JPH10231439A - Pigment composition and coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a blue pigment composition and a coating composition appearing to be a quality product and having clarity, color developing properties and profundity. SOLUTION: The pigment composition is obtained by simultaneously converting cobalt phthalocyanine and/or lowly chlorinated cobalt phthalocyanine and copper phthalocyanine and/or lowly chlorinated copper phthalocyanine into a pigment. The content of the cobalt phthalocyanine and/or the lowly chlorinated cobalt phthalocyanine used is 20-80wt.% based on the pigment composition. The coating composition is prepared by using the above pigment composition. This coating composition any contain 1-30wt.%, based on the pigment composition, metal phthalocyanine having substituents other than chlorine atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a vivid color,
More particularly, the present invention relates to a pigment composition having an excellent depth feeling and a coating composition using the pigment composition. More specifically, as a coloring pigment, cobalt phthalocyanine and / or low chlorinated cobalt phthalocyanine, and copper phthalocyanine and / or low chlorinated copper The present invention relates to a pigment composition containing phthalocyanine and a coating composition using the pigment composition.

[0002]

2. Description of the Related Art Copper phthalocyanine pigments, which are known as the most representative of the blue pigments, have been used for a wider range of applications because of their sharp hues, high coloring power and fastness. It has been widely used for coloring inks and resins in addition to paints for automotive coatings and the like.

[0003] However, in the coating of automobiles and building materials, there is a growing demand for a paint having a sense of quality, ie, a sense of depth, which cannot be obtained with conventional copper phthalocyanine pigments.

On the other hand, several years ago, a large number of pigments in which a metal other than copper was coordinated with phthalocyanine have been studied, and they have been used in color materials or in applications other than color materials. In particular, cobalt phthalocyanine has been attempted to be used for paints for automobiles and the like, and a deep feeling not found in copper phthalocyanine has been obtained.

[0005]

However, when cobalt phthalocyanine is used alone as a pigment, it is inferior to copper phthalocyanine in terms of sharpness and color development, and therefore, it is inferior in any of sharpness, color development and deepness. At present, an excellent coating composition has not yet been obtained.

The present invention has been made in view of the above-mentioned problems of the prior art, and has a high-quality blue pigment composition having unprecedented sharpness, coloring, and depth. It is an object to provide a coating composition.

[0007]

The inventors of the present invention have conducted intensive studies and have found that a low chlorinated or unchlorinated cobalt phthalocyanine pigment or a mixture thereof is mixed with a low chlorinated or unchlorinated copper. The present inventors have found that a pigment composition which solves the above-mentioned problems can be obtained by simultaneously pigmentating phthalocyanine or a mixture thereof, thereby completing the present invention. That is, the pigment composition of the present invention is characterized in that cobalt phthalocyanine and / or low chlorinated cobalt phthalocyanine and copper phthalocyanine and / or low chlorinated copper phthalocyanine are simultaneously pigmented.

A feature of the pigment composition of the present invention is that it can be obtained by simultaneously pigmenting two or more kinds of pigments. In this regard, two or more kinds of powders are simply blended to form a mixture. Are distinguished from those.

The pigment composition of the present invention has such a property that two or more components are mixed in one crystal or one crystal aggregate, and as if the whole were one component.
For example, when the crystal stability or weather resistance of one component is poor, deterioration with time is usually observed as a change in hue. However, this is improved in the pigment composition of the present invention, and the overall resistance is improved. Alternatively, when there is a difference in the dispersibility of two or more types of components, a phenomenon in which the hue differs depending on the degree of dispersion of each component may occur, but in the pigment composition of the present invention, two or more types of components have one crystal. This dispersibility of the individual components does not differ from each other because they are mixed together in one or a single crystal aggregate and behave as if the whole were a single component. Absent.
Furthermore, when two or more kinds of components having different particle diameters are blended, depending on the angle at which the coating film is viewed, the pigment having a small particle diameter is hidden by a large pigment, so that the hue may look different. As described above, such a phenomenon is not observed in the composition since each component behaves as if it were one component as a whole.

