JP2971996B2 - Rutile-type titanium dioxide-coated graphite flake pigment and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel graphite flake pigment having excellent properties in light fastness, weather fastness and color, and a method for producing the same.

[0002]

2. Description of the Related Art In general, pigments for topcoat paints for automobiles, pigments for building material paints, pigments for printing inks and pigments for plastic coloring used outdoors have high opacity, as well as various physical properties such as light resistance and weather resistance. Excellent color is required. In the automotive topcoat paint industry, pigments with excellent light resistance and weather resistance, which are highly concealable and have high design properties, are expected, but especially in the above-mentioned applications, a flaky black surface having a smooth surface. Graphite has an effect of increasing concealment by its black color and also has an effect of absorbing transmitted light, and is preferred as a metal oxide coating substrate for developing interference colors.

Conventionally, graphite pigments obtained by coating graphite with titanium dioxide are disclosed in JP-B-49-3824, JP-B-49-16531 or JP-A-52-874.
These are known and described in, for example, Japanese Patent Publication No. 22-222, but these known pigments are not satisfactory in terms of the appearance of interference colors, light resistance, and weather resistance.

[0004]

OBJECTS OF THE INVENTION It is an object of the present invention to provide graphite flake pigments having excellent light fastness, weather fastness and color properties which are not satisfied by the prior art, and a process for producing the same. In the prior art titanium dioxide-coated graphite pigment, a uniform and dense coating was not obtained, and as a result, interference colors with high saturation could not be developed, and the color could be sufficiently controlled. It has a problem to be solved that is not possible, and since the coated titanium dioxide is anatase type titanium dioxide, paints, inks and plastics using this pigment are
It was not satisfactory in light resistance and weather resistance, and had a problem to be solved in which the color changed over time.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a graphite flake pigment characterized in that oxidized graphite flake particles are coated with rutile-type titanium dioxide hydrate and / or rutile-type titanium dioxide. To provide.

[0006] The present invention also relates to a method of manufacturing a semiconductor device, comprising the steps of:
A graphite flake pigment characterized by being coated with rutile-type titanium dioxide hydrate and / or rutile-type titanium dioxide. Further, the present invention provides a method for producing these novel graphite flake pigments. Hereinafter, the present invention will be described in detail. The novel graphite flake pigment of the present invention is
In particular, it is preferable to manufacture by the following methods 1) to 4).

1) An oxidized graphite flake particle is suspended in water, and a metal salt selected from a tin metal salt, a zinc metal salt, a lithium metal salt and an antimony metal salt and a titanium metal salt are added to the suspension. And an aqueous solution in which a basic substance is dissolved at the same time,
Tin on the surface of the oxidized graphite flake particles,
Deposit a mixed oxide hydrate of a metal oxide hydrate selected from zinc, lithium and antimony and a titanium dioxide hydrate, and simultaneously add an aqueous solution of a titanium metal salt and an aqueous solution of a basic substance And depositing titanium dioxide hydrate, filtering the resulting solid material, washing, drying and calcining.

2) The oxidized graphite flake particles are suspended in water, and the suspension is mixed with an aqueous solution of a metal salt selected from a tin metal salt, a zinc metal salt, a lithium metal salt and an antimony metal salt and a basic solution. An aqueous solution in which the substance is dissolved is simultaneously added, and a hydrate of a metal oxide selected from tin, zinc, lithium, and antimony is deposited on the surface of the oxidized graphite flake particles. A method comprising simultaneously adding an aqueous solution and an aqueous solution of a basic substance, depositing titanium dioxide hydrate, filtering the obtained solid substance, washing, drying and calcining.

[0009] 3) A method characterized in that rutile-type titanium dioxide is coated by using the graphite flake particles oxidized in the production method of 1), the surfaces of which are previously coated with silicon dioxide.

4) In the manufacturing method of 2), the above 3)
A method of coating rutile-type titanium dioxide using graphite flake particles previously coated with silicon dioxide as in the method of the above.

