JPH10158537A - Red pigment, its production and cosmetic using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a red pigment in which a cochineal pigment is stably fixed in a state assuming a bright red color, provide a method for efficiently producing the red pigment and prepare a makeup cosmetic containing the red pigment. SOLUTION: This method for producing a red pigment comprises bringing a powdery barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose or a nylon resin treated with a hydroxide or a carbonate of an alkali metal or a water-soluble aluminum salt into contact with an aqueous solvent containing a lake substance of a cochineal pigment finely dispersed in the presence of a fixing promoter comprising the hydroxide or carbonate of the alkali metal and the water-soluble aluminum salt. The makeup cosmetic is prepared by formulating 100 pts.wt. basic composition of the cosmetic with 0.01-50 pts.wt. red pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel red pigment,
The present invention relates to a production method thereof and a cosmetic containing the red pigment. More specifically, the present invention relates to a red pigment in which a cochineal dye is firmly fixed to a specific carrier, a method for producing the same, and a makeup cosmetic containing the red pigment.

[0002]

2. Description of the Related Art A red pigment, "cochineal pigment (main component: carmine), has been conventionally found in the female body of a cockscomb L. (Coccus cacti L.) parasitizing cactus species in the desert regions of Mexico, Central America and South America. Acid) "is known to be included. This cochineal dye is difficult to keep the red color tone stable,
Up to now, it has not been easy to immobilize in a state of giving a bright red color.

On the other hand, powdery barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose and nylon resins are used as extenders and white pigments for cosmetics.

[0004] "Dyeing pigments" in which a dye is deposited on an extender pigment are known. The dye pigment is prepared by dispersing the extender pigment in an aqueous solution in which the dye is dissolved, and adding a precipitant such as tannin and antimonyl potassium tartrate or a resin soap or a metal salt to deposit the dye on the extender pigment. It is a thing. However, dyes dyed by this method are basic dyes and acid dyes,
It is not a mordant dye such as a cochineal dye, and the color tone of the obtained pigment is not thin and vivid. In addition, it is known that cochineal pigment can be converted into a water-insoluble lake by treating it with a precipitant such as potassium alum (potassium aluminum sulfate) or lime milk [fine powder slaked lime (calcium hydroxide)]. I have. From this, it is expected that if a carrier substance such as an extender or a white pigment is dispersed in an aqueous solution in which a cochineal dye is dissolved and a precipitant such as potassium alum is added thereto, the cochineal dye will adhere to the carrier substance. You. However, even if this conventional method is applied, it is difficult to immobilize the cochineal dye on a carrier substance in a state of displaying a bright red color,
Its color is purple. As described above, a red pigment in which a cochineal dye is stably immobilized on a carrier substance in a state of giving a bright red color has not been found so far.

[0005]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a red pigment obtained by stably immobilizing a cochineal dye in a vivid red state, and using this as a cosmetic ingredient. It is intended to be used as.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies on stably immobilizing a cochineal dye in a vivid red color, and as a result, have found that the cochineal dye can be fixed with an alkali metal hydroxide or carbonate. By contacting a specific carrier substance treated with a water-soluble aluminum salt with an aqueous solvent in which a lake of a cochineal dye is finely dispersed in the presence of an adhesion promoter, the cochineal dye exhibits a bright red color, The present inventors have found that they can easily and firmly adhere to the carrier substance, and have completed the present invention based on this finding.

That is, the present invention is obtained by fixing a cochineal dye to a carrier material selected from powdered barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose and Niro resin. The hue of the pigment is from 5.0 RP to 10.0 in the Munsell color system.
An object of the present invention is to provide a makeup cosmetic comprising 0.01 to 50 parts by weight of a red pigment and 100 parts by weight of the basic composition of the cosmetic fixed to the range of RP.

According to the present invention, the red pigment is
Powdered barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose or nylon resin treated with an alkali metal hydroxide or carbonate and a water-soluble aluminum salt, and further an alkali metal hydroxide or carbonate And a water-soluble aluminum salt in the presence of an adhesion promoter, by contacting an aqueous solvent in which a lake of the cochineal dye is finely dispersed.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a carrier substance to which a cochineal dye is fixed is selected from powdery barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose and nylon resin. Is used.

