JP2003277646A - Colored flake pigment having elution resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain colored flake pigment having elusion resistance, which is useful as a new material contributing to diversification of cosmetics and coatings by a slippery feeling in powder and visual effect and coating protection effect in a coating layer and comprises an anionic coloring matter safe to the human body as a coloring source. <P>SOLUTION: The colored flake pigment having elusion resistance, which has a hydrotalcite type coloring composition containing a coloring matter anion on an inorganic flaky particle as the coating layer is produced by reacting a soluble anionic coloring matter with a plurality of soluble metal salts to become a raw material for double hydroxide and a urea-containing base for neutralization in an aqueous suspension containing the inorganic flaky particle, precipitating and forming the hydrotalcite type coloring composition on the inorganic flaky particle, further reacting the composition with a solution of a titanyl salt and a urea-containing salt for neutralization, and adding hydrous titanium oxide to the coating layer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a usefulness in terms of a slippery feeling in powder and a visual effect and a coating protecting effect in a coating layer, and in addition, it is a coloring agent in the field of make-up cosmetics and the like in which harmlessness to the human body is required. The present invention relates to an elution-resistant colored flake pigment, a method for producing the same, and a cosmetic obtained by blending the flake pigment.

[0002]

2. Description of the Related Art Conventionally, when an inorganic flake pigment is used as a coloring agent having a special effect, an inorganic coloring component such as iron oxide is added to a coating layer of flake particles, or an inorganic or organic coloring agent is added to the particles. The method of coating the surface has been taken. However, coloring with an inorganic coloring component has a limited hue and low saturation, and coloring with an organic pigment limits the dyes that can be applied in terms of harmlessness to human body and elution resistance. For this reason, the present inventors, food hygiene law or Pharmaceutical Affairs Law, food,
A coloring composition in which a dye anion of an anionic tar dye specified for pharmaceuticals, quasi-drugs and cosmetics is introduced between layers of a hydrotalcite-type inorganic layered double hydroxide (hydrotalcite-type coloring composition) Called))
A method for producing a uniform coating layer on the surface of inorganic flake particles such as talc, mica, sericite, kaolin, etc. was found, and a colored flake pigment with a high saturation in hues of red, yellow and blue was developed (JP 2001 -234090). Furthermore, a colored pearlescent flake pigment was developed by applying this method to pearlescent inorganic flake particles.

[0003]

Since the coloring in the colored flake pigments and the colored pearlescent flake pigments by the present inventors is caused by the anionic dye which is originally soluble,
It has a tendency to liberate and elute the dye anion in an aqueous vehicle or an organic solvent vehicle such as alcohol or ester. This tendency differs depending on the type of dye, and for example, the food dye Blue No. 1 dye used for coloring blue is extremely water-soluble, so even if it is fixed between the layers of the hydrotalcite-type crystal structure to be the flake pigment coating layer. However, the elution of the dye anion into the electrolyte solution cannot be sufficiently suppressed. Red 201 dye, which is used for coloring red, shows an elution property that is not negligible in alcohols and esters. In order to use these new flake pigments in a wide variety of vehicles, enhanced elution resistance is needed.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have found that inorganic flake-like particles can be hydrotalized to seal open end faces of a layered crystal structure containing dye anions to prevent elution. After depositing and forming a coating layer with a site-type coloring composition, as a result of various attempts to deposit and form metal hydroxides, it was found that hydrous metal oxides, especially hydrous titanium oxide are effective for this purpose. ,
The present invention has been completed.