The graphite flake particles used in each of the above production methods have a particle size of 0.5 to 150 μm and a thickness of 0.05 to 10 μm, preferably a particle size of 1 to 60 μm and a thickness of 0.1 to 0.3 μm. A black opaque plate-like crystal having a smooth surface is desirable. In each of the above production methods, as a method of oxidizing the graphite flake particles,
For example, there are the following methods (a) to (c).

(A) A method in which graphite flake particles are heated and oxidized at 200 to 500 ° C. in an oxygen-containing atmosphere.

(B) A method in which graphite flake particles are suspended in water and then oxidized using a water-soluble oxidizing agent.

(C) The graphite flake particles are heated and oxidized at 200 to 500 ° C. in an oxygen-containing atmosphere, and the oxidized graphite flake particles are suspended in water and then oxidized using a water-soluble oxidizing agent. How to handle.

The water-soluble oxidizing agent used in the above oxidation treatment includes hydrogen peroxide, sodium peroxide, sodium perchlorate, potassium permanganate, potassium manganate, potassium chromate, sodium chromate, dichromate. Examples include those selected from potassium, sodium bichromate, formic acid, acetic acid, nitric acid, potassium nitrate, sodium nitrate, ammonium nitrate, sulfuric acid, potassium sulfate, and sodium sulfate, and these may be used alone or in combination. it can.

In the present invention, by using the above-mentioned oxidized graphite flake particles, the above-mentioned metal oxide and silicon dioxide can be uniformly and
The effect of being able to cover densely is obtained.

In the above-mentioned respective processes, when the operation is performed using graphite flake particles not subjected to oxidation treatment instead of the graphite flake particles subjected to oxidation treatment, a corresponding pigment is obtained, but the appearance of interference colors is obtained. In this regard, it is not enough.

In each of the above methods 1) and 2), the surface of the graphite flake particles to be used is previously hydrated with a metal oxide such as zirconium oxide, cobalt oxide, manganese oxide, chromium oxide or cerium oxide. The thing which covered the thing may be used.

Examples of the titanium metal salt used in each of the above-mentioned production methods include titanium tetrachloride, titanyl sulfate, titanium trichloride, monotitanium sulfate, dititanium sulfate and titanium tribromide. Are not limited to these examples.

The aqueous solution of a basic substance used in each of the above-mentioned production methods is not particularly specified, but examples thereof include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonium solution.

As a method for coating the surface of the oxidized graphite flake particles with silicon dioxide in the above processes 3) and 4), the oxidized graphite flake particles are stirred and suspended in water, and the suspension is added to the suspension. A method is preferable in which an aqueous alkali silicate solution and an aqueous acidic solution are simultaneously added to deposit silicon dioxide on the surface of the oxidized graphite flake particles. The reason is that the surface of graphite flake particles obtained by oxidizing silicon dioxide can be easily and uniformly coated. More specifically, the oxidized graphite flake particles are stirred and suspended in water to a concentration of 3 to 15% by weight.
The temperature of the aqueous suspension is raised to 90 ° C. and maintained at a constant temperature, and the pH of the aqueous suspension is adjusted to 1.5 to 11, preferably 1.8 to 3.0 using an acidic aqueous solution or an aqueous solution of a basic substance. And 8
Adjusted to a constant value of any of 10 to 10, and an aqueous alkali silicate solution is added using a metering pump. At the same time, add an acidic aqueous solution while maintaining a predetermined pH with a metering pump,
Silicon dioxide is deposited and coated on the surface of the oxidized graphite flake particles.

As the above alkali silicate, alkali silicates selected from sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, potassium silicate and sodium silicate can be used. The concentration is 0.2 as silicon dioxide.
~ 5% by weight is preferred. The supply rate of the aqueous alkali silicate solution was 1 m ² per unit surface area of the graphite flake particles.
0.1 × 10 ⁻⁵ as silicon dioxide per minute
It is preferable to supply at a dropping speed of 10 to ^10-5 mol.