As the barium sulfate, for example, "barium arsenate" having an average particle diameter of 4 to 10 μm obtained by pulverizing natural barite and separating it in air or water depending on the difference in specific gravity, or When sodium sulfate acts on an aqueous solution of barium sulfide, or "precipitable barium sulfate" having an average particle diameter of 0.1 to 15 μm precipitated by allowing sulfuric acid to act on an aqueous solution of barium chloride, or when barium sulfate is precipitated. A plate-like diameter of 5 to 10 μm, a thickness of 0.1 to 10 μm, settled to form a plate-like crystal.
“Plate-shaped barium sulfate” of 0.4 μm or fine “spherical particulate barium sulfate” having a crystal shape of 0.1 μm is exemplified.

Next, as titanium oxide (titanium dioxide), for example, rutile-type titanium fine powder, anatase-type titanium fine powder having an average particle diameter of 0.1 to 0.5 μm, and rutile-type and anatase-type fine powders having high chemical purity. Particles of 10
Ultrafine titanium oxide particles as fine as 50 nm are exemplified.

Next, as talc, kaolin, mica and sericite, for example, talc powder having an average particle diameter of 3 to 15 μm, kaolin powder having an average particle diameter of 0.3 to 5 μm, and kaolin powder having an average particle diameter of 4 to 6 μm Mica, sericite (sericite) having an average particle diameter of 3 to 7 μm, and fired sericite (fired sericite) obtained by firing and pulverizing sericite are exemplified.

Next, as the powdered cellulose, for example, crystalline cellulose having an average particle diameter of 5 to 40 μm and an average particle diameter obtained by hydrolyzing cellulose acetate having an average particle diameter of 8 to 10 μm are used.
μm finely divided spherical cellulose and the like.

As the nylon powder, nylon powder having an average particle diameter of 1 to 40 μm obtained by finely pulverizing a polyamide polymer resin or fiber such as nylon 6, nylon 6.6, nylon 11 and nylon 12, is used. And nylon fine particles having a true spherical shape and an average particle size of about 5 μm.

In the present invention, one of the above-mentioned powdery carrier substances may be used alone, or two or more of them may be used in combination.

On the other hand, the lake of the cochineal dye used in the present invention is aluminum, calcium or a lake of aluminum and calcium, which is prepared by adding an aluminum salt or a calcium salt or both to an aqueous solution of a cochineal dye. It may be prepared, or a commercially available cochineal dye lake product may be used. Commercially available products include, for example, carmine [Matsumoto Trading Co., Ltd. and Iwase Cosfa Co., Ltd.], carmine lake [Ina Trading Co., Ltd.], carmine "San Ai" [San-Ei Gen FFI Co., Ltd. )] And the like, and are respectively a lake of aluminum or calcium or a lake of aluminum and calcium.

The red pigment of the present invention is obtained by firmly immobilizing a cochineal dye on the above-mentioned powdery carrier substance. The production method is as follows.
The powdered carrier material is treated with an alkali metal hydroxide or carbonate and a water-soluble aluminum salt. Next, [Second
Step of Fixing Step], the desired red pigment is produced by contacting the powdery carrier material treated in the first step with an aqueous solvent in which a lake of cochineal dye is finely dispersed in the presence of a fixing accelerator. can do.

In the first pretreatment step in the method of the present invention, a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt are used as a treating agent for the powdery carrier material. Here, examples of the hydroxide of the alkali metal include sodium hydroxide and potassium hydroxide, and examples of the carbonate of the alkali metal include sodium carbonate and potassium carbonate. And
On the other hand, examples of the water-soluble aluminum salt include potassium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, and aluminum ammonium sulfate dodecahydrate.
Decahydrate, aluminum acetate, aluminum sulfate, aluminum chloride, sodium aluminum chloride and the like can be mentioned. These alkali metal hydroxides or carbonates may be used alone or in combination of two or more. Also, the water-soluble aluminum salt may be used alone or in combination of two or more. Furthermore, the combination of a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt may be freely selected.

