JPS5931705A - Cosmetic blended with natural dyestuff pigment - Google Patents

Abstract

PURPOSE:A cosmetic having improved shade, chroma, and tinting power, and good dispersibility, containing natural dyestuff pigment as an active ingredient, obtained by adsorbing a natural dyestuff on porous magnesium and/or calcium aluminate silicate. CONSTITUTION:A cosmetic blended with natural dyestuff pigment obtained by adsorbing a natural dyestuff on porous magnesium and/or calcium aluminate silicate. For example, flavonoid dyestuff such as shisonin, callistephin, etc. and quinone dyestuff such as laccaic acid, alkannin, etc. may be used as the natural dyestuff pigment. The amounts of the aluminate silicate and the natural dyestuff in the natural dyestuff pigment are preferably about (10:1)-(10:20) (weight ratio). The natural dyestuff pigment, for example, is obtained by blending the aluminate silicate with the natural dyestuff in water, etc., treating the blend at 20-100 deg.C, drying and powdering it. Preferably the prepared pigment is further treated with a metal salt solution.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cosmetics containing novel natural pigments.

Conventionally, natural pigments, especially bi-soluble natural pigments, are mainly used as food additives. In this case, they are used in a solution state, slurry state, or in a dry state after removing the solvent from those states. In many cases, this method of use as a dye (in some cases, the dye tends to elute in the product, causing discoloration, bleaching, coloring of the product, etc.)
There are problems such as staining on 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 suitable for use in cosmetics, the present inventor discovered that porous fine powders of magnesium salts or calcium salts of silicate aluminate can easily be made from natural pigments. We discovered that the dye can be fixed by adsorption and fixation, and that it does not have the above-mentioned problems and is excellent as a pigment, and based on this knowledge, we have completed the present invention.

That is, the present invention provides a cosmetic composition characterized by containing a porous magnesium salt and/or calcium salt of aluminosilicate (a natural coloring pigment to which a dinatural pigment is adsorbed).

The fixing properties of the natural color pigments applied to 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 shisonin,
Callisteinin, gelfinidin, cyanine, laflor yellow, cacao pigment, kouryan pigment, rutin, lafuanine, chryzanthemine, flavonoid pigments such as hibiscus pigment, laccaic acid, cochineal pigment, kermes pigment, alizarin, shikonin, quinone pigment such as plucanene, chlorophyll, Porphyrin pigments such as phycosoanin, hemoglobin, myoglobin, and hemocyanin, other beet red, hematin, brasilein, curcumin, monascus pigment, riboflavin, curron, gardenia enzyme-treated pigment, indigo, tone, Asenyaku, Gobaiko, Huangbai, or β-carotene , lycopene, lutein,
Oil-soluble pigments such as fucoxanthin, cabzanthin, annatto-gardenia yellow pigment, canthaxanthin, and cryptoxanthin can be employed.

Examples of silicon acid aluminates include magnesium aluminate silicate and calcium aluminate silicate.

For example, the formula MO-A1203.2Si02, MO(OAI
JS+Os)2, or their hydrates (xH□0
, X is about 0 to at least 4, and even more than that has water absorption (reaching from -). In the above formula, M represents a weakly basic metal such as magnesium or calcium.

That is, there are magnesium metasilicate aluminate, calcium metasilicate aluminate, or a mixed composition salt of magnesium and calcium. Furthermore, 2MO・Al2O3・
Examples include dimagnesium silicate aluminate (or calcium) represented by 5IO8.xH2O.

These silicate aluminates are porous powders, in which fine particles that are essentially bi-amorphous form secondary particles and have a large specific surface area. The above compositional formula is generally expressed as a representative central value, but in reality,
This includes those having compositions similar to this. The property is water,
C2 is insoluble in alcohols, etc., but C2 is partially soluble in alkalis or acids.