The acidic aqueous solution is not particularly specified, but examples thereof include aqueous solutions of hydrochloric acid, sulfuric acid and nitric acid.

The metal salt selected from tin, zinc, lithium and antimony used in each of the above-mentioned production methods is used to make the crystal structure of titanium dioxide rutile. Examples of these metal salts include stannous chloride, stannic chloride, stannous sulfate, zinc chloride, zinc sulfate, zinc nitrate, lithium chloride, lithium sulfate, lithium nitrate, antimony oxychloride, antimony trichloride, etc. However, use of a tin salt is desirable in terms of performance and handling. These metal salts can be used alone or in combination, and can be used in an amount of 0.01 to 50% by weight as a metal oxide based on the coated titanium dioxide.

In each of the above-mentioned production methods, graphite flake particles obtained by oxidizing a hydrate of an oxide of a metal selected from tin, zinc, lithium and antimony and hydrate of titanium dioxide, or graphite flake particles coated with silicon dioxide. The method for coating the surface itself is not specified, but any conventionally used coating method can be used.

In each of the above-mentioned production methods, the surface of the oxidized graphite flake particles or the graphite flake particles coated with silicon dioxide is adjusted to a desired amount of titanium dioxide hydrate by adjusting the coating amount of titanium dioxide hydrate. A coated graphite flake pigment can be easily obtained. At this time, before coating the titanium dioxide hydrate, a metal selected from tin, zinc, lithium and antimony to be coated for rutile of titanium dioxide is an aqueous solution of a metal salt thereof, or an aqueous solution of the metal salt. A preferred method is to drop a basic aqueous solution composed of sodium hydroxide or the like simultaneously with a mixed solution obtained by adding an aqueous solution of titanium chloride to the mixture and to deposit them as hydrates of these metal oxides.

More specifically, the above-mentioned production method is described below. 1 to 20% by weight of oxidized graphite flake particles or silicon dioxide-coated graphite flake particles
Aqueous suspension, preferably 3-10% by weight, is stirred and maintained at a temperature of 50-100 ° C., preferably 70-80 ° C., and a suitable acidic substance such as hydrochloric acid is added. After adjusting the pH of the suspension to a predetermined value in the range of 0.5 to 5.0, an aqueous solution of the metal salt is supplied with stirring using a metering pump, and the aqueous solution of the basic substance is simultaneously , The pH of the aqueous suspension is maintained constant. The aqueous solution of the metal salt is preferably 0.01 to
A concentration of 5.0 mol / l. The supply of the aqueous solution of the metal salt is performed at a rate of 0.01 × 10 ⁻⁵ to 30 × 10 ⁵ per minute per unit surface area of 1 m ² of the oxidized graphite flake particles or silicon dioxide-coated graphite flake particles.
It is preferable to supply at a dropping rate of × 10 ⁻⁵ mol / l. The concentration of the aqueous solution in which the basic substance is dissolved is preferably 0.025 to 10 mol / l.

According to the above-described method, a hydrate of an oxide of a metal selected from tin, zinc, lithium and antimony and a hydrate of titanium dioxide are oxidized on the surfaces of graphite flake particles or silicon dioxide-coated graphite flake particles. Although coated, gold, red, blue, and green interference colors can be developed according to the amount of the aqueous solution of these metal salts dropped. Further, when the desired interference color is developed, simultaneous dropping of the aqueous solution of the metal salt and the aqueous solution of the basic substance can be stopped. Next, the pH value is adjusted using an aqueous solution in which a basic substance is dissolved so as to have a pH value specified for industrial wastewater, the suspension is filtered, and the produced pigment is collected by filtration. Is desirable. The filtered pigment contains a water-soluble neutralizing salt. Therefore, it is preferable to wash the pigment with ion-exchanged water in order to enhance water resistance, light resistance, and weather resistance. 10 more
Dry at 0-200 ° C for 2-20 hours, 450-1000
Firing at 0.1 ° C. for 0.15 to 10 hours in an atmosphere that suppresses thermal decomposition of graphite, such as air or an inert gas, is desirable from the viewpoint of enhancing weather resistance and light resistance.