As a specific method of the “first-stage pretreatment step”, the above-mentioned powdery carrier substance is dispersed in an aqueous solution in which a water-soluble aluminum salt is dissolved, and then the alkali metal hydroxide is stirred while stirring. Alternatively, a method of adding an alkali metal carbonate is simple. The alkali metal hydroxide or carbonate used here may be gradually added as it is, or may be added in the form of an aqueous solution. This first
The treatment in the step may be performed at room temperature, but is preferably performed at a temperature of about 40 to 80 ° C. for about 30 minutes to 1 hour.

The amount of the water-soluble aluminum salt used for treating the powdery carrier material in this [first stage pretreatment step] is 20 to 30% by weight based on the carrier material. As 0.3 to 3.0% (W / V
%) Is appropriate. The alkali metal hydroxide or carbonate to be added here is used in an amount of 1.0 to 25.0% by weight based on the amount of the carrier substance. % (W / V%) is appropriate.

After performing this [first stage pretreatment step], the powdery carrier substance is dehydrated and taken out by a known means such as filtration or centrifugation, and is then taken out in the following [second stage fixation step]. ]
Used for

Next, in the [second fixing step] in the method of the present invention, a fixing accelerator is used. The adhesion promoter used herein is composed of a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt. The hydroxide or carbonate of an alkali metal used in the above [first stage pretreatment step] The same as the basic aluminum salt is used. Also in this [second fixing step], the hydroxide or carbonate of an alkali metal and the water-soluble aluminum salt may be used alone or in combination of two or more. Further, in the [first-stage pretreatment step] and the [second-stage fixing step], different alkali metal hydroxides or carbonates and water-soluble aluminum salts may be used.

As the aqueous solvent in this [second fixing step], a mixed solvent of water and a water-soluble organic solvent is preferable. As this water-soluble organic solvent, for example, methyl alcohol, ethyl alcohol, propyl alcohol,
Alcohols such as isopropyl alcohol are preferred,
These may be used alone or in combination of two or more. The mixing ratio of water and the water-soluble organic solvent is such that the water-soluble organic solvent is 0.1 to 0.6 per volume of water.
The capacitance part is appropriate.

Next, the amount of the cochineal dye used is 1 to the powdery carrier material treated in the first stage as a lake.
It can be arbitrarily selected in the range of from 80% by weight to 80% by weight, and can be fixed to the carrier material.

As a specific method of this [second fixing step], first, a lake substance of a cochineal dye is added to an aqueous solvent, and high-speed stirring is performed using a high-speed disperser such as a homodisper or a homomixer. Finely disperse the lake of the dye. Then, the powdery carrier material treated in the first stage is added thereto with stirring and dispersed, and a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt are added as adhesion promoters in a simple manner. Here, the lake product of the cochineal pigment finely dispersed in the aqueous solvent is 0.1%.
It is adjusted to a concentration of about 3.0% (W / V%). Further, the hydroxide or carbonate of an alkali metal and the water-soluble aluminum salt used here may be gradually added as they are, but it is preferable to use them by dissolving them in water. The second fixing step may be performed at room temperature, but is preferably performed at a temperature of about 40 to 60 ° C. for about 30 minutes to 1 hour.

In this [second stage fixing step], the alkali metal hydroxide or carbonate used as the fixing treatment agent is added in an amount of 0.2 to 8 with respect to the powdery carrier material treated in the first stage. 0.0% by weight, and the water-soluble aluminum salt was present in an amount of 0.1% based on the powdered carrier material treated in the first stage.
Use between 2 and 20.0% by weight. When these are used in the form of an aqueous solution, they are each used in an amount of 0.2 to 5.0% (W /
(V%).

