JPH0132263B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel natural pigment, and its object is to provide a pigment made from a natural pigment. Conventionally, natural pigments, especially water-soluble natural pigments, have been mainly used as food additives. in this case,
It is often used in a solution state, slurry state, or in a dry state with the solvent removed from those states, and when used as a dye, the dye tends to elute in the product. There are problems such as discoloration, decolorization, coloring of things that come into contact with it, and staining of the skin. These are disadvantages when used in cosmetics, and improvements are desired, particularly in terms of safety due to absorption into the skin. As a result of intensive research to develop excellent pigments using natural pigments, the present inventor found that porous fine powder of magnesium salt or calcium salt of silicon aluminate easily adsorbs and immobilizes natural pigments. The inventors have found that this pigment adheres well, and that it is excellent as a pigment without the above-mentioned problems, and based on this knowledge, they have completed the present invention. That is, the present invention provides the following natural color pigment. Flavonoid-based porous magnesium salt and/or calcium salt of aluminosilicate, which is a secondary particle powder consisting of fine particles of 1 mμ to 1 μ and a specific surface area in the range of 100 to 400 m ² /g (BET method) A natural pigment characterized by adsorbing a natural pigment selected from pigments, quinone pigments, carotenoid pigments, and monascus pigments. Flavonoid-based porous magnesium salt and/or calcium salt of aluminosilicate, which is a secondary particle powder consisting of fine particles of 1 mμ to 1 μ and a specific surface area in the range of 100 to 400 m ² /g (BET method) A natural product characterized by being adsorbed with a natural pigment selected from pigments, quinone pigments, carotenoid pigments, and monascus pigments, and fixed by treatment with a metal salt solution consisting of aluminum, barium, zinc, or zirconium. color pigment. The fixing properties of the natural color pigments of the present invention are further increased by further fixing treatment with a metal salt (aqueous solution). Examples of natural pigments in the present invention include flavonoid pigments such as shisonin, calistefin, delphinidin, cyanin, safrole yellow, cacao pigment, kourian pigment, rutin, rauanine, chrysanthemine, and hibiscus pigment;
latukaic acid, carminic acid (cochineal pigment),
Kermes pigment, alizarin, shikonin, quinone pigments such as alkannin, crocin, gardenia enzyme-treated pigment, β-carotene, lycopene, fucoxanthin, capsanthin, annatto-gardenia yellow pigment,
Carotenoid pigments such as canthaxanthin and cryptoxanthin, and other Monascus pigments can be employed. Examples of the aluminate silicate include magnesium aluminate silicate and calcium aluminate silicate.
For example, the formula MO・Al ₂ O ₃・2SiO ₂ , MO
(OAlSiO ₃ ) ₂ or their hydrates (xH ₂ O, x
The average temperature ranges from 0 to at least 4, and higher values can be reached by water absorption). In the above formula, M represents a weakly basic compound such as magnesium or calcium. That is, there are magnesium metasilicate aluminate, calcium metasilicate aluminate, or a mixed composition salt of magnesium and calcium. moreover
Examples include dimagnesium silicate aluminate (or calcium) represented by 2MO・Al ₂ O ₃・SiO ₃・xH ₂ O. These silicate aluminates are porous powders, with essentially amorphous fine particles forming secondary particles and having a large specific surface area. Although the above-mentioned compositional formula is generally expressed as a representative central value, the actual composition includes compositions that are close to this. It is insoluble in water, alcohol, etc., but partially soluble in alkalis or acids. Examples of magnesium aluminate silicate include those having the composition shown in Table 1-1 below. Except for 0.1 to 0.8% of water-soluble matter, the remainder is water. However, this water can be contained and retained in an even larger amount, from a few percent or less, depending on the purpose.

[Table] As magnesium metasilicate aluminate or dimagnesium silicate aluminate, those commercially available as antacids can also be used. Note that it is naturally possible to use a material using Ca in place of the above-mentioned Mg, a material using Ca partially, or a mixture thereof. Examples using Ca are shown in Table 1-2.