The graphite flake pigment according to the present invention has excellent color fastness and excellent light fastness and weather resistance as compared with the conventional titanium dioxide coated graphite flake pigment.

Hereinafter, Examples and Comparative Examples of the present invention will be described, and weather resistance tests performed on the pigments obtained in each of the Examples will be described.

Comparative Example 1 Graphite flake particles having a particle size of 1 to 100 μm and an average particle size of 36 μm (PB-85 manufactured by Nishimura Graphite Co., Ltd.) 1
240 ml of ion-exchanged water is added to 5 g, and the mixture is stirred and suspended. 0.15 g of potassium permanganate is added to the obtained suspension, and the mixture is stirred at room temperature for 18 hours to perform an oxidation treatment.
After this oxidation treatment, the suspension was filtered, the graphite flake particles were separated by filtration, washed with ion-exchanged water, and then filtered.
Dry at 15 ° C. for 15 hours. 1000 ml of ion-exchanged water is added to 10 g of the oxidized graphite flake particles, and the mixture is stirred and suspended to prepare a suspension. The temperature is maintained at 75 ° C. and weakly bubbled with air. To this suspension, 24.6 g of 35% by weight hydrochloric acid and 49.3% by weight of titanium trichloride 49.3 g in 200 ml of ion-exchanged water were added.
g of the titanium trichloride solution to which g had been added.
The suspension is dropped at a dropping rate of 75 ml / min with stirring until the pH of the suspension becomes 2.1. Thereafter, a titanium trichloride solution is added dropwise at the same rate, and at the same time, a 9.76% by weight aqueous sodium hydroxide solution is added dropwise to maintain the pH at 2.1.

In this manner, 1837 ml of an aqueous solution of titanium trichloride is added dropwise. After the addition is completed, the pH is raised to 5 using an aqueous solution of 9.76% by weight of sodium hydroxide, and the suspension is filtered to obtain a solution of titanium dioxide hydrate. An object-coated graphite flake pigment is obtained. The pigment was washed with ion exchanged water, filtered, dried at 200 ° C. for 15 hours,
Firing at 30 ° C. for 30 minutes gives a titanium dioxide-coated graphite flake pigment exhibiting excellent red interference. X
Observation of the crystal structure of titanium dioxide of this pigment by line analysis reveals that all of the pigments are of anatase type. For the weather resistance test of this pigment,
The measurement was performed using a sunshine weather meter (Suga Test Machine).

Example 1 4 pieces of graphite flake particles (PB-85 manufactured by Nishimura Graphite Co., Ltd.) having a particle size of 1 to 100 μm and an average particle size of 36 μm were prepared.
Heat oxidation treatment is performed in air at 50 ° C. for 30 minutes. 20 g of the heated and oxidized graphite flake particles are stirred and suspended in 500 ml of ion-exchanged water, and 0.2 g of potassium permanganate is added to the aqueous suspension, followed by stirring at room temperature for 15 hours to perform oxidation treatment. After this oxidation treatment, the oxidized graphite flake particles obtained by filtering this suspension are washed with ion-exchanged water to remove the remaining potassium permanganate. Next, 250 g of ion-exchanged water was added to 20 g of the oxidized graphite flake particles and stirred to form a suspension, and the temperature was maintained at 75 ° C.
A 10% by weight aqueous hydrochloric acid solution is added to adjust the pH to 1.8. To this suspension, a solution obtained by mixing 13.2 ml of 53 g / l stannic chloride pentahydrate and 1.86 ml of an aqueous solution of 407 g / l titanium tetrachloride was dropped at a rate of 0.2 ml / min. At the same time, a 5% by weight aqueous sodium hydroxide solution is added dropwise so as to maintain the pH at 1.8. Thus, a mixed oxide hydrate of titanium dioxide hydrate and tin dioxide hydrate is deposited on the surface of the graphite flake particles.