That is, the present invention provides that a hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers is provided as a coating layer on the surface of an inorganic flake particle, and a hydrous titanium oxide is further added. An elution-resistant colored flake pigment characterized by having as an adduct to a coating layer, and as a method for producing the same, a soluble anionic dye in an aqueous suspension containing inorganic flake particles and the layered compound water. A plurality of soluble metal salts, which are raw materials of oxides, are reacted with a neutralizing base to deposit and form the hydrotalcite-type layered double hydroxide on the surface of the inorganic flake particles, and then the suspension is formed. The method is characterized by adding a titanyl salt solution and a neutralizing base to the reaction, and adding hydrous titanium oxide to the layered double hydroxide, and further containing the elution-resistant colored flake pigment. It is a cosmetic which is characterized in.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A hydrotalcite-type coloring composition is a hydrotalcite formed from a divalent metal ion (M) such as magnesium, calcium or zinc and a trivalent metal ion (M ') such as aluminum. Type layered double hydroxide [M _{1-x M'x} (OH) ₂ ] (A ^n- ) _{x / n} · m H ₂ O
(0.2 ≦ x ≦ 0.33), a coloring composition having a layered crystal structure obtained by introducing a dye anion as an interlayer anion (A ⁿ⁻ ). To produce this, there are roughly three methods. There is. First, A ^n-is Cl ^- is Cl
This is an ion exchange method in which a hydrotalcite form is contacted with an aqueous solution of an anionic dye to perform anion exchange. Secondly, CO ₃
Formed hydrotalcite is calcined at about 500 ° C, dehydrated and decarboxylated to form amorphous oxide, then reacted with dye anion in aqueous solution to regenerate the hydrotalcite structure in anion-exchanged form. It is a construction method. Third,
This is a direct production method of precipitating a dye anion type hydrotalcite by mixing a plurality of metal salt solutions according to the above compositional formula, a dye solution and a neutralization equivalent of a base solution by an appropriate method. Although either method may be employed for the present invention, this direct production method is most suitable for the purpose of obtaining a dark colored flake pigment.

From the viewpoint of harmlessness to the human body, the metal salts used in the production method of the present invention include chlorides such as magnesium, calcium, zinc, etc., sulfates, nitrates, etc., and trivalent metals. For aluminum, aluminum chloride, sulfate, nitrate, etc. and sodium aluminate are used. As the basic substance used for neutralization, sodium hydroxide, ammonia, urea or the like can be used. As anionic dyes, food yellow No. 4 (Tartrazine), yellow No. 5 (Sunset Y)
ellow FCF), Blue No. 1 (Brilliant Blue FCF), Red No. 3 (Erythrosine), Red No. 104 (Floxine B), Red 20
Soluble anion dyes selected from tar dyes for foods, pharmaceuticals, quasi-drugs, and cosmetics, such as No. 1 (Lithol RubineB), which are defined by the Food Sanitation Law or the Pharmaceutical Affairs Law are used.

In the manufacturing process, each of the above-mentioned raw materials is dissolved in water (suspended ones having low solubility such as red No. 210 are suspended), and 2 to 4 or 5 depending on the type of anionic dye. After a separate solution of seeds (if urea is added), it is finally combined with the suspension in which the inorganic flake particles are dispersed and mixed together. A flake particle suspension and a raw material solution that can be mixed with the dye solution in advance are placed in the reaction tank, and the other raw material solutions are dropped and mixed therein while being well stirred. The combination of raw material solutions that can be mixed in advance is determined in consideration of the reactivity of each raw material. For dyes lacking acid resistance and basic resistance such as food color blue No. 1, in order to keep the pH of the dye solution from 3 to 9 in the reaction tank, it is recommended to use It is also necessary to simultaneously add the Japanese base solution dropwise. A basic dye such as Red No. 201 can be mixed in advance with a sodium aluminate solution or a neutralizing base solution. After completion of the dropping and mixing, the mixture is heated and aged at 80 ° C. or higher to gradually produce a hydrotalcite-type coloring composition containing dye anions on the surface of the inorganic flake particles.

The surface of the inorganic flake particles can be coated with the hydrotalcite-type coloring composition by the above-mentioned method. However, the properties of the coating differ significantly depending on the raw material used and the neutralization method. In the method in which metal chloride is used as a raw material and neutralized with sodium hydroxide, the coating becomes an aggregate of fine particles, and the smoothness of the particle surface is lost. It has been found that replacing one-sixth of the sodium hydroxide with urea in the same raw material gives a uniform and smooth coating.

A titanyl sulfate solution is practical as a titanyl salt that is a source of hydrous titanium oxide. After completion of coating with the hydrotalcite-type coloring composition, the mixture is cooled to room temperature and then added with urea, and heated to 80 ° C. or higher to allow the hydrolysis reaction to proceed.