[Table] The single particle diameter is approximately 1 mμ to 1 μ, preferably approximately 10 mμ to 1 μ, and the average particle diameter of the powder (secondary particles) is preferably from 1 to 2 μ to a maximum of approximately 500 μ. . It is preferable to use fine powder having a specific surface area of about 100 to 400 m ² /g according to the BET method. It is desirable that the 10% slurry has a pH value of about 6 to 10. The ratio of silicate aluminate to natural pigment used in the present invention is approximately 10:1 to 10:20, preferably 10:
The ratio is approximately 5 to 10:15 (weight ratio), but the limit is not definitive. In the present invention, metal salts to be included in order to improve pigment fixation and dark color without impairing the hue of natural pigments include, for example, aluminum, barium,
Salts of non-toxic metals such as zinc and zirconium. Formate, acetate, hydrochloride, sulfate, nitrate, carbonate, alum salt, etc. can be used as salts of these metals. For example, aluminum, barium, etc. Acetate, aluminum, barium, zirconium, zinc hydrochloride, alum, etc. are used. Fixation treatment with these metal salts is not necessary depending on the purpose, but when used, the amount is approximately 0.5 to 80%, preferably 1 to 40%, based on the silicate aluminate (dry weight). It is understood that the above-mentioned metal salt is water-soluble and is fixed by the action of the acid residue and the surface of the magnesium silicate aluminate particles adsorbing the natural pigment during the fixing treatment. The natural color pigment of the present invention is produced, for example, as follows. Aluminate silicate and natural pigment in water, e.g.
methanol, ethanol, n-propanol, isopropanol, propylene glycol, glycerol, acetone, butanol (primary, secondary, tertiary), ethylene glycol, at a concentration of ~10% or as necessary to improve solubility. 1.3
- A mixture obtained by mixing in water containing an appropriate amount of a water-soluble organic solvent such as butanediol, such as a dispersion or slurry, is heated to about 20 to 100°C. washing with water,
Natural color pigments are produced by drying and pulverizing. The pigment thus produced is treated with a solution of the metal salt, for example, an aqueous solution of about 0.01 to 20%,
Similarly, by washing with water, drying, crushing or crushing, a natural color pigment with better dye fixation and deep color is produced. The pigment of the present invention has excellent hue, saturation, and coloring power, and also has good dispersibility in water, oil, emulsion, and powder systems, and is extremely effective for coloring cosmetics and foods, for example. It is. Hereinafter, the present invention will be explained in detail with reference to Examples. Example 1 (parts indicate parts by weight) Lactukaic acid 10 parts, manufactured by Fuji Chemical Industry Co., Ltd., trade name Neusilin uFL ₂ Magnesium silicate aluminate 100
1 part and 600 parts of a 5% aqueous propylene glycol solution was boiled at about 100°C for 1 hour,
After cooling, it was left for 24 hours. The precipitate was separated, washed with water until the liquid became colorless, and then dried at 50°C for 10 hours. After drying, the powder was ground using a hammer mill to obtain a pigment. This pigment was measured using a color difference meter (Keihin Densokki Unit 603).
As a result of measurement, the L value according to the Hunter display method is:
25.96, a value: 24.49, b value: -2.79, exhibiting a bright reddish-purple color. The results of the same dissolution test as in Example 3 below showed that the dissolution amount after 4 hours was 10 ppm or less. When this pigment was used in cosmetics such as lip color, cheek color, eye color, face powder, manicure, and body powder, it was found to be sufficiently satisfactory as a pigment. Example 2 A mixture obtained from 50 parts of latsukaic acid, 100 parts of the same magnesium metasilicate aluminate as in Example 1, and 600 parts of a 5% aqueous propylene glycol solution was boiled at about 100° C. for 30 minutes. After cooling, it was left to stand for 24 hours, and the precipitate was separated, washed, and dried at 50°C for 10 hours. After drying, the powder is crushed using a Raikai machine.