Further, 80 ml of a 407 g / l aqueous solution of titanium tetrachloride and 80 ml of a 10% by weight aqueous hydrochloric acid solution are used.
60 ml of titanium tetrachloride solution is dropped at a dropping rate of 0.2 ml / min. At the same time, a 5% by weight aqueous solution of sodium hydroxide is dropped to maintain the pH at 1.8, thereby depositing titanium dioxide hydrate. . After the completion of the dropwise addition of 160 ml of the titanium tetrachloride solution, the pH was adjusted from 1.8 to 6.0 by adding a 5% by weight aqueous solution of sodium hydroxide, and the solid substance was separated by filtration, washed with ion-exchanged water and washed with Drying at 15 ° C. for 15 hours gives a gold interference titanium dioxide hydrate-coated graphite flake pigment with excellent color development. If this is further calcined at 520 ° C. for 30 minutes in air, a gold interference titanium dioxide-coated graphite flake pigment having more excellent coloring properties is obtained. Observation of the crystal structure of titanium dioxide of this pigment by X-ray analysis reveals that the pigment is all rutile. In addition, carbon arc
When this pigment is subjected to a weather resistance test using a sunshine weather meter (Suga Test Machine), it is found that the pigment has much better weather resistance than the anatase-type titanium dioxide-coated graphite flake pigment of the comparative example.

Example 2 Graphite flake particles (PB-85 manufactured by Nishimura Graphite Co., Ltd.) having a particle size of 1 to 100 μm and an average particle size of 36 μm were mixed with 4
Heat oxidation treatment is performed in air at 50 ° C. for 30 minutes. 20 g of the heat-oxidized graphite flakes are stirred and suspended in 500 ml of ion-exchanged water, 0.2 g of potassium permanganate is added to the aqueous suspension, and the mixture is stirred for 15 hours to carry out oxidation treatment. After this oxidation treatment, the suspension is filtered to obtain oxidized graphite flake particles. This is washed with ion exchanged water to remove the remaining potassium permanganate. Following this washing, 250 g of ion-exchanged water was added to 20 g of the oxidized graphite flake particles and stirred to prepare a suspension, which was maintained at 75 ° C., and a 10% by weight aqueous hydrochloric acid solution was added. To this suspension whose pH is adjusted to 1.8, 8.8 ml of 53 g / l stannic chloride pentahydrate aqueous solution is added dropwise at a rate of 0.2 ml / min while maintaining the pH at 1.8. To this end, tin dioxide hydrate is deposited on the surface of the graphite flake particles by dropwise addition of a 5% by weight aqueous sodium hydroxide solution.

Further, 160 ml of a titanium tetrachloride solution comprising 80 ml of a 407 g / l aqueous solution of titanium tetrachloride and 80 ml of a 10% by weight aqueous hydrochloric acid solution were added dropwise at a rate of 0.2 ml / min, and the pH was simultaneously adjusted to 1.8. A 5% by weight aqueous sodium hydroxide solution is added dropwise to maintain the titanium dioxide hydrate. After completion of the dropwise addition of 160 ml of the titanium tetrachloride solution, a 5% by weight aqueous solution of sodium hydroxide was added to adjust the pH to 1.8 to 6.0, the solid substance was separated by filtration, and ion exchange was performed. Washed with water 130
Drying at 15 ° C. for 15 hours gives a violet interference pigment with excellent color development. If this is further calcined at 520 ° C. for 30 minutes in air, a purple interference titanium dioxide-coated graphite flake pigment with more excellent coloring properties is obtained. Observation of the crystal structure of titanium dioxide of this pigment by X-ray analysis reveals that the pigment is all rutile. Further, a weather resistance test of this pigment using a carbon arc sunshine weather meter (Suga Test Machine) reveals that the weather resistance is considerably superior to the anatase type titanium dioxide-coated graphite flake pigment of the comparative example.

