JPH10110113A - Colored stainless flake pigment and coating material having colored metal gloss - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject inexpensive pigment capable of producing by a simple method, exhibiting appearance having bright color and having metal gloss by coating stainless flake surface with a titanium compound comprising water-containing titanium dioxide and titanium dioxide. SOLUTION: The surface of stainless flake (preferably having 0.3-0.9μm thickness and 20-30μm average particle diameter) is coated with a titanium compound comprising a water-containing titanium dioxide and titanium dioxide. The pigment is preferably obtained by adding an inorganic salt of titanium to water, dissolving the inorganic salt in water by heating the mixture until 50 deg.C, dispersing stainless flake into water so as to become 10wt.% disperse concentration, adding the inorganic salt of titanium to the dispersion to control concentration as titanium dioxide to <=7wt.%, boiling the dispersion while stirring to hydrolyze the inorganic salt of titanium and successively carrying out neutralization, water washing, drying, grinding and baking of hydrolyzed material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored stainless flake pigment whose particle surface is coated with a titanium compound, and a colored metallic luster paint containing the pigment.

[0002]

2. Description of the Related Art Titanium-based mica pigments having a titanium dioxide layer formed on the surface of fine flaky mica have a pearl luster and interference colors, and have been widely used as pigments for cosmetics, paints, plastics and the like. Although it is used, a color exhibiting a vivid chromatic appearance close to white has not been obtained. To solve this problem, coloring pigments such as iron oxide, navy blue, chromium oxide, carbon black, and carmine were added to the generated mica titanium-based pigments, but safety, stability, light resistance, and chemical resistance There was a problem in the properties, solvent resistance, heat resistance and the like. In order to further solve these problems, a colored mica titanium pigment in which the surface of mica particles is coated with titanium dioxide and further coated with a titanium compound such as low-order titanium oxide or titanium oxynitride (Japanese Patent Publication No. 4-61032, Tokuhei 4
No. 61033, Japanese Patent Publication No. 5-46385).

[0003] However, such colored mica titanium pigments are produced by a very complicated method. The method for producing the colored titanium mica pigment that coats the low order titanium oxide is as follows. First, an aqueous solution of an inorganic salt of titanium (for example, titanyl sulfate) is hydrolyzed in the presence of mica, and the surface of the mica particles is coated with hydrous titanium dioxide. Then add this to 500-10
Heat reduction at a temperature of 00 ° C with one or two or more kinds of gases having a reducing power such as hydrogen gas or ammonia gas, or mixing with metallic titanium, and under low oxygen conditions 500 to
After heat reduction at 1000 ° C., the mica is coated with a titanium compound containing low titanium oxide. Further, an aqueous solution of an inorganic salt of titanium (for example, titanyl sulfate) is hydrolyzed in the presence of the mica coated with the titanium compound to deposit hydrous titanium dioxide on the surface of the particles, and then dried and calcined to obtain titanium dioxide. This is a method for producing a titanium pigment.

[0004] A method for producing a colored mica titanium-based pigment coated with titanium oxynitride is as follows. First, hydrous titanium dioxide is precipitated on the surface of the mica particles in the same manner as in the case of the lower titanium oxide. Next, this is heated and reduced at a temperature of 500 to 1000 ° C. with ammonia gas or a mixed gas of ammonia gas and an inert gas such as helium gas, argon gas, nitrogen gas, and mica is formed with a titanium compound containing titanium oxynitride. Cover. Further, the surface thereof is coated with titanium dioxide in the same manner as in the case of low-order titanium oxide, thereby producing a colored mica titanium pigment. As described above, the conventional colored mica titanium-based pigments have to be very expensive because they are manufactured by a complicated method. Further, a glossier pigment has been demanded.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide a pigment which can be produced in a simple manner, is inexpensive, has a vivid chromatic appearance and has a metallic luster.
It is another object of the present invention to provide an inexpensive colored glossy paint by blending the colored metallic glossy pigment.

[0006]

Means for Solving the Problems In addition to the mica and flaky iron oxide conventionally used as a substrate, the present inventors have shown a bright chromatic appearance when coated with titanium dioxide and have a metallic luster. As a result of examining the base material, it was found that stainless flake was suitable. The interference color pigment based on stainless steel flake has excellent properties such as safety, stability, light resistance, chemical resistance, solvent resistance, and heat resistance. Was completed. That is, the present invention is characterized by a colored stainless flake pigment in which the surface of the stainless flake is coated with hydrous titanium dioxide and a titanium compound of titanium dioxide, and a colored metal obtained by blending the above colored stainless flake pigment. It features a glossy paint. This will be described in more detail below.