Examples of magnesium aluminate silicate include those having the composition shown in Table 1-1 below. Water soluble (3) Except for 0.1-08%, the remainder is water. However, this water has the ability to hold an even larger amount from less than the desired number φ.

Table 1-1 As magnesium metasilicate aluminate or nimamagnesium silicate aluminate, those commercially available as antacids can also be used.

(4) Furthermore, the above-mentioned M,! If Ca is used instead of i'f2,
Alternatively, it is of course possible to use partially (using diCa) or a mixture thereof. Examples using Ca are shown in Tables 1-2f.

Table 1-2 The single particle diameter is approximately -f: about 1 mμ to 10 μ, preferably about 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 about 500 μ. Use the one. The specific surface area is 10 according to the BET method.
It is preferable to use a fine powder of about 0 to 4 oomyg. It is desirable that the 10% slurry has a PII value of about 6 to 1 ().

Natural color pigment of the present invention (aluminum silicate used in -
The ratio of acid salt to natural pigment is 1:1 to 10:20.
(weight ratio), but the limit is not definitive.

In the present invention, the metal salts contained in order to improve dye fixation and color deepening are, for example, aluminum, iron,
Salts of non-toxic metals such as copper, lead, and zirconium.Formate, acetate, hydrochloride, sulfate, nitrate, carbonate, alum salt, etc. can be used as salts of these metals.For example, aluminum ,,i, Copper acetate, aluminum, iron, copper, zirconyl 13, lead hydrochloride, iron, copper sulfate, and others (using alum, iron alum, etc.). Although the fixing treatment is not necessary depending on the purpose, when it is used, the amount of silicate aluminate (dry heavy paper) is approximately 0.5 to 80%, preferably 1 to 40%.

It is understood that the above-mentioned metal salts are water-soluble and are fixed due to the action of fixation treatment (the surface of magnesium silicate aluminate particles adsorbing acid residues and natural pigments).

Pigments such as cyanine, sosonine, cacao pigments, kouryan, hibiscus pigments, and carminic acid contain water because they remain soluble in water when adsorbed only on porous magnesium salts and/or calcium salts of aluminosilicate. When used in cosmetics, it requires a metal salt solution (secondary fixation).

Preferred metal salt solutions include pigments (regardless of the pigment, acetates, hydrochlorides, sulfates of aluminum, iron, zinc, calcium, magnesium, zirconium, etc.), alum, iron alum, and the like.

The natural color pigment used in the cosmetic composition of the present invention is produced, for example, as follows.

Aluminate silicate and natural pigment in water, e.g. 1-10%
or to improve solubility (methanol, ethanol, n-propanol, inpropanol, propylene glycol, chrycerol,
Acetone, butanol (7) (il, 2nd. 3rd), ethylene glycol, 1
A mixture obtained by mixing in water containing an appropriate amount of a water-soluble organic solvent such as 3-butanediol, such as a dispersion or slurry, is treated at about 20 to 100°C.

Natural color pigments are produced by washing, drying, and grinding (-).

If the pigment produced in this way is treated with a solution of the metal salt, for example, an aqueous solution of about 00% to 20%, and similarly washed with water, dried, crushed or crushed, it will be better in terms of dye fixation and deep color. Natural color pigments are produced.

The pigment of the present invention has excellent hue, saturation, and coloring power, and also has good dispersibility in all oil-based, emulsified-based, and powder-based systems, and is extremely effective for coloring cosmetics.

Hereinafter, the natural color pigments applied to the present invention will be explained in detail with reference to production examples.

Production Example 1 (Parts indicate parts by weight) 10 parts of laccaic acid, manufactured by Fuji Chemical Industry ■, trade name Neusilin uFL2, 100 parts of magnesium aluminate silicate (8) and 5% propylene glycol aqueous solution 600 parts
The resulting mixture was boiled at about 100° C. for 1 hour, cooled, and left for 24 hours. The precipitate was washed with water in a trench where the p solution became colorless, and then dried at 50° C. for 10 hours. After drying, a pigment was obtained by crushing with a hammer mill.