Example 3 4 pieces of graphite flake particles (PB-85 manufactured by Nishimura Graphite Co., Ltd.) having a particle size of 1 to 100 μm and an average particle size of 36 μm
Heat oxidation treatment is performed in air at 50 ° C. for 30 minutes. 20 g of the heated and oxidized graphite flakes are stirred and suspended in 500 ml of ion-exchanged water, 0.2 g of potassium permanganate is added to the aqueous suspension, and the mixture is stirred for 15 hours to perform an oxidation treatment. After this oxidation treatment, the suspension is filtered to obtain oxidized graphite flake particles. This is washed with ion exchanged water to remove the remaining potassium permanganate. After this washing, 250 g of ion-exchanged water is added to 20 g of the oxidized graphite flake particles, and the mixture is stirred to prepare a suspension. The temperature was maintained at 60 ° C., and a 5% by weight aqueous sodium hydroxide solution was added to adjust the pH to 9.5.
Then, 24 g of a 1.7% by weight aqueous sodium silicate solution as silicon dioxide is added at a dropping rate of 0.2 ml / min using a metering pump. At the same time, a 3.5% by weight aqueous hydrochloric acid solution was added dropwise using a metering pump to adjust the pH to 9.
Maintain at 5. After the completion of the dropwise addition of the aqueous sodium silicate solution, a 3.5% by weight aqueous hydrochloric acid solution is added to adjust the pH to 6.0, and then the silicon dioxide-coated graphite flake particles are collected by filtration.

Further, the water-soluble neutralized salt remaining on the silicon dioxide-coated graphite flake particles is washed away with ion-exchanged water and dried at 105 ° C. for 15 hours. After drying, rutile-type titanium dioxide is coated in the same manner as in Example 1 using the silicon dioxide-coated graphite flakes. X-ray analysis of the obtained titanium dioxide crystals of the pigment shows that all are covered with rutile-type titanium dioxide. In addition, a weather resistance test of this pigment with a carbon arc sunshine weather meter (Suga Test Machine) reveals that the pigment has much better weather resistance than the anatase type titanium dioxide pigment of the comparative example.

Example 4 Graphite flake particles (PB-85 manufactured by Nishimura Graphite Co., Ltd.) having a particle size of 1 to 100 μm and an average particle size of 36 μm
Heat oxidation treatment is performed in air at 50 ° C. for 30 minutes. 20 g of the heat-oxidized graphite flakes were stirred and suspended in 500 ml of ion-exchanged water, and 0.2 g of potassium permanganate was added to the aqueous suspension, followed by stirring for 15 hours.
Perform oxidation treatment. After this oxidation treatment, the suspension is filtered to obtain oxidized graphite flake particles. This is washed with ion exchanged water to remove the remaining potassium permanganate. After this washing, 250 g of ion-exchanged water is added to 20 g of the oxidized graphite flake particles, stirred and suspended, and the temperature is maintained at 60 ° C., and a 5% by weight aqueous sodium hydroxide solution is added to adjust the pH to 9.5. Then, 24 g of a 1.7% by weight aqueous sodium silicate solution as silicon dioxide is added at a dropping rate of 0.2 ml / min using a metering pump. At the same time, a 3.5% by weight aqueous hydrochloric acid solution is added dropwise using a metering pump to maintain the pH at 9.5.
After the completion of the dropwise addition of the aqueous sodium silicate solution, a 3.5% by weight aqueous hydrochloric acid solution is added to adjust the pH to 6.0, and then the silicon dioxide-coated graphite flake particles are collected by filtration.