[0011]

[Function] Although it is not known in what form hydrous metal oxide, especially hydrous titanium oxide is added to the coating layer of the hydrotalcite-type coloring composition, the effect of suppressing elution to the intercalation dye anion is remarkable. Therefore, it is presumed that it deposits on the open end of the layered structure and has a sealing action.

[0012]

EXAMPLES Next, typical examples and formulation examples will be given to show specific embodiments of the present invention, but the technical scope of the present invention is not limited thereto.

Example 1 21.6 g of food dye Blue No. 1 (purity 91.6%) and wet ground talc powder (FK-300S manufactured by Yamaguchi Mica Co., Ltd., average particle size: 17.8 μ)
_{m) 50.0g, ZnCl 2 13.6g,} AlCl 3 · 6H 2 O 12.1g and urea
Dispense 41.9g into a 2L Erlenmeyer flask to make a uniform aqueous dispersion with a total volume of 1,500mL. Then, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours. A neutralization reaction proceeds with the decomposition of urea, and a hydrotalcite-type coloring composition is formed on the surface of the talc powder. After completion of aging, the mixture was cooled to room temperature, 60 mL of 0.2 M titanyl sulfate solution and 64.2 g of urea were added, and the mixture was heated to 100 ° C and heated to 24
Stir at reflux for hours. After aging, cool to room temperature,
The product is filtered, repeatedly washed with water until the filtrate becomes colorless, and then dried at 50 ° C. By this method, 73.5 g of blue flake pigment (Ti content: 0.8%) was obtained. The product was obtained as a powder with less agglomeration during drying and a good slippery feel, and showed elution to the extent that a pale blue color was observed with 1% saline.

Example 2 Food dye Blue No. 1 (purity 91.6%) 1.35 g and pearl mica (Engelhard, average particle size: 28 μm, TiO ₂ coverage: 17%) 50.0 g, ZnCl ₂ 0.85 g, AlCl ₃ · 6H ₂ takes O 0.76 g and urea 2.62g in Erlenmeyer flasks 2L, the total amount, 50
Make 0 mL of uniform aqueous dispersion. Then heat to 100 ° C
The mixture is stirred under reflux for a time to form a hydrotalcite-type coloring composition on the surface of the pearl mica particles. Thereafter, the same procedure as in Example 1 was carried out to obtain 51 g of a blue pearlescent flake pigment having elution resistance to the extent that blue color cannot be visually recognized with 1% saline solution.

Example 3 Red No. 201 (purity 92.5%) 11.6 g, 0.5 N-NaOH 300 mL, wet ground talc powder (FK-300S manufactured by Yamaguchi Mica Co., Ltd., average particle size: 17.8 μm) 50.0 g, MgCl ₂・ 6H ₂ O 20.3g, AlCl ₃・ 6H ₂ O
Take 12.1 g and 41.9 g of urea in a 2 L Erlenmeyer flask,
Make a uniform dispersion with a total volume of 1,500 mL. Then, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours to form a hydrotalcite-type coloring composition on the talc powder surface. Thereafter, the same procedure as in Example 1 is carried out, and red flake pigment having elution resistance to the extent that red color cannot be visually recognized with 1% saline solution and ethanol.
I got 70g.

Example 4 1.4 g of Red No. 201 (purity 92.5%), pearl mica (Chimisulon Super Blue manufactured by Merck & Co., average particle size: 10-60 μ)
m, TiO ₂ coverage: 55%) 50.0g, ZnCl ₂ 3.4g, AlCl ₃・ 6H ₂
Take 3.0 g of O and 10.5 g of urea in a 2 L Erlenmeyer flask,
Make a uniform dispersion with a total volume of 1,500 mL. Next, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours to form a hydrotalcite-type coloring composition on the surface of the pearl mica particles. Thereafter, the same procedure as in Example 1 is performed so that the interference color and the red color are superimposed,
52.3 g of a colored pearlescent flake pigment whose red elution was invisible with 1% saline and ethanol was obtained.