As the pigmentation method for obtaining the pigment composition of the present invention, various conventionally known methods can be used. The most typical example is a sulfuric acid purification method. This involves first mixing two or more pigment components (generally, a crude pigment before micronization is used) as a powder, dissolving it in concentrated sulfuric acid, etc., and then contacting it with water, etc. To recrystallize or reprecipitate. In addition, the target pigment composition can be obtained by mechanically kneading with a sand mill, a ball mill, a kneader, or the like in the presence or absence of a solvent.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Low chlorinated cobalt phthalocyanine and low chlorinated copper phthalocyanine which can be used as a pigment component in the present invention are obtained by introducing 1 to 4 chlorines as substituents into the phthalocyanine ring of cobalt phthalocyanine and copper phthalocyanine, respectively. It was done. If the number of chlorine substituents is more than 4, the resulting pigment composition will deviate from the intended color tone, which is not preferred.

In the pigment composition of the present invention, the total content of cobalt phthalocyanine and low chlorinated cobalt phthalocyanine is preferably 20 to 80% by weight of the whole pigment composition. If this content is less than 20% by weight,
The effect of adding the low-chlorinated or non-chlorinated cobalt phthalocyanine compound is small, and a paint having a deep feeling cannot be obtained. On the other hand, when the content exceeds 80% by weight, it is not preferable because sharpness and color development due to the low-chlorinated or non-chlorinated copper phthalocyanine compound cannot be obtained.

The coating composition of the present invention contains the above-mentioned pigment composition. In order to enhance dispersibility and color development, the pigment composition contains a metal phthalocyanine having a substituent other than chlorine. The derivative is added to the pigment composition by 1 to
You may contain in the range of 30 weight%.

As the metal phthalocyanine derivative which can be used, in addition to various copper phthalocyanine derivatives conventionally used, other different metal phthalocyanine derivatives containing cobalt may be used. Among metal phthalocyanine derivatives,
Particularly, a copper phthalocyanine derivative and a cobalt phthalocyanine derivative are preferable.

Examples of the metal phthalocyanine derivative include:
Sulfonated copper phthalocyanine, sulfonated cobalt phthalocyanine, sulfonamide copper phthalocyanine, sulfonamide cobalt phthalocyanine, phthalimide methyl copper phthalocyanine, phthalimide methyl cobalt phthalocyanine, aminomethyl copper phthalocyanine, aminomethyl cobalt phthalocyanine, carboxylate copper phthalocyanine, carboxylate cobalt phthalocyanine, etc. Is mentioned.

The vehicle component of the paint for adding the pigment composition is not particularly limited, and components conventionally used in the paint field are used. For example, acrylic resin,
Alkyd resin, polyester resin, amino resin, epoxy resin and these modified resins and the like as a main component, further amino resin, isocyanate compound,
A curing agent such as a blocked isocyanate compound and a polyamide resin or a crosslinking agent can also be used in combination.

In the coating composition of the present invention, a solvent generally used in the field of coatings, such as xylene, toluene, various alcohols and organic acid esters, can be used as a solvent.

The coating composition of the present invention may contain the above-mentioned vehicle component, solvent, and phthalocyanine pigment as components, and as a glittering material, a metal having a thickness of 0.2 to 1.5 μm and an average particle diameter of 10 to 50 μm. Foil or mica may be added. The metal foil and mica may be those generally used, and examples of the metal foil include aluminum foil and tin foil, and examples of the mica include ordinary mica and coated mica. The blending amount of the metallic foil or the mica glittering material is 0.1 to 10 by weight ratio to the phthalocyanine pigment.
It is preferable to set it in the range. In addition, other commonly used coloring pigments and various paint additives may be blended. Production method and coating method of the coating composition of the present invention,
The drying method is not particularly limited, and a commonly used method can be employed.

[0019]

Hereinafter, examples of the present invention will be described in comparison with comparative examples. In the following description, “parts” or “%” means “weight basis” unless otherwise specified.