Further, the water-soluble neutralized salt remaining on the silicon dioxide-coated graphite flake particles is washed away with ion-exchanged water and dried at 105 ° C. for 15 hours. After drying, rutile-type titanium dioxide is coated in the same manner as in Example 2 using the silicon dioxide-coated graphite flakes. X-ray analysis of the obtained titanium dioxide crystals of the pigment shows that all are covered with rutile-type titanium dioxide. In addition, a weather resistance test of this pigment with a carbon arc sunshine weather meter (Suga Test Machine) reveals that the pigment has much better weather resistance than the anatase type titanium dioxide pigment of the comparative example.

The weather resistance test was performed as described below. [Weather resistance test] Paint resin for automotive top coating, acrylic
Using a melamine thermosetting resin, a test plate was prepared by a two-coat, one-bake method, and an exposure test was performed with a carbon arc sunshine weather meter (Suga Test Machine) to obtain a color against the color tone before the test. The change ΔE value is evaluated.

Preparation of Test Coated Plate Super Luck F47 Black (Nippon Paint Co., Ltd.) was applied to a bondy-treated mild steel plate at 35 to 40 μm,
Bake at 0 ° C. for 30 minutes. The coated plate is polished with # 600 sandpaper, washed and dried at 110 ° C., coated with a base paint described below to a thickness of 18 to 20 μm, and further coated with a top clear paint described below. Apply top clear coating to a film thickness of
It was baked at 0 ° C. for 20 minutes to obtain a test coated plate.

<Base Coatings> Pigments of Examples and Comparative Examples of the Present Invention (Each Test) 20 Parts by Weight Acrydec 47-712 (Dainippon Ink Kogyo Co., Ltd.) 70 parts by weight Super Beckamine G821-60 (Dainippon Ink Industry Co., Ltd.) 30 parts by weight Ethyl acetate 50 Parts by weight Toluene ………………………………………………… 30 parts by weight n-butanol ............ 10 parts by weight Solvesso # 150 ........................ 40 parts by weight

<Top Clear Paint> Acrydec 44-179 ... 14 parts by weight Super Beckamine L117-60 ............... 6 parts by weight Toluene .............................. 4 parts by weight MIBK ... 4 parts by weight butyl cellosolve 3 parts by weight

Using a carbon arc sunshine weather meter (Suga testing machine),
It is performed under the conditions of rainfall and a black panel temperature of 63 ° C. for 12 minutes out of 60 minutes. The results are shown below.

[0046]

[Table 1]

Applications of the Pigment of the Present Invention Examples of the use of the graphite flake pigment coated with rutile titanium dioxide of the present invention include pigments for automotive top coatings, pigments for plastic coloring, pigments for printing inks, pigments for home appliance coatings, and building material coatings. Pigments, pigments for wax coatings, pigments for cosmetics, and the like. The pigment of the present invention is extremely suitable for pigments such as paints, plastics and inks used outdoors because of its excellent weather resistance and light resistance. When used as a pigment for automotive top coatings,
The pigment of the present invention is used in an overcoat layer, particularly in a base coat layer, in combination with an organic pigment, a carbon black pigment, a metal powder such as aluminum powder or a pearl pigment based on mica, or used alone. It can be used in a proportion of 0.1 to 50% by weight with respect to the base coating resin. An example of the application example is shown below.

Application Example 1 Acrylic-melamine resin Composition: Acrydec 47-712 (Dainippon Ink Industries, Ltd.)
70 parts by weight Super Beckamine G-821-60 (Dainippon Ink Industries, Ltd.) 30 parts by weight Pigment obtained in Example 1 Thinner for acrylic / melamine resin Composition: ethyl acetate …………………………… 50 parts by weight Toluene …………………………………………………………… 30 parts by weight n-butanol …………………………………………………………………………………………………………………………………………………………………………… 40 100 parts by weight and 20 parts by weight of the pigment obtained in Example 1 are mixed and adjusted to a viscosity suitable for spray coating (12 to 15 seconds with a Ford cup # 4) using an acrylic / melamine resin thinner. Then, a base coat layer is formed by spray coating.