[0007] Conventional mica titanium-based pigments are prepared by adding an aqueous solution of an inorganic salt of titanium (for example, titanyl sulfate) in which mica is dispersed, as shown in a patent of Dupont (Japanese Patent Publication No. 43-25644). It is common to decompose and deposit hydrous titanium dioxide on the surface of mica, followed by firing. The thus obtained titanium mica pigment exhibits various interference colors depending on the thickness of the titanium dioxide coating layer formed on the surface of the mica particles. Interference color is silver, gold, red, violet, blue, depending on the content of titanium dioxide in the produced pigment.
Changes to green. Table 1 shows the relationship between the interference color and the thickness of the titanium dioxide coating layer on the mica particle surface.

[0008]

[Table 1]

As described above, since the hue of the interference color changes depending on the thickness of the titanium dioxide coating the substrate, the amount of the titanium dioxide to be coated must be changed depending on the type (density) and shape (flake shape) of the substrate. Must.

[0010]

Embodiments of the present invention will be described below. In the present invention, the titanium compound coated on the stainless flake surface includes hydrated titanium dioxide and titanium dioxide. As the type of stainless flake used in the present invention, any type such as commercially available SUS304, SUS316 and SUS316L can be used, and SUS304 and SUS316L are particularly preferable.
The thickness of the stainless flake is preferably from 0.2 to 3.0 μm, more preferably from 0.3 to 0.9 μm. The average particle size is preferably 10 to 50 μm, more preferably 20 to 30 μm
It is.

The precipitation or deposition of hydrous titanium dioxide on the surface of stainless flakes is performed as follows. The weight of the titanium dioxide to be deposited is determined with respect to the weight of the stainless steel flake of the base material, and the required weight of the inorganic salt of titanium is calculated. This is added to water and dissolved by heating to about 50 ° C. If it is difficult to dissolve, add a small amount of sulfuric acid and dissolve completely. Next, the stainless steel flakes are dispersed in water. If necessary, dispersion may be carried out using a disperser such as a homomixer. The dispersion concentration of the stainless flake may be about 10% by weight. After adding a solution of the inorganic salt of titanium to the dispersion to adjust the concentration as titanium dioxide to 7% by weight or less, the mixture is heated to 80 ° C. or higher while stirring, and preferably boiled. As a result, the inorganic salt of titanium is hydrolyzed and deposited on the surface of the stainless flake to form a hydrous titanium oxide layer. After completion of the hydrolysis, the mixture is neutralized, washed with water, dried, crushed and fired. Since the hue of the developed interference color changes depending on the drying and baking temperatures, the baking temperature is determined based on the required hue.

For example, a thickness of 0.3 to 0.9 μm and an average particle size of 20 to
Using 30μm SUS316L stainless steel flakes as base material, 40
When calcined at 0 ° C., the calculated value of titanium dioxide content in the interference color pigment is about 3% by weight, red-purple, about 6% by weight blue, and about 9% by weight green.

The thus obtained interference color pigment is mixed and dispersed in a coating resin diluted with an appropriate amount of a solvent to obtain a colored metallic luster coating. The compounding amount of the interference color pigment is 1 to 2 with respect to 200 parts by weight of the resin solids for coating.
The amount is preferably 00 parts by weight, more preferably 50 to 100 parts by weight. The paint resin used in the colored metallic glossy paint of the present invention is an acrylic resin, an alkyd resin, a silicone resin,
Conventionally used resins such as vinyl butyral resin, vinyl chloride resin, urethane resin, unsaturated polyester resin, fluororesin, melamine resin, urea resin, epoxy resin and phenol resin can be used. Solvents used are aromatic hydrocarbons such as toluene and xylene, olefin compounds, cycloolefin compounds, naphthas, methanol, ethanol, alcohol compounds such as isopropanol, ketone compounds such as methyl ethyl ketone,
Conventionally used compounds such as ester compounds such as butyl acetate, chlorine compounds such as trichloroethylene, monoether monoesters of glycol, and water can be used. These coating resins and solvents may be used alone or as a mixture of two or more.

The colored stainless flake pigment coated with the titanium compound of the present invention has a vivid chromatic appearance and metallic luster, is excellent in various properties, and can be easily manufactured at low cost. Also, by blending the colored stainless flake pigment, an inexpensive colored metallic luster paint having excellent various properties and having a coating film having an interference color and metallic luster can be obtained.

[0015]

Next, the present invention will be described with reference to examples and comparative examples. Example 1 Stainless flake 100g (SUS316L commercial product, thickness 0.5
μm, average particle size 25 μm) was added to 800 ml of water, and the mixture was sufficiently stirred and dispersed (substrate dispersion liquid). 10 g of titanyl sulfate crystals (titanium dioxide content: 32%) were added to 100 ml of water and dissolved while heating (aqueous titanyl sulfate solution). 0.1 g of concentrated sulfuric acid was added to the substrate dispersion, and the mixture was heated. Then, the entire aqueous solution of titanyl sulfate was added, and the mixture was maintained at 100 ° C. for 5 to 10 minutes with stirring. After cooling, the mixture was filtered, washed with water, and dried. The dried product was calcined at 400 ° C. for 0.5 to 1 hour, cooled and pulverized to recover 103 g of stainless flake pigment powder. The resulting powder exhibited a red-purple metallic luster in both appearance color and interference color.