As a result of measuring this pigment with a color difference meter (Keihin Densokki Model 603), the L value was 25.96 according to the Hunter display method.
．． a value: 24.49. It exhibits a bright reddish-purple color with a b value of 2.79. The results of the same elution test as in Example 3 below showed that the elution amount after 4 hours was 10 ppm or less.

Production Example 2 A mixture obtained from 50 parts of laccaic acid, 100 parts of magnesium metasilicate aluminate as in Production Example 1, and 600 parts of a 5% aqueous propylene glycol solution was heated at about 100°C for 30 minutes.
Boiled for 0 minutes d1: Processed. After cooling, the mixture was left to stand for 24 hours, and the precipitate was washed and dried at 50° C. for 10 hours. After drying, the powder was crushed using a Raikai machine (2) and added to 250 parts of an aqueous solution containing 4% aluminum acetate and 2% acetic acid.
After heating at 0°C for 1 hour, the mixture was cooled to room temperature. After leaving it for 24 hours, the precipitate was taken from house to house and washed with water until the Oki liquid became colorless.
It was dried at 50°C for 15 hours. It was ground in the same manner as above to obtain a pigment. This pigment has an L value of 22.73. a value: 20.27
It exhibited a deep reddish-purple color with a b value of 187.

Production Example 3 A mixture obtained from 40 parts of carminic acid, 1.00 parts of magnesium aluminate silicate as in Production Example 1, and 500 parts of water was boiled at about 1.00°C for 30 minutes and then cooled. Leave it at room temperature for 24 hours, remove the precipitate from door to door, wash it with water, and then heat it to 50°C.
, and dried for 15 hours. A pigment was obtained by crushing the dried product.

Production Example 4 The pigment obtained in Production Example 3 above was mixed with 1 part of aluminum acetate.
% and 200 parts of an aqueous solution containing 0.5% acetic acid, and heated at 65° C. for 30 minutes. 24 hours after cooling to room temperature
I left it for a while. The precipitate was washed from door to door until the p solution became colorless, dried at 50° C. for 15 hours, and then ground to obtain a pigment. This is L value: 1637°a value: 15.07 and b
It exhibits a deep reddish-purple color with a knee value of 2.63.

Take 0.5g of the pigment obtained in this way and add 25+++
/C every 60 minutes for the p solution immediately after ~240 minutes after being dispersed in water.
The color was measured over time using a bispectral photometer (Hitachi Model 139). The results are shown in Table 2.

For comparison purposes, a commercially available aluminum carminate lake pigment was similarly bidispersed in water, and time-lapse spectrophotometric colorimetry of P liquid was carried out. The results are also shown in Table 2.

Table 2 Note that the elution concentration was calculated using two absorbance measurements.

(11) That is, this pigment showed an elution amount of about 1/4 of the commercial product immediately after dissolution, and an elution amount of about 17100 after 4 hours.

Production Example 5 A mixture obtained from 50 parts of Monascus dye, 100 parts of magnesium aluminate silicate as in Production 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 filtered out and washed with water. After washing, the mixture was dried at 50°C for 15 hours, added to 200 parts of an aqueous solution containing 0.5 g of powdered 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 washed with water. After washing, it was dried at 50°C for 15 hours and ground in the same way (-) to obtain a pigment.

This is L value: 46.35. a value: 27.81 and b
It has a value of 12.68 and exhibits a bright red color.

Production Example 6 50 parts of laccaic acid and the same alkali silicate as in Production Example 1 were cooled to temperature and left for 24 hours. The precipitate was washed by draining water from the furnace (12). After washing and drying at 50°C for 115 hours, it was added to 250 parts of an aqueous solution containing 5% powdered sodium stannate and 5% citric acid, heated at 50°C for 30 minutes, and then left at room temperature for 24 hours. Separate the sediment from door to door and wash it 5.
After drying at 0°C for 115 hours, the mixture was ground to obtain a pigment. This is L
Value: 36.67, a value: 27.10 and b value: IL,
40 and exhibits a bright red color.