The mixture was added to 250 parts of an aqueous solution containing 4% aluminum acetate and 2% acetic acid, heated at 50°C for 1 hour, and then cooled to room temperature. After standing for 24 hours, the precipitate was separated, washed with water until the liquid became colorless, and dried at 50°C for 15 hours. It was ground in the same manner as above to obtain a pigment. This pigment exhibited a deep reddish-purple color with an L value of 22.73, an a value of 20.27, and a b value of -1.87. Example 3 A mixture obtained from 40 parts of carminic acid, 100 parts of magnesium aluminate silicate as in Example 1, and 500 parts of water was boiled at about 100° C. for 30 minutes and then cooled.
The mixture was left at room temperature for 24 hours, and the precipitate was separated, washed with water, and dried at 50°C for 15 hours. A pigment was obtained by crushing the dried product. Example 4 The pigment obtained in Example 3 above was added to 200 parts of an aqueous solution containing 1% aluminum acetate and 0.5% acetic acid, and heated at 65° C. for 30 minutes. After cooling to room temperature, it was left for 24 hours. The precipitate was separated, washed until the liquid became colorless, dried at 50°C for 15 hours, and then ground to obtain a pigment. This is L value: 16.37, a value:
It exhibits a deep reddish-purple color with a b value of 15.07 and a b value of -2.63. Take 0.5g of the pigment obtained in this way and make 25ml
Immediately after dispersion in water and after 240 minutes, the color of the liquid was measured every 60 minutes using a spectrophotometer (Hitachi Model 139).
The results are shown in Table 2. For comparison, a commercially available aluminum carminate lake pigment was similarly dispersed in water and the color of the liquid was measured spectrophotometrically over time. The results are also shown in Table 2.

[Table] The elution concentration was calculated based on the measured value of absorbance. That is, this pigment showed an elution amount of about 1/40 of the commercial product immediately after dissolution, and about 1/100 of the commercial product after 4 hours. Example 5 A mixture obtained from 50 parts of Monascus dye, 100 parts of magnesium aluminate silicate as in Example 1, and 500 parts of water was boiled at about 100°C for 15 minutes and cooled to room temperature. After standing for 24 hours, the precipitate was separated and washed with water. After washing, the powder was dried at 50°C for 15 hours and ground in a hammer mill. The powder was added to 200 parts of an aqueous solution containing 0.5% potassium alum and heated at 65°C for 30 minutes.
After cooling to room temperature, it was left to stand for 24 hours, and the precipitate was separated and washed with water. After washing, it was dried at 50°C for 15 hours and ground in the same manner to obtain a pigment. This is L value: 46.35, a value:
27.81 and b value: 12.68, giving it a bright red color. Example 6 A mixture obtained from 50 parts of latsukaic acid, 100 parts of magnesium aluminate silicate as in Example 1, and 500 parts of water was boiled at about 100°C for 30 minutes, cooled to room temperature, and left for 24 hours. The precipitate was separated and washed with water. After washing and drying at 50°C for 15 hours, the ground powder was dissolved in an aqueous solution containing 5% zinc acetate and 5% acetic acid.
After heating at 50°C for 30 minutes, the mixture was left at room temperature for 24 hours. The precipitate was separated, washed, dried at 50°C for 15 hours, and then ground to obtain a pigment. This is L value: 36.67, a
Value: 27.10, b value: 11.40, and exhibits a bright red color. Example 7 Example 1 was repeated to produce a pigment, except that 100 parts of calcium aluminate metasilicate was used instead of 100 parts of magnesium aluminate metasilicate. This is L value: 38.72, a value: 22.55 and b
It has a value of 0.47 and exhibits a bright reddish-purple color. When used in cosmetics, it was sufficiently satisfactory as a pigment. Example 8 In Example 2, calcium aluminate metasilicate was used instead of magnesium aluminate metasilicate.
A pigment was produced by repeating Example 2 using 100 parts.
