excellent in terms of gloss effects.

Regarding non-aggregation and non-crystallinity, color separation stability, which is a particular problem in practical use, will be explained. The paint shown in Table 2 is cut using a titanium oxide base paint so that the ratio of pigment to titanium oxide is 171O to prepare a light color paint.

The pigment compositions of the present invention were then diluted with butyl acetate, the viscosity was adjusted, and then injected into test tubes to observe changes in the glass wall. In all cases, the pigment compositions according to the present invention showed less color separation over time than the comparative pigments alone.

Example 35 A pigment composition (r) was obtained according to the method described in Example 4 of Japanese Patent Publication No. 64-5070. That is, C,1,Pi
gment Blue 15:1 (100 copies), N-
(2-Carboxy-5-nitrobenzoyl)aminomethylcopper phthalocyanine (5 parts) and benzoic acid (8 parts) were made into a slurry using water (1000 parts), and after adjusting the pH to 9.5, the mixture was heated at 80-85°C. Stirred for 1 hour. After cooling to 50°C, an aqueous solution of aluminum sulfate (5 parts) was added to adjust the pH to 4.
, 5, filtered, washed with water, dried and ground to obtain a pigment composition (r).

Further, piperidinoacetamidomethyl copper phthalocyanine was synthesized according to the method described in Reference Example 1 of Japanese Patent Publication No. 58-28303, and 5 parts were converted to C, 1, Pigment Bl.
ue 15:1 (100 parts) in powder form to obtain a pigment composition (S). The method for synthesizing piperidinoacetamidomethyl copper phthalocyanine is shown below.

Copper phthalocyanine (10 parts) in polyphosphoric acid (150 parts)
, paraformaldehyde (4 parts) and chloroacetamide (8 parts) were added, and the mixture was stirred at 120°C for 4 hours. water(
After diluting with 1000 parts), it was filtered and washed with water to obtain a blue paste. Then add piperidine (8 parts) and water (200 parts).
Part) was added to the paste and stirred at 100°C for 6 hours, followed by filtration, washing with water, drying and pulverization to obtain piperidinoacetamidomethyl copper phthalocyanine (13 parts).

These pigment compositions and the pigment composition according to Example 2 (b)
was dispersed in the same manner as in Examples 18 to 34 to obtain acid-curing paints. The measurement results of viscosity are shown in Table 2.

Table 3 February 1991 date

Claims (1)

[Scope of Claims] 1. 100 parts by weight of pigment, 0.5 to 30 parts by weight of an organic dye or organic dye derivative having a sulfonic acid group, and 0.5 to 30 parts by weight of an aromatic carboxylic acid having 7 to 16 carbon atoms.
Pigment composition consisting of 40 parts by weight of aluminum salt. 2. The pigment composition according to claim 1, which comprises a mixed aluminum salt of an organic dye or an organic dye derivative having a sulfonic acid group and an aromatic carboxylic acid having 7 to 16 carbon atoms. 3. A coating composition comprising the pigment composition according to claim 1 or 2 and an acid-curable coating varnish.