Production Example 7゜In Production Example 1, magnesium metasilicate aluminate 1
A pigment was produced by repeating Production Example 1 using 100 parts of calcium aluminate metasilicate instead of 00 parts. This is the L value: 38.72. a value: 22.55 and b value: 0.4
7 and exhibits a bright reddish-purple color. When used in cosmetics, it was sufficiently satisfactory as a pigment.

Production Example 8 A pigment was produced by repeating Production Example 2 using 100 parts of calcium aluminate metasilicate instead of magnesium metasilicate aluminate.

This is L value: 34.35. It has an a value of 22.50 and a b value of 040, and exhibits a deep reddish-purple color.

Production Example 9 Instead of magnesium metasilicate aluminate in Production Example 1, magnesium silicate aluminate manufactured by the same company (product name Fuji Chemical) was used.
A pigment was obtained in the same manner as in Production Example 1 using Neusilin A]).A pigment with no play of color compared to the pigment according to Production Example X was obtained.

L value: 37.81. a value: 20.20. b value:
248 Production Example 10 A pigment was obtained in the same manner as in Production Example 2 using the same magnesium aluminate silicate as in Production Example 8. A pigment with no play of color was obtained compared to the pigment of Production Example 2.

L value: 35.51. a value: 20.03. b value:
233 The natural color pigments obtained as described above can be used in cosmetics such as lip color, cheek color, face powder,
Manicure, body powder, eye color z 7'L'
S) i: Used by blending into outerwear, cream foundation, hand cream, etc.

Examples of the following (2) cosmetics are shown. The blending proportions are based on weight.

Example 1 Cake-shaped eye color meter 100.00 (ch)"
10 parts of Pig-A purple root ethanol extract was coated with 90 parts of magnesium metasilicate aluminate (pigment treated with -40% aluminum acetate solution).

A is a high-speed mixer (~Nsiel type mixer) (2 pieces (15
) After high-speed mixing for 2 minutes, grind and mix using a grinder.

Mix this in a Henschel mixer with B at 80°C.
Mix at low speed for 2 minutes, then cool to 20° C. (after cooling, add C and mix at low speed for 2 minutes. After pulverizing the mixture in a pulverizer, take it out and press.

Example 2 Powder eye color meter 100.0 (after mixing A at high speed for 2 minutes in a Henschel mixer, grinding and mixing with a grinder. Mix this and B at low speed for 5 minutes in a Shell mixer, Grind it using a grinder (second grinder) and take it out.

(16) Example 3 Face powder meter 100.0(%)”P
After fixing to 50 parts of ig-C laccaic acid and 100 parts of calcium aluminate metasilicate, Pigment A treated with (2) an aqueous solution (2) containing 4.0% aluminum acetate and 2.0% thiacetic acid was added in a Henschel mixer. After high-speed mixing for 2 minutes in a pulverizer, pulverize and mix in a pulverizer, add B to this, mix at low speed for 5 minutes in a Fusiel mixer, pulverize in a pulverizer (second time), and take out.

Example 4 Pressed powder meter 100.0 (琼”Pi
g-D 40 parts of carminic acid was fixed with 100 parts of magnesium aluminate metasilicate (2), and then Pigment A treated with (2) an aqueous solution containing 1% aluminum diacetate and 05% arsenic acid (2) in a shell mixer. Mix at high speed for 2 minutes, then crush and mix using a crusher.Add this (2B) and mix at low speed for 5 minutes in a Henschel mixer.After crushing with a crusher, take out and press.

Example 5 Cheek color meter 1.00.0 (%)”
Pig-E After fixing 50 parts of laccaic acid to 100 parts of magnesium aluminate metasilicate, Pigment A, which had been treated with an aqueous solution containing 40% aluminum acetate and 2.0% acetic acid, was mixed at high speed in a Henschel mixer for 2 minutes. Mix, pulverize with a pulverizer, add B after mixing, and mix in a Henschel mixer for 5 minutes.
Mix at low speed for 1 minute, crush in a crusher, then crush and press.