In this way, the aqueous solvent in which the lake substance of the cochineal dye was finely dispersed and exhibited a red color became colorless and transparent as the fixing treatment proceeded, and the cochineal dye became vivid in the powdery carrier substance. It is firmly fixed in a red color. After the fixing treatment, the carrier on which the dye is fixed and fixed is taken out by a known means such as filtration or centrifugation,
After drying, if necessary, a pulverization (crushing) treatment is performed to obtain a red pigment having a Munsell color system having a desired color of 5.0 RP to 10.0 RP in the form of fine powder having excellent fastness.

The cochineal dye is also used as a coloring agent for foods, and the above-mentioned powdery carrier substances have high safety, and the red pigment of the present invention in which the cochineal dye is fixed to the carrier substance is It can be used very suitably as a coloring agent for cosmetics.

The makeup cosmetic of the present invention contains the above-mentioned red pigment as a coloring agent, and the compounding amount is 0.01 to 100 parts by weight of the basic composition of the cosmetic.
It is selected in the range of 50 parts by weight. The optimum amount of the red pigment is selected within the above range according to the type of the cosmetic.

The basic composition in the makeup cosmetic of the present invention is not particularly limited, and is a basic composition conventionally used in various makeup cosmetics, for example, eye shadow, blusher, foundation, lipstick, nail polish and the like. Can be mentioned. The makeup cosmetic of the present invention may optionally contain other coloring agents such as inorganic pigments and organic pigments. The method for preparing the makeup cosmetic of the present invention is not particularly limited, and a method conventionally used for preparing a makeup cosmetic can be used.

[0031]

The red pigment of the present invention is a pigment in which a cochineal dye is firmly fixed to a specific powdery carrier substance in a state of giving a deep red to a dark vivid red, and is soluble in water or water-soluble. Even under the conditions of the presence of the organic solvent, the fixed dye does not elute, has excellent extensibility on the skin, and is suitably used as a coloring agent for cosmetics and the like. Further, the makeup cosmetic of the present invention also contains the red pigment, has a vivid color tone, and has good adhesiveness to the skin and a good feeling of use such as spreading and familiarity. For example, it is suitably used as an eye shadow, a blusher, a foundation, a lipstick, a beautiful nail material, and the like.

[0032]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The physical properties of the obtained pigment were determined as follows. (1) Appearance By visual observation. (2) Hue H, lightness V, and chroma C A wavelength of 380 to 380 is measured by a spectrophotometer using an integrating sphere [Spectrophotometer "Ubest50" manufactured by JASCO Corporation].
780 nm reflection spectrum measurement, a C light source (daylight including a blue sky) as a standard light source, a color calculation program for obtaining Munsell coordinates according to a color system based on a two-degree field of view determined by the International Commission on Illumination (CIE) Industrial Co., Ltd., T
SV-433 color calculation program]. Note that R represents a red hue region, P represents a purple hue region, B represents a blue hue region, and Y represents a yellow hue region. (3) Dye dissolution test 0.5 g of the prepared pigment was placed in a test tube, and 10 ml of a mixture of ethanol and water in a volume ratio of 1: 9 was added.
After shaking for 0 minutes, the mixture was allowed to stand, and the coloring state of the supernatant was visually observed to confirm the elution of the dye.