Example 2 A stainless flake pigment was produced in the same manner as in Example 1 except that 20 g of titanyl sulfate crystals (titanium dioxide content: 32%) were used, and 106 g of a powder were recovered. The resulting powder exhibited blue metallic luster in both appearance color and interference color.

Example 3 A stainless flake pigment was produced in the same manner as in Example 1 except that 30 g of titanyl sulfate crystals (titanium dioxide content: 32%) was used, and 109 g of a powder was recovered. The resulting powder exhibited a green metallic luster in both appearance color and interference color.

The stainless flake pigment powder obtained in Examples 1 to 3 was used as a sample and evaluated by the following method. (1) Appearance color, interference color: visually identified. (2) Acid resistance: 5 g of a sample was placed in a 50 ml colorimetric tube, 30 ml of a 10% hydrochloric acid solution was added thereto, and the mixture was dispersed.
The color after time was visually observed. (3) Alkali resistance: 5 g of a sample was placed in a 50 ml colorimetric tube, and 30 ml of a 10% sodium hydroxide solution was added thereto to disperse the mixture. The mixture was allowed to stand, and the color after 24 hours was visually observed. (4) Solvent resistance: 4 g of the sample was placed in a 50 ml colorimetric tube, 20 ml of a xylene solution was added to the tube, dispersed, left standing, filtered, and the color of the filtrate was visually observed. (5) Light fastness: 20 g of a sample was put into a small stainless steel vat in a thin layer and irradiated with an ultraviolet lamp for 120 hours, and then compared with the color before irradiation with the naked eye. (6) Heat resistance: 5 g of a sample was placed in a 20 ml magnetic crucible, fired in the air at 400 ° C. for 1 hour, cooled, and visually compared with the color before firing. Table 2 shows the evaluation results. The judgments in Table 2 are as follows. ○ ‥‥ The color tone is stable without any change. Δ 色 The color tone slightly changed and fading was observed. × 色 Discolored and changed to white. As can be seen from Table 2, the colored stainless steel flake pigment coated with the titanium compound of the present invention has excellent color tone and excellent acid resistance, alkali resistance, solvent resistance, light resistance, and heat resistance.

[0019]

[Table 2]

Example 4 To 66 g of a melamine alkyd resin, 10 g of the red-purple metallic luster stainless flake pigment obtained in Example 1 and 6 g of thinner were added and dispersed with a paint shaker to obtain a red-purple metallic luster paint. The paint is coated on a mild steel plate with a bar coder.
Apply to 83μm, leave at room temperature for 30 minutes, 120 ℃
For 30 minutes to obtain a test coating film.

Example 5 A test coating film was obtained in the same manner as in Example 4 except that 10 g of the blue metallic luster pigment obtained in Example 2 was used.

Example 6 A test coating film was obtained in the same manner as in Example 4 except that 10 g of the green metallic luster pigment obtained in Example 3 was used.

The test coating films obtained in Examples 4 to 6 were evaluated by the following methods. (1) Gloss: visually identified. (2) Acid resistance (stability): The test coating film was immersed in a 10% hydrochloric acid solution at 20 ° C., allowed to stand, and one day and seven days later, the surface of the test coating film was visually observed. (3) Alkali resistance (stability): Test film at 20 ° C, 10%
The surface of the test coating film was immersed in a sodium hydroxide solution, allowed to stand for 1 day, and after 7 days, and visually observed. (4) Light resistance: The test coating film was irradiated with an ultraviolet lamp for 48 hours, and the color difference (ΔE) before and after the irradiation was measured by a color difference meter. Table 3 shows the results of these evaluations. As can be seen from Table 3, the colored metallic luster paint of the present invention has excellent metallic luster, and is also excellent in acid resistance, alkali resistance, and light resistance.

[0024]

[Table 3]

[0025]

According to the present invention, it is possible to obtain a colored stainless flake pigment which has a vivid chromatic appearance and metallic luster, is excellent in various properties, is inexpensive and is easy to produce.
Further, by adding this pigment, a colored metallic glossy paint having excellent metallic luster and coating film characteristics can be provided.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshinori Yamamoto 3-14-1, Funatari, Itabashi-ku, Tokyo Inside Nihonashiki Chemical Industry Co., Ltd.

Claims (2)

[Claims] 1. A colored stainless flake pigment, wherein the surface of the stainless flake is coated with hydrated titanium dioxide or a titanium compound of titanium dioxide. 2. A colored metallic luster paint comprising the colored stainless flake pigment according to claim 1.