This is L value: 34.35, a value: 22.50 and b value: 0.40
It has a deep reddish-purple color. Example 9 A pigment was obtained in the same manner as in Example 1 except that magnesium aluminosilicate manufactured by the same company (product name: Fuji Chemical [Neusilin A]) was used instead of magnesium metasilicate aluminate in Example 1. A pigment with less color observance than the pigment of Example 1 was obtained. L value: 37.81, a value: 20.20, b value: 2.48 Example 10 A pigment was obtained in the same manner as in Example 2 using the same magnesium aluminate silicate as in Example 9. A pigment with less color compliance than the pigment of Example 2 was obtained. L value: 35.51, a value: 20.03, b value: 2.33 Example 11 20 parts of rutin and 100 parts of magnesium aluminate silicate, the same as in Example 1, were dissolved and mixed in 800 parts of hot water, and then heated at about 100°C. Boil for 20 minutes, cool to room temperature, leave for 24 hours, filter out the precipitate, wash, and heat at 50℃ for 10 minutes.
Dry for an hour. After drying, the crushed powder was added to 250 parts of an aqueous solution containing 4% barium chloride and heated at 60°C.
After heating for 30 minutes, it was cooled and left at room temperature for 24 hours.
The precipitate was filtered, washed, dried at 50°C for 15 hours, and ground to obtain a pigment. This is L value: 35.78, a value: -
5.28, and b value: 23.41, exhibiting a bright yellow color. Example 12 30 parts of annatto-gardenia yellow pigment and 100 parts of magnesium aluminate silicate as in Example 9 were added to hot water at 60°C.
After dissolving and mixing in 800 parts and stirring for 30 minutes,
It was cooled and left for 24 hours. After filtering the precipitate and washing
It was dried at 40°C for 15 hours. After drying, the pulverized powder was added to 250 parts of an aqueous solution containing 1% zirconium sulfate, heated at 65° C. for 30 minutes, cooled, and left at room temperature for 24 hours. The precipitate was filtered, washed, dried at 50°C for 15 hours, and ground to obtain a pigment. This is L value: 48.32,
It has an a value of -9.46 and a b value of 28.45, and exhibits a pale yellow color. Comparative Test Using the natural color pigments of the present invention (Samples A and B) and the colored porous powders (Samples C and D) of JP-A-53-113036, which is the prior art of the present invention, the degree of coloration was determined. A comparative test was conducted on (Samples) Sample A Sample that was subjected to only adsorption treatment (latsukaic acid) in Example 2 and dried (first step only). Sample B Further treated with metal salt (aluminum acetate) (Example 2 itself). Sample C Based on Production Example 9 of the above publication. However, 1% by weight
Lactukaic acid 50 instead of calsamine aqueous solution
g, 200ml of 5% propylene glycol aqueous solution
was used, and 2% by weight of aluminum chloride was not added (no metal salt treatment). Sample D The above C combined with 2% by weight aluminum chloride (metal salt treated product). (Evaluation method) Take 0.2g of each sample from A to D, add 2.0g of titanium dioxide powder and 1.2g of castor oil, repeat 50 revolutions of the Huber-type muller three times, transfer to a glass cell, and measure with a colorimeter. It was measured with The colorimetric value is
The degree of coloration (K/S) was determined from the reflectance between 400 and 700 nm using Kubelkamunk's formula, and the summed value (Σ(K/S)) for every 20 nm was calculated to compare the degree of coloration. The results are shown in Table 3.

[Table] As is clear from the results in Table 3, it can be seen that the product of the present invention has far superior tinting power compared to the comparative product.

Claims (1)

[Scope of Claims] 1. A porous magnesium salt of aluminosilicate which is a secondary particle powder consisting of fine particles of 1 mμ to 1 μ and having a specific surface area in the range of 100 to 400 m ² /g (BET method); A natural color pigment characterized in that a natural pigment selected from flavonoid pigments, quinone pigments, carotenoid pigments, and monascus pigments is adsorbed on/or calcium salt. 2 Flavonoids are added to the porous magnesium salt and/or calcium salt of aluminosilicate, which is a secondary particle powder consisting of fine particles of 1 mμ to 1 μ and with a specific surface area in the range of 100 to 400 m ² /g (BET method). It is characterized by adsorption treatment of natural pigments selected from pigments, quinone pigments, carotenoid pigments, and monascus pigments, and fixation treatment by treatment with a metal salt solution consisting of aluminum, barium, zinc, or zirconium. Natural color pigment.