(Example 1) 98 in a 2 liter beaker
% Sulfuric acid (2,000 parts), into which monochloro copper phthalocyanine (Cyanine Blue F-1102, Sanyo Dyeing Co., Ltd.)
60 parts) and 120 parts of cobalt phthalocyanine (O-270 phthalocyanine, Sanyo Dyeing Co., Ltd.) are added.

After stirring at 50 ° C. for 2 hours, the mixture is poured into 10 liters of water while stirring. The phthalocyanine pigment composition 1 was obtained by filtration, washing with water, drying and pulverization.

The pigment composition 1 was blended according to Table 1 and mixed by stirring with a stirrer, and then the mixture was dispersed by a small bead mill to prepare a coating composition of this example.

[0023]

[Table 1]

(Example 2) 850 parts of sodium chloride was put into a 2 liter kneader, and 200 parts of ethylene glycol was added thereto to prepare monochloro copper phthalocyanine (cyanine blue F-11).
02, 50 parts of Sanyo Dye (manufactured by Co., Ltd.), cobalt phthalocyanine (O-270 phthalocyanine, Sanyo Dye Co., Ltd.)
100 parts).

This is kneaded at 80 ° C. for 7 hours and then redispersed in hot water. After the salt was completely removed by filtration and washing with hot water, phthalocyanine pigment composition 2 was obtained by drying and grinding.

This pigment composition 2 was prepared in the same manner as in Example 1 except that
The coating composition of this example was prepared by mixing and dispersing according to the following.

(Comparative Example 1) 98 in a 2 liter beaker
% Sulfuric acid (2,000 parts), and monochloro copper phthalocyanine (Cyanine Blue F-1102, Sanyo Dyeing Co., Ltd.)
180 parts).

After stirring at 50 ° C. for 2 hours, the mixture is poured into 10 liters of water with stirring.

A monochloro copper phthalocyanine pigment was obtained by filtration, washing with water, drying and pulverization.

This pigment was blended and dispersed according to Table 1 in the same manner as in Example 1 to prepare a coating composition of this comparative example.

(Comparative Example 2) 98% in a 2 liter beaker
2000 parts of sulfuric acid was added thereto, and cobalt phthalocyanine (O-270 phthalocyanine, manufactured by Sanyo Dyeing Co., Ltd.) was added thereto.
Add 0 parts.

After stirring at 50 ° C. for 2 hours, the mixture is poured into 10 liters of water while stirring. A cobalt phthalocyanine pigment was obtained by filtration, washing with water, drying and pulverization.

This pigment was blended and dispersed according to Table 1 in the same manner as in Example 1 to prepare a coating composition of this comparative example.

Comparative Example 3 The monochloro copper phthalocyanine pigment and the cobalt phthalocyanine pigment prepared in Comparative Examples 1 and 2 were mixed in 23 parts each to obtain a pigment composition.

This was blended and dispersed according to Table 1 in the same manner as in Example 1 to prepare a coating composition of this comparative example.

(Aluminum Foil Paint) The compositions shown in Table 2 were stirred and mixed with a stirrer to prepare an aluminum foil paint. This aluminum foil paint is used by being mixed with the paint compositions of Examples 1 and 2 and Comparative Examples 1 to 3 as described later.

[0037]

[Table 2]

(Topcoat paint) The following ingredients were stirred and mixed with a stirrer to prepare a topcoat paint. This topcoat paint is used to form a topcoat covering the coating film, as described later.

[0039]

[Table 3]

The coating compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were applied to a steel sheet, dried, and the above-prepared top coat was applied and baked at 150 ° C. for 30 minutes. To make a painted plate. The coating film performance on this coated plate was evaluated, and the results are shown in Table 4. Each evaluation item is as follows.

The hue and tinting strength were measured using a multi-source spectrophotometer M
It was measured using SC-IS-2B (manufactured by Suga Test Instruments Co., Ltd.).

The gloss was measured using a digital variable-angle gloss meter UGV-5D.
(Manufactured by Suga Test Instruments Co., Ltd.).

The feeling of depth was judged by visually observing the coated plate at a low angle under white light.