(19) Example 6 Cream Foundation D [Fragrance 0,5
8 total 100.00 (%)
(20) Mix A at 85°C (twice), mix with a Henschel mixer, grind and mix with a pulverizer, add C, and mix at 85°C. Add B,
Mix for 10 minutes at the same temperature in an emulsifying pot to emulsify. The mixture is cooled to 40° C. while being mixed, D is added, and the mixture is further mixed for 2 minutes and then taken out.

Example 7 Lip Color Meter 100.0 (%) B was mixed in a ball mill for 24 hours to form a paste.

This paste is heated to 90° (2 degrees), mixed with A previously heated to 90°, and cooled. When molding, melt at 90°, pour into the mold, and cool. and remove it.

Example 8 Body powder meter 100.0 (灼”Pi
g-F A pigment in which 50 parts of Monascus pigment was fixed with 100 parts of magnesium aluminate metasilicate (1), and then further fixed with an aqueous solution containing 05% potassium alum.

A was mixed at high speed for 2 minutes in a shell mixer, and then ground and mixed in a grinder. Add B to this, mix at low speed for 5 minutes in a Hempfel mixer, and pass through a blower shifter.

Example 9. ] 1nd Cream 1Tcarboxyvinyl Polymer 0 (Aqueous Solution 160D
(10% triethanolamine aqueous solution 16C (purified water)
Dissolve and mix 6217A at 85°C, and transfer to an emulsification pot.

B and C were dissolved and mixed in advance at 85°C.
and mix for 5 minutes at 80°C to emulsify. While mixing, cool to 45°C, add E, and further cool to 30°C while mixing.

(23) Usage test by 40 women (used for 1 month) The dissolution properties for artificial sweat (PH5, 56) were investigated and it was found that there were no problems as shown below.

) Prescription composition of artificial sweat Sodium chloride 6248g Lactic acid 844L-Lysine
0.64L-aspartic acid
027 Urea
1639L-Asparagine 0.28
Threonine 0.57 Glutamine 0.29 Glycine
0.80 Alanine 071 Paris 7 0
．． 24 Inleucine 015 Hydroxyproline 0.90 Sodium pyrrolidone carboxylate 122 Calcium chloride
017 Potassium chloride
3.97 serin
228 Sodium hydroxide
0.20 purified water to 1000 shoulder
M) was dispersed and the dissolution property after stirring for 3 hours was calculated from the measured value of absorbance. (Hitachi Model 139 Spectrophotometer) As mentioned above, when a commercially available product is used, it exhibits considerable dissolution (on the contrary, in the case of the present invention, dissolution is suppressed, and both stain the skin). There is no problem with wearing it at all.

Furthermore, in order to prove that the natural color pigment according to the present application does not change color or bleach, a light resistance test was conducted using a xenon lamp tester.

(27) Xenon lamp tester test results Example 2. Example 4. In both Example 5, the ΔE value was lower than that of commercially available Sunset Yellow Lake, and the light resistance (2) was in a cylinder that could be used.

In each of the examples, no particular discoloration or decolorization was observed after being left at room temperature for 3 months.

Patent applicant Asamichi Kato (28), patent attorney and agent for Pola Chemical Industries, Ltd.

Claims (2)

[Claims] (1) Porous magnesium salt of aluminosilicate and/or
Or, a cosmetic product characterized by blending a natural color pigment in which a natural colorant is adsorbed to a calcium salt. (2) Porous magnesium salt of aluminosilicate and/or
Cosmetics characterized by incorporating natural color pigments which have been fixed by adsorbing calcium salts (two natural pigments) and fixing them by treating with metal salt solutions (two treatments) consisting of aluminum, iron, copper, zinc or zirconium.