Example 1 (1) 10 g of potassium aluminum sulphate dodecahydrate was added to 600 ml of purified water and dissolved, and then, with stirring, barium sulfate powder [manufactured by Sakai Chemical Industry Co., Ltd .:
Plate-shaped barium sulfate "Plate-shaped barium sulfate H", purity 98
%, Particle size 5-10 μm × 0.2 μm, median diameter 7.4
16 μm], and dispersed therein. The temperature of the aqueous solution was raised to 50 ° C., and 1% (W / V%) while stirring was continued.
50 ml of potassium hydroxide aqueous solution was added, and
For 30 minutes. Thereafter, the barium sulfate powder was removed by filtration and air-dried. (2) 120 ml of ethyl alcohol in 480 ml of purified water
and 6 g of a cochineal pigment aluminum calcium lake [Carmine "San-A" manufactured by San-Ei Gen FFI Co., Ltd.] was added thereto. 2,000 rotations (R /
M) and rotated at high speed for 10 minutes to finely disperse to prepare a dye bath. Next, while stirring the dyeing bath, the entire amount of the barium sulfate powder prepared in (1) was added and dispersed therein, the temperature of the dyeing bath was raised to 50 ° C., and 0.1 g of 0.1 as a fixing promoter was maintained while stirring. 90 ml of a 6% (W / V%) aqueous solution of potassium aluminum sulfate dodecahydrate was added dropwise, and then 1%
(W / V%) 8 ml of aqueous potassium hydroxide solution was added dropwise,
The mixture was further stirred at 50 ° C. for 1 hour. Thereafter, the red barium sulfate powder was filtered off, dried at 50 ° C., and pulverized in a mortar to obtain 9.9 g of a fine powdery pigment having a deep red appearance. The filtrate was colorless and transparent, and had a pH of 5. In addition, despite drying at 50 ° C., the cochineal dye firmly fixed did not fade and exhibited a bright deep red color, confirming that the obtained pigment was excellent in heat resistance. FIG. 1 shows the spectral reflection spectrum of the red pigment thus obtained. The hue H determined from this spectrum was 8.4 RP (purple red), the lightness V was 4.4, and the chroma C was 6.6. Further, as a result of the dye solubility test, no dye was eluted from the obtained pigment, which was favorable.

Comparative Example In place of 6 g of the aluminum calcium lake of the cochineal pigment in Example 1, a cochineal pigment extracted from the dried insect body of a non-lake carrot beetle ["Cochineal powder" manufactured by Alps Pharmaceutical Co., Ltd .: Price E: 54
4.1 (10%, 1 cm, absorption wavelength 495 nm)] 3 g
Pigment was produced in exactly the same manner as in Example 1 except for using. The pigment obtained in this way had a purple color with "dullness (turbidity)". This spectral reflection spectrum is shown in FIG. The hue H obtained from this spectrum was 8.6P (purple), the lightness V was 4.2, and the chroma C was 3.8. Furthermore, as a result of the dye solubility test,
A large amount of red dye eluted from the obtained pigment. Thus, it was confirmed that a red pigment could not be obtained or immobilized with a cochineal dye that was not laked.

Examples 2 to 8 Powdered titanium oxide (Example 2), talc (Example 3), kaolin (Example 4), mica (Example 5), sericite (Example 6) as carrier materials , Cellulose (Example 7) and a nylon resin (Example 8), and aluminum calcium lake [Carmine "San-A" manufactured by San-Ei Gen FFI Co., Ltd.] as a lake of cochineal dye. In the same manner as in Example 1 under the conditions shown in Tables 1 to 4, pigments exhibiting a bright deep red color were obtained. The spectral reflectance spectra of the pigments obtained in Examples 2 to 8 are shown in FIGS. 3 (Example 2), 4 (Example 3), 5 (Example 4), FIG. 6 (Example 5), and FIG. Example 6), FIG.
This is shown in (Example 7) and FIG. 9 (Example 8). Further, the results of the dye solubility tests of the pigments obtained in these examples were all good, and no dye was eluted from the obtained pigments. The titanium oxide described in Tables 1 to 4 is manufactured by Ishihara Sangyo Co., Ltd .: ultrafine titanium oxide “T
TO-55 (A) (average particle diameter 0.04 μm) ”, talc indicates“ Talc S (average particle diameter 18 μm) ”manufactured by Toshiki Pigment Co., Ltd., and kaolin indicates“ Tohoku Pigment Co., Ltd. ” : “Kaolin A (average particle size 0.5 μm)”
And mica is manufactured by Toshiki Pigment Co., Ltd .: “Mica M
(Average particle diameter: 20 μm) ”, and sericite manufactured by Toshiki Pigment Co., Ltd .:“ Serisite J (average particle diameter: 4.3)
μm) ”, and the cellulose is manufactured by Chisso Corporation: spherical cellulose“ Cell Flow C-25 (average particle size 8 to 10 μm).
m) ", and the nylon resin is a spherical nylon fine particle“ SP-500 (average particle diameter 5 μm) ”manufactured by Toray Industries, Inc.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[Production of Cosmetic] Example 9 Production of Lipstick (A) Component 7 parts by weight of red pigment of Example 1 Castor oil 45 parts by weight (B) Component 9 parts by weight of candelilla wax 8 parts by weight of solid paraffin Beeswax 5 Parts by weight Carnauba wax 5 parts by weight Lanolin 11 parts by weight Isopropyl myristate 10 parts by weight The above-mentioned component (A) is kneaded with a three-roller, and this is added to the dissolved mixture of the (B) component and mixed again with the three-roller. After kneading, the mixture was redissolved, poured into a mold, and cooled to obtain a lipstick. The red pigment of the present invention also had good dispersibility, and the color tone, adhesion, elongation, and touch of the obtained lipstick were extremely good.