[0044]

[Table 4]

The coating films of Examples 1 and 2 have the same hue as the coating films of Comparative Examples 1 to 3, and are superior in coloring power to the coating films of Comparative Examples 1 and 3; Approximately the same value as the coating film of Comparative Example 2 used in Example 1.
As for the gloss, the coating films of Examples 1 and 2 were compared with Comparative Example 1
The coatings of Examples 1 and 2 are superior to the coatings of Comparative Examples 1 and 3 and almost the same as the coatings of Comparative Example 2 using cobalt phthalocyanine alone. The result was the same.

Next, 90 parts of the coating compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 3 were added to the aluminum foil coating 10
Parts were blended to obtain a metallic color paint composition. This was coated on a steel plate, dried, and further coated with the topcoat paint prepared above, and baked at 150 ° C. for 30 minutes to obtain a coated plate. The coating film performance on this coated plate was evaluated, and the results are shown in Table 5. Each evaluation item is as follows.

The hue was evaluated in the same manner as in Table 4.

Flip-flop characteristics (characteristics in which the color tone and brilliancy change depending on the angle at which the painted surface is viewed, and those with little change are considered good) were visually judged. The sense of depth was determined in the same manner as in Table 4.

Regarding the sharpness, the degree of turbidity and white blur was visually determined.

The weather resistance was measured using a Super Xenon Weather Meter SC750-WN (manufactured by Suga Test Instruments Co., Ltd.).
A 1000-hour accelerated test was performed, and the color difference before and after being applied to a meter was measured and expressed as a ΔE value.

The crystal stability is determined by adding 5 parts of pigment to xylene 200
After the mixture was heated and refluxed for 2 hours, the filtered and dried sample was analyzed by X-ray diffraction, and it was determined that the smaller the change from the analysis result of the original pigment, the more stable the pigment composition.

[0052]

[Table 5]

The coatings of Examples 1 and 2 have the same hue as the coatings of Comparative Examples 1 to 3, are superior to the coatings of Comparative Examples 1 and 3 in the flip-flop property and the sense of depth, and show the cobalt phthalocyanine. Was used alone or the same as or better than the coating film of Comparative Example 2. Further, regarding the sharpness, the coating films of Examples 1 and 2 were equivalent to the coating film of Comparative Example 1 using copper phthalocyanine alone, and were superior to the coating films of Comparative Examples 2 and 3. Further, the weather resistance and the crystal stability were equivalent to or slightly inferior to the coating film of Comparative Example 1 using copper phthalocyanine alone, but were superior to Comparative Examples 2 and 3 in which only cobalt phthalocyanine was used alone or in combination. became.

[0054]

As described above, according to the present invention, by using a pigment in which cobalt phthalocyanine and / or low chlorinated cobalt phthalocyanine and copper phthalocyanine and / or low chlorinated copper phthalocyanine are simultaneously pigmented,
Conventional copper phthalocyanine and cobalt phthalocyanine, furthermore, having a color tone, clarity, color development, deepness, luxury feeling that could not be obtained only by mixing these,
Moreover, it is possible to provide a coating composition having excellent weather resistance and crystal stability, and it can be said that the coating composition is useful as a coating material that can be used for automobiles, building materials, and the like.

Claims (5)

[Claims] 1. A pigment composition characterized in that cobalt phthalocyanine and / or low chlorinated cobalt phthalocyanine and copper phthalocyanine and / or low chlorinated copper phthalocyanine are simultaneously pigmented. 2. The pigment composition according to claim 1, wherein the content of cobalt phthalocyanine and / or low chlorinated cobalt phthalocyanine is 20 to 80% by weight of the total pigment composition. 3. A coating composition comprising the pigment composition according to claim 1 or 2. 4. A metal phthalocyanine derivative having a substituent other than chlorine is added in an amount of 1 to 30% by weight based on the pigment composition.
The coating composition according to claim 3, wherein the composition is blended in the range of: 5. A thickness of 0.2 to 1.5 μm and an average particle size of 10
The coating composition according to claim 3, further comprising a metal foil or mica having a thickness of from 50 μm to 50 μm.