Application Example 2 This example shows one application example used for coloring plastic. Polyethylene resin (pellet) ... 100 parts by weight Pigment obtained in Example 1 ... 1 part by weight Zinc stearate ... …………………… 0.2 parts by weight Liquid paraffin …………………………… 0.1 parts by weight The pellets are dry-blended and molded using an injection molding machine.

Application Example 3 This example shows one application example of gravure ink used as a pigment for printing ink. CCST media (nitrocellulose resin, Toyo Ink Co., Ltd.) 10 parts by weight Pigment obtained in Example 1 ... 8 ... 8 Parts by weight NC102 solvent (Toyo Ink Co., Ltd.) was added to the ink having the above composition, and Zancup No. 20 seconds viscosity at 3
Adjust and print.

Application Example 4 This example shows an application example used as a cosmetic pigment. The pigment of the present invention (particle size: 4.5 μm or less) 40 parts by weight talc 24 talc 24 parts by weight talc 24 Parts by weight Mica ............................................................... 10 parts by weight Zinc stearate ............... 5.0 parts by weight Zinc laurate ... 3.0 parts by weight Colored pigments ............... ... 10 parts by weight Hexadecyl myristate 5.5 parts by weight Isopropyl lanolin fatty acid 2.5 parts by weight 2.5 parts by weight Parts by weight Preservatives ………………………………………… Appropriate amount A cake-type eyeshadow is made using the above amount.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09C 1/44-1/46 C09C 3/06 A61K 7/02 C09D 7/12

Claims (6)

(57) [Claims] 1. The graphite flake particles which have been subjected to an oxidation treatment are coated with one or more metal oxide layers containing rutile titanium dioxide and / or rutile titanium dioxide hydrate. Graphite flake pigment based on flake particles. 2. The method of claim 1, wherein the oxidized graphite flake particles are coated with one or more metal oxide chips containing rutile titanium dioxide and / or rutile titanium dioxide hydrate together with silicon dioxide. There are graphite flake pigments based on the graphite flake particles. 3. A method for producing a graphite flake pigment coated with rutile-type titanium dioxide, comprising suspending oxidized graphite flake particles in water, and adding the suspension to a tin metal salt, a zinc metal salt, and a lithium metal. An aqueous solution in which a metal salt selected from a salt and an antimony metal salt and a titanium metal salt are dissolved and an aqueous solution in which a basic substance is dissolved are simultaneously added to the surface of the graphite flake particles, tin, zinc, lithium, and A mixed oxide hydrate of a hydrate of an oxide of a metal selected from antimony and a hydrate of titanium dioxide is deposited, and an aqueous solution of a titanium metal salt and an aqueous solution of a basic substance are simultaneously added, and titanium dioxide is added. A method for producing a graphite flake pigment, comprising depositing a hydrate, filtering the obtained solid substance, washing, drying and calcining. 4. A method for producing a rutile-type titanium dioxide-coated graphite flake pigment, wherein oxidized graphite flake particles are suspended in water.
An aqueous solution in which a metal salt selected from a tin metal salt, a zinc metal salt, a lithium metal salt and an antimony metal salt is dissolved and an aqueous solution in which a basic substance is dissolved are simultaneously added, and on the surface of the graphite flake particles, Depositing a hydrate of an oxide of a metal selected from tin, zinc, lithium and antimony, further adding an aqueous solution of a titanium metal salt and an aqueous solution of a basic substance simultaneously to deposit titanium dioxide hydrate, The solid material obtained is filtered off, washed, dried and
A method for producing a graphite flake pigment, characterized by firing. 5. The method for producing a graphite flake pigment according to claim 3, wherein the oxidized graphite flake particles have a surface coated with silicon dioxide. 6. The method for producing a graphite flake pigment according to claim 4, wherein said oxidized graphite flake particles have a surface further coated with silicon dioxide.