Example 10 Production of Lipstick (A) Component Red pigment of Example 2 7 parts by weight Castor oil 45 parts by weight (B) Component Candelilla wax 9 parts by weight Solid paraffin 8 parts by weight Beeswax 5 parts by weight Carnauba wax 5 parts by weight Lanolin 11 parts by weight Isopropyl myristate 10 parts by weight The above component (A) was kneaded with a three-roller, added to the dissolution mixture of the component (B), kneaded again with the three-roller, and then re-dissolved. Then, the mixture was poured into a mold and cooled to obtain a lipstick. The red pigment of the present invention also had good dispersibility, and the color tone, adhesion, elongation, and touch of the obtained lipstick were extremely good.

Example 11 Production of Smoke Red (A) Component Red pigment of Example 1 3 parts by weight Talc 80 parts by weight Kaolin 9 parts by weight Zinc myristate 5 parts by weight (B) Component Liquid paraffin 3 parts by weight The above (A) Stir the ingredients well with a blender and mix,
The component (B) was sprayed there, further stirred and mixed by a blender, processed by a pulverizer, and then pressed into a mold to obtain a blusher. The color, adhesion, elongation, touch, and water resistance (sweat resistance) of the obtained blusher were extremely good.

[Brief description of the drawings]

FIG. 1 is a spectral reflection spectrum diagram of a red pigment obtained in Example 1.

FIG. 2 is a spectral reflection spectrum diagram of a purple pigment obtained in a comparative example.

FIG. 3 is a spectral reflection spectrum diagram of a red pigment obtained in Example 2.

FIG. 4 is a spectral reflection spectrum diagram of a red pigment obtained in Example 3.

FIG. 5 is a spectral reflection spectrum diagram of a red pigment obtained in Example 4.

FIG. 6 is a spectral reflection spectrum diagram of a red pigment obtained in Example 5.

FIG. 7 is a spectral reflection spectrum of the red pigment obtained in Example 6.

FIG. 8 is a spectral reflection spectrum diagram of a red pigment obtained in Example 7.

FIG. 9 is a spectral reflection spectrum of the red pigment obtained in Example 8.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yuko Noda 5396-2, Kamiogino, Atsugi-shi, Kanagawa Den Color Co., Ltd.

Claims (5)

[Claims] 1. The color of a pigment obtained by fixing a cochineal dye to a carrier material selected from powdery barium sulfate, titanium oxide, talc, kaolin, mica, sericite, cellulose and nylon resin. Red pigment fixed in the range of 5.0 RP to 10.0 RP in the Munsell color system. 2. Barium sulfate in the form of a powder treated with a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt;
Titanium oxide, talc, kaolin, mica, sericite,
Contacting a cellulose or nylon resin with an aqueous solvent in which a lake of a cochineal dye is finely dispersed in the presence of an adhesion promoter comprising a hydroxide or carbonate of an alkali metal and a water-soluble aluminum salt. A method for producing a red pigment. 3. The method according to claim 2, wherein the lake of the cochineal dye is aluminum, calcium or a lake of aluminum and calcium. 4. The method according to claim 2, wherein the aqueous solvent is a mixed solvent of water and alcohol. 5. A cosmetic composition having a basic composition of 100 parts by weight,
A makeup cosmetic comprising 0.01 to 50 parts by weight of the red pigment according to claim 1.