Example 5 Red No. 201 (purity 92.5%) 1.4 g, pearl mica (manufactured by Engelhard, average particle size: 28 μm, TiO ₂ coverage: 60-82)
%) 50.0g, ZnCl ₂ 3.4g, AlCl ₃・ 6H ₂ O 3.0g and urea 1
Transfer 0.5 g to a 2 L Erlenmeyer flask to make a uniform dispersion with a total volume of 1,500 mL. Next, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours to form a hydrotalcite-type coloring composition on the surface of the pearl mica particles. Thereafter, the same procedure as in Example 1 was carried out to obtain 53.0 g of a colored pearlescent flake pigment in which the interference color and the red color overlap with each other and the red color elution cannot be visually observed with 1% saline and ethanol.

Example 6 3.0 g of yellow No. 4 (purity 89.4%), wet ground talc powder (FK-300S manufactured by Yamaguchi Mica Co., Ltd., average particle size: 17.8 μm) 50.0 g, Zn
Cl ₂ 13.6 g, take AlCl ₃ · 6H ₂ O 12.1g and urea 16.8g in Erlenmeyer flasks 2L, a uniform dispersion of the total amount of 1,500 mL. Then, the mixture is heated to 100 ° C. and stirred under reflux for 24 hours to form a hydrotalcite-type coloring composition on the talc powder surface. Thereafter, the same procedure as in Example 1 was carried out to obtain 65.5 g of a yellow flake pigment having elution resistance to the extent that yellow color cannot be visually recognized with 1% saline solution.

Example 7 Yellow No. 5 (91.6%) 12.4 g, Pearl mica (Nippon Koken Kogyo KK, color: silver, particle size: 5-30 μm, TiO ₂ coverage:
38%) 50.0 g, taken MgCl ₂ · 6H ₂ O 20.3g, the AlCl ₃ · 6H ₂ O12.1g and urea 41.9g in Erlenmeyer flasks 2L, the total amount, 50
Make 0 mL of uniform aqueous dispersion. Then heat to 100 ° C
Stir at reflux for hours. A neutralization reaction proceeds with the decomposition of urea, a hydrotalcite-type coloring composition is formed on the surface of the pearl mica particles, and a vivid orange yellow color is formed. Less than,
An orange-yellow pearlescent flake pigment having elution resistance to the extent that coloring is not visually recognizable with 1% saline solution is carried out in the same manner as in Example 1.
I got 71g.

Example 8 The blue flake pigment obtained in Example 1 was used to prepare an emulsified eye shadow according to the following formulation. Powder: Pigment of the present invention (Example 1) 18 parts Kaolin 2 parts Aqueous phase: Purified water 55 parts Butylene glycol 5 parts Glycerin 1 part Oil content: Stearic acid 3 parts Isopropyl myristate 8 parts Liquid paraffin 5 parts Propylene glycol monolaurate 3 Part manufacturing method: Powders are mixed with a blender, and this is added to an aqueous phase part which is heated and dissolved at about 75 ° C, and mixed by stirring. Separately, about oil
It is heated and melted at 75 ° C., added to the above powder dispersion with stirring, uniformly dispersed with a homomixer, and then stirred and cooled to room temperature.

Example 9 Using the red flake pigment obtained in Example 3, a lipstick was prepared according to the following formulation. Oil: Microcrystalline wax 10 parts Ceresin 10 parts Glyceryl triisooctanoate 10 parts Vaseline 10 parts Glyceryl triisoglycerate 20 parts Powder: Titanium dioxide 2 parts Inventive pigment (Example 3) 18 parts Process: Heat wax and oil Thaw and mix evenly. Powder is added to this and uniformly dispersed with a homomixer, then poured into a mold and rapidly cooled to form a stick.

Example 10 Using the red pearlescent flake pigment obtained in Example 4, a nail enamel was prepared according to the following formulation. Resin: Nitrocellulose (viscosity 1/2 second) 10 parts Alkyd resin 10 parts Plasticizer: Acetyltributyl citrate 5 parts Solvent: Ethyl acetate 25 parts Butyl acetate 45 parts Ethyl alcohol 5 parts Powder: Pigment of the present invention (Example 4 ) Proper amount production method: Take a part of alkyd resin and a part of acetyltributyl citrate, add a pigment and knead well. The remaining components are separately mixed and dissolved in a closed container, the pigment kneaded product is added thereto, and the mixture is stirred and uniformly dispersed.

[0023]

[Effects of the Invention] A novel colored flake pigment that is clear in color and excellent in elution resistance is created using a tar dye, which is safe for the human body, as a coloring source, and is useful in cosmetics and coating applications where the human body is harmless. Brings with it the possibility of becoming a colorant.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] December 18, 2002 (2002.12.
18)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

In the manufacturing process, each of the above-mentioned starting materials is dissolved in water (suspended ones having low solubility such as Red No. 201 are suspended), and 2 to 4 or 5 depending on the type of anionic dye. After a separate solution of seeds (if urea is added), it is finally combined with the suspension in which the inorganic flake particles are dispersed and mixed together. A flake particle suspension and a raw material solution that can be mixed with the dye solution in advance are placed in the reaction tank, and the other raw material solutions are dropped and mixed therein while being well stirred. The combination of raw material solutions that can be mixed in advance is determined in consideration of the reactivity of each raw material. For dyes lacking acid resistance and basic resistance such as food color blue No. 1, in order to keep the pH of the dye solution from 3 to 9 in the reaction tank, it is recommended to use It is also necessary to simultaneously add the Japanese base solution dropwise. A basic dye such as Red No. 201 can be mixed in advance with a sodium aluminate solution or a neutralizing base solution. After completion of the dropping and mixing, the mixture is heated and aged at 80 ° C. or higher to gradually produce a hydrotalcite-type coloring composition containing dye anions on the surface of the inorganic flake particles.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takasada Ishii             Minamiyama Nitta, Ina, Kozai-cho, Hohan-gun, Aichi             258-8 F-term (reference) 4C083 AB242 AB432 AC012 AC022                       AC102 AC122 AC242 AC342                       AC352 AC392 AC422 AD092                       AD262 BB25 BB26 CC01                       CC11 CC13 CC14 CC28 DD11                       DD23 DD31 EE01 EE06 EE09                       FF01                 4J037 AA26 AA27 CA08 CA09 CA11                       CA12 CB18 DD02 DD10 EE02                       EE03 EE04 EE28 EE33 EE43                       FF02 FF09 FF25 FF29

Claims (8)

[Claims] 1. A hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of an inorganic flake particle, and further has hydrous titanium oxide as an adduct to the coating layer. An elution-resistant colored flake pigment characterized in that: 2. The pigment according to claim 1, wherein the inorganic flake particles are natural clay minerals selected from talc, mica, sericite, kaolin or artificial clay minerals. 3. The pearlescent inorganic flake particles obtained by coating a natural clay mineral selected from talc, mica, sericite, kaolin or an artificial clay mineral with a metal oxide having a high refractive index. The pigment according to claim 1, wherein 4. The hydrotalcite-type layered double hydroxide is a double hydroxide of at least one selected from divalent metals of magnesium, calcium and zinc and aluminum. The described pigment. 5. The anion derived from a soluble anion dye selected from tar dyes for foods, pharmaceuticals, quasi-drugs, and cosmetics specified by the Food Sanitation Law or the Pharmaceutical Affairs Law. The pigment according to claim 1. 6. A hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers as a coating layer on the surface of an inorganic flake particle, and further contains titanium oxide hydroxide as an adduct to the coating layer. A method for producing an elution-resistant colored flake pigment, comprising: a soluble anionic dye in an aqueous suspension containing inorganic flake particles and a plurality of soluble metal salts as raw materials for the layered double hydroxide. And a base for neutralization are reacted to deposit and form the hydrotalcite-type layered double hydroxide on the surface of the inorganic flake particles, and then a titanyl salt solution and a base for neutralization are added to the suspension. The reaction is carried out to add a hydrous titanium oxide to the layered double hydroxide, and a method for producing an elution-resistant colored flake pigment, comprising: 7. The method according to claim 6, wherein at least a part or all of the neutralizing base is urea. 8. A hydrotalcite-type layered double hydroxide containing a dye anion between crystal structure layers is provided as a coating layer on the surface of the inorganic flake particles, and further, hydrous titanium oxide is provided as an adduct to the coating layer. A cosmetic comprising an elution-resistant colored flake pigment characterized in that: