JPH10194928A - Fibroin pigment and makeup cosmetic - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a monascus pigment-bound fibroin pigment having good durability (e.g. bleeding resistance, thermal resistance and light resistance), color, luster, feeling and moisture retention, and further to obtain makeup cosmetics. SOLUTION: This fibroin pigment is obtained by adding regenerated fibroin powder to an alcohol dissolving slightly water-soluble or water insoluble monascus pigment obtained by culturing the Monascus pigment-producing microorganism belonging to genus monascus, under an alkaline condition of pH>=8 to bind the monascus pigment with the regenerated fibroin. The makeup cosmetics are obtained by formulating the fibroin pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pigment obtained by binding a hardly water-soluble or water-insoluble Monascus pigment to a regenerated fibroin powder, and a makeup cosmetic containing the pigment.

[0002]

2. Description of the Related Art Conventionally, tar dyes commonly used in cosmetics and the like are legally permitted to be used in cosmetics after they become harmful to the human body such as carcinogenicity and mutagenicity. Has been decreasing year by year. Natural pigments are highly safe pigments (colorants) that replace the tar pigments.
In particular, Monascus purpureus (Monascus P)
urpureus and Monascus Anka (Monas)
It is known that Monascus pigment-producing bacteria belonging to the genus Monascus, such as C. anka), produce red pigments, and are widely used as natural coloring agents in the food field. The Monascus pigment-producing bacterium produces a poorly water-soluble or water-insoluble alcohol-soluble pigment mainly composed of Monascorbrin and rubropunctatin. However,
This Monascus dye alone is inferior in light resistance and heat resistance,
In addition to a large hue difference due to H, it could not be used in cosmetics because it bleeds with water, sweat or other cosmetics.

[0003] Japanese Patent Publication No. 5-59885 discloses that in order to improve such disadvantages of natural dyes, a coloring pigment obtained by mordant dyeing a regenerated fibroin powder with a Monascus dye previously modified to be water-soluble is prepared. It has been proposed to be incorporated into cosmetics.

[0004]

However, the pigment disclosed in the above publication is obtained by mordant dyeing using a water-soluble aluminum salt as a mordant, and it is necessary that the Monascus dye used be water-soluble. And in order to make the Monascus pigment water-soluble, a water-soluble amino compound,
For example, it is necessary to previously denature the Monascus dye into a water-soluble complex using a water-soluble protein, peptide, amino acid, or the like, which has a disadvantage of increasing the number of steps. Furthermore, in the case of the water-soluble Monascus dye, the cyclic ether moiety, which is the affinity group of the compounds such as Monascorbrin and rubropunctatin, which constitutes the Monascus dye, has already been bonded to the water-soluble amino compound. The chemical affinity with the amino group of fibroin powder is low. Therefore, it is difficult for the resulting fibroin pigment bound with the water-soluble Monascus dye to sufficiently improve the bleeding resistance.

[0005]

Means for Solving the Problems The present inventors have intensively studied to improve the above-mentioned drawbacks of the prior art, and as a result, found that poorly water-soluble or water-insoluble Monascus dye obtained by culturing Monascus dye-producing bacteria belonging to the genus Monascus. Pigment obtained by adding regenerated fibroin powder under alkaline conditions of pH 8 or more to an alcohol in which is dissolved, and combining the Monascus pigment with the regenerated fibroin powder has good durability (bleed resistance, light resistance, heat resistance). And a sufficient color tone, the gloss, the feel and the moisturizing property are superior to those of the fibroin itself, and a pigment which is safe for the human body can be obtained economically. Further, the makeup cosmetics containing the above pigment of the present invention have bleed resistance, moisture retention, adhesion, extensibility,
The present invention was found to be excellent in color tone and to give a moist feeling and a silky feeling to the skin, and to obtain a stable makeup effect, thereby completing the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The water-insoluble or water-insoluble alcohol-soluble Monascus pigment used in the present invention is obtained by culturing a Monascus pigment-producing bacterium in a medium. As the culture medium, a culture medium containing a known and commonly used saccharide or the like as a main component can be used. Examples of such sugars include glucose, fructose, sucrose, maltose, dextrin,
Starch and the like can be exemplified. Further, the medium may contain a nitrogen source, minerals and vitamins, and examples of such other medium components include nitrogen sources such as ammonium sulfate, ammonium nitrate and potassium nitrate, potassium phosphate, magnesium sulfate, and chloride. Minerals such as potassium and ferrous sulfate, and vitamins such as yeast extract can be exemplified.

The temperature and pH of the medium can be selected from known conditions, for example, about 20 ° C. to about 40 ° C. and pH about 4 to about 8. The culture time is usually about 48 to about 120.
About an hour. Culture is performed under aerobic conditions, usually
A liquid culture method is adopted. Extraction of pigment from cells
A water-soluble organic solvent such as alcohol can be used, and it can be efficiently extracted in 5 to 20 times the amount of cells.

[0008] The water-insoluble or water-insoluble alcohol-soluble Monascus dye obtained by the above method contains about 10 or more types of dyes. Includes Ankaflavin, orange-red rubropunctatin, monascorbrin, red-purple monascorbramine, rubropanctamine.

The regenerated fibroin powder referred to in the present invention is a regenerated fibroin in the form of fine powder which is regenerated (precipitated) by coagulating an aqueous solution of silk fibroin. The method for preparing such regenerated fibroin powder is disclosed in, for example, Japanese Patent Publication No. 58-38449. According to this, copper-ethylenediamine aqueous solution, copper hydroxide-ammonia aqueous solution, copper hydroxide-alkali-glycerin aqueous solution, lithium bromide aqueous solution, calcium or magnesium or zinc chloride or nitrate or thiocyanate aqueous solution, sodium thiocyanate After dissolving silk fibroin in at least one solution selected from the group consisting of aqueous solutions, mixing a coagulable salt into a 3 to 20% by weight aqueous fibroin solution obtained by dialysis, blowing air, isoelectric coagulation, ultrasonic treatment Regenerated fibroin powder is obtained by coagulating and depositing fibroin by at least one method such as stirring at a high shear deformation rate, followed by dehydration, drying and pulverization. Fibroin obtained by this method has an average molecular weight of 50,000 or more, is non-fibrous, has a molecular orientation of 1/2 or less of natural silk thread, and has a bulk density of 0.1 to 0.7 g when dried. / Cm ³
And at least 50% by weight of heat-insoluble silk fibroin (β structure). The recrystallized degree of the regenerated fibroin powder used in the present invention is preferably from 10 to 35%, more preferably from 15 to 30%, from the viewpoint of color tone and feel of the compounded cosmetic. The average particle size of the regenerated fibroin powder is 1 from the viewpoint of dispersibility when blended into a makeup cosmetic, familiarity with the skin, and smoothness.
It is preferably adjusted to 100 μm, and particularly preferably adjusted to 5 μm to 30 μm.

[0010] Another regenerated fibroin powder used in the present invention is prepared by the method disclosed in Japanese Patent Publication No. 63-97711 by adding a suspension of the regenerated fibroin powder as described above to the regenerated fibroin powder. A method of mixing 0.5 to 100% by weight of N, N'-dialkylaminoethyl methacrylate and reacting the acrylate at about 30 to 100 ° C in the presence of about 0.1 to 10% by weight of a radical polymerization catalyst. Is obtained by
For example, a regenerated fibroin powder in which a polymer of N, N'-dialkylaminoethyl methacrylate is fixed at about 20% by weight or 50% by weight can be preferably exemplified (hereinafter, referred to as a DM-treated product in the present invention). As these regenerated fibroin powders, commercially available ones can also be used. For example, Silk Powder I
Commercially available products such as M (regenerated fibroin powder) or DM-silk powder (an N, N'-dialkylaminoethyl methacrylate polymer is fixed at about 20% by weight) (all manufactured by Kanebo Silk Elegance). .

The formation of the complex between the hardly water-soluble or water-insoluble alcohol-soluble Monascus pigment and the regenerated fibroin powder is carried out by extracting the regenerated fibroin powder from the cultured cells as described above by extracting the Monascus pigment with an alcohol solvent. PH8.
It can be formed by stirring under alkaline conditions of 0 or more for 1 to 4 hours. The conjugate may be separated by centrifugation or suction filtration, and if necessary, washed with water and dried to obtain a Monascus dye-bound fibroin powder.

The water-insoluble or water-insoluble and alcohol-soluble Monascus pigment of the present invention is not only soluble in alcohol, which is an extractant after cultivation, but also solidified by adding a drying step to the extract to alcohol again. Dissolved ones can also be used. Then, the binding between the Monascus pigment and the regenerated fibroin powder is performed using an alcohol under an alkaline condition of pH 8.0 or more, and preferably under a pH condition of 9 to 11. Examples of the alkali used to adjust the pH under such pH conditions include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, and the like. In the system in which the Monascus pigment is combined with the regenerated fibroin powder in the present invention, ethyl alcohol is used as the alcohol.If necessary, other alcohols such as methyl alcohol, iso-propyl alcohol, n-propyl alcohol, N-butyl alcohol and the like can also be used. Further, the use of alcohol containing water of 95% by weight or less can also be exemplified.

The amount of the monascus pigment-bound fibroin pigment in the makeup cosmetic of the present invention is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, based on the total weight of the components. %. Also,
The makeup cosmetic of the present invention may further contain other coloring inorganic pigments or organic pigments as required in addition to the above-mentioned monascus dye-binding fibroin pigment. Further, the base compounded in the makeup cosmetic of the present invention is not particularly limited, and is a base of a commonly used makeup cosmetic such as an extender, an oily substance, and a fragrance. Examples of the makeup cosmetics referred to in the present invention include lipstick, lip balm, eyeshadow, blush, foundation, mascara, nail color and the like.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments. The percentages shown in the examples are percentages by weight except for the degree of crystallinity.
Means The test methods of the bleed resistance and light resistance of the Monascus dye-bound fibroin pigment of the present invention and the practical test (sensory test) of makeup cosmetics are as follows.

(1) Light fastness test Three samples were prepared, one was housed in a sunshine box (glass case) and exposed to direct sunlight for three days, and one was placed under a fluorescent lamp. After exposure for 2 weeks, the remaining one was stored in a dark place as a non-exposed sample, and the color of the sample after irradiation was compared with that of the unexposed sample by visual observation to determine the light fastness from the degree of color change. .

(2) Heat resistance test Two samples were prepared, one was stored for 2 months and 6 months in a thermostat adjusted to an internal temperature of 40 ° C, and one was stored in a cool and dark place (5 ° C) for 2 months. After 2 months and 6 months, the colors of the sample at 40 ° C. and the temperature in a cool and dark place (5 ° C.) were compared with the naked eye, and the heat resistance was determined from the degree of color change.

(3) Bleed resistance test 1 g of a sample was weighed with 100 g of water / ethyl alcohol (1: 1).
Disperse in the mixed solution and heat-treat in 70 ° C. hot water for 1 hour.
The degree of elution of the dye into the water / ethyl alcohol mixture was visually evaluated, and 1 ml of the supernatant was accurately taken up to 10 ml, and the absorbance at 490 nm was measured.

The light resistance, heat resistance and bleed resistance (visual observation) were evaluated according to the criteria shown in Table 1.

[0019]

[Table 1]

(4) Practical test The make-up cosmetic samples were used for two months, and their color tone, adhesion to skin, touch, transparency to skin, gloss, and extensibility were evaluated by 30 female panelists. It was evaluated by a test (practical test).

Example 1 (Monascus dye-bound fibroin pigment of the present invention) Glucose 5%, dipotassium phosphate 0.8%, potassium nitrate 0.2%, sodium chloride 0.1%, magnesium sulfate 0.05%, yeast PH consisting of 0.05% extract
15 liters of 6.0 medium is placed in an 80 liter yeast tank and sterilized at 121 ° C. for 20 minutes. After cooling, this was inoculated with 3% of a seed of Monascus purpureus IF04518, and cultured at 30 ° C. for 96 hours at aeration rate of 10 liter / min, stirring at 250 rpm and back pressure of 0.3 kg / cm ² .
Next, the culture solution was centrifuged to obtain 600 g of bacterial cells (water content of 70 g).
%). 300 g of 95% ethyl alcohol was added to 30 g of the cells, and the mixture was stirred and extracted at room temperature for 1 hour to obtain a Monascus pigment extract. The Monascus pigment in this extract was sparingly soluble in water, but soluble in ethyl alcohol. Next, 500 g of regenerated fibroin powder (crystallinity 30%) was added to the dye extract, and the pH was adjusted to 9.5 to 10.0 with a 30% aqueous sodium hydroxide solution. After stirring for 2 hours, the mixture was adjusted to pH 6.5 with 2N hydrochloric acid, filtered by suction, and the solid was washed with water and dried to obtain 503 g of a monascus dye-bound fibroin pigment of dark reddish brown.

Example 2 (Monascus dye-bound fibroin pigment of the present invention) To 30 g of the cells obtained in Example 1 was added 200 g of 95% ethyl alcohol, and the mixture was stirred and extracted at room temperature for 1 hour, and 195 g of Monascus dye extract was obtained. Obtained. The Monascus pigment in this extract was sparingly soluble in water, but soluble in ethyl alcohol. Next, 100 g of regenerated fibroin powder (crystallinity: 10%) was added to this extract, and the pH was adjusted to 10.5 with a 30% aqueous sodium hydroxide solution.
After stirring at 1 ° C. for 1 hour, the pH was adjusted to 6.5 with 2N hydrochloric acid, followed by suction filtration, and the solid content was washed with water and dried to obtain 101 g of a dark reddish brown Monascus dye-bound fibroin pigment.

Example 3 (Monascus Dye-Binding Fibroin Pigment of the Present Invention) N, N 'was added to the Monascus dye extract obtained in Example 2.
-300 g of silk powder (DM-silk powder, manufactured by Kanebo Silk Elegance) having about 20% of a polymer of dialkylaminoethyl methacrylate fixed thereto was added, and the pH was adjusted to 10.0 with a 30% aqueous sodium hydroxide solution. After stirring at ℃ for 1 hour, pH was adjusted with 2N hydrochloric acid.
The mixture was adjusted to 6.5 and then suction-filtered, and the solid content was washed with water and dried to obtain 301 g of a dark reddish-brown Monascus dye-bound fibroin pigment.

Comparative Example 1 (Fibrin pigment bound to monascus dye by mordant treatment) Based on Example 1 of JP-A-56-65049, sodium glutamate, a water-soluble amino acid compound, was added to a slightly water-soluble Monascus dye to bind to glutamic acid. Monascus water-soluble dye was produced. Next, Tokuho 5-59
No. 885, 150 g of this water-soluble Monascus dye was dissolved in 20 l of water and 3
A 0% aqueous sodium hydroxide solution was added to adjust the pH to 11, and this was used as a dyeing liquor. 500 g of regenerated fibroin (crystallinity: 31%) was dispersed in this dyeing liquor.
After dyeing for an hour, 50 ml of a 10% aqueous solution of aluminum ammonium alum was added, and mordant treatment was performed at 70 ° C. for 30 minutes. After mordant, 4N hydrochloric acid was added to adjust the pH to 5, filtered, washed with water and dried to obtain a red-brown Monascus dye-bound fibroin pigment.

The contents of the monascus dye-bound fibroin pigment obtained in Examples 1 to 3 and the monascus dye-bound fibroin pigment obtained by mordant treatment obtained in Comparative Example 1 are summarized in Table 2 below.

(1) Outline of the above various fibroin pigments

[0027]

[Table 2]

Eight kinds of samples (samples 1 to 8) obtained by blending the above-mentioned fibroin pigments with the compositions of oily and powdery makeup cosmetics shown in Tables 3 and 4 below were tested by the above-mentioned evaluation test method. And the test results shown in Tables 5 to 8 below were obtained. In addition, the bleeding resistance evaluated the bleeding property of the fibroin pigment itself.

(2) Composition of makeup cosmetics 1) Oily makeup cosmetics (samples 1 to 4)

[0030]

[Table 3]

2) Powder makeup cosmetic (samples 5 to 5)
8)

[0032]

[Table 4]

(3) Test results 1) Bleed resistance (index is a numerical value when the absorbance of Example 1 is 1.0)

[0034]

[Table 5]

By visual observation of the test results, Examples 1 to
The supernatant of Example 3 was slightly reddish purple and transparent, and the supernatant of Comparative Example 1 was dark reddish purple. From these visual observations and evaluation of the absorbance, the fibroin to which the poorly water-soluble Monascus dye of Examples 1 to 3 was bound was used. The pigment was superior in bleed resistance to the fibroin pigment in which the water-soluble Monascus dye of Comparative Example 1 was mordanted.

2) Light fastness

[0037]

[Table 6]

[0038]

[Table 7]

3) Heat resistance

[0040]

[Table 8]

Example 4 (lipstick of the present invention) 47 parts (hereinafter referred to as "parts by weight") of castor oil, 4 parts of carnauba wax,
A mixture of 7 parts of candelilla wax, 7 parts of solid paraffin, 10 parts of lanolin, and 15 parts of octyldodecanol was mixed at 80 ° C.
After heating and melting, the Monascus dye-bound fibroin pigment of the present invention (Example 1) was added to the molten mixture in an amount of 1%.
After adding 0 parts and uniformly kneading, it was melted again, poured into a mold, and cooled to obtain a lipstick of the present invention. The obtained lipstick did not show any change in color tone in the above-mentioned light resistance test (3 days in direct sunlight, 2 weeks in fluorescent light), and a heat resistance test (40 ° C. × 2)
(6 months, 40 ° C. × 6 months), there was no change in color tone. In addition, when the above-mentioned practical test was performed on this lipstick, most of the panelists found that the color tone, adhesion, touch (moist feeling, silky touch), moisture retention, lip transparency, gloss,
The extensibility was evaluated as good. On the other hand, Embodiment 4
A lipstick using the fibroin pigment mordanted with the water-soluble Monascus dye obtained in Comparative Example 1 instead of using the fibroin pigment to which the poorly water-soluble Monascus dye of Example 1 was bound was obtained in the same manner. In practical tests, more than half of the lipsticks were evaluated as having good color tone, adhesion, touch (moist feeling, silky touch), moisturizing, lip clarity, gloss, and extensibility. A large change in color tone was observed in the sex test (3 days in direct sunlight, 2 weeks in fluorescent light).

[0042]

Industrial Applicability The fibroin pigment and makeup cosmetic of the present invention are excellent in bleed resistance, light resistance, heat resistance, moisture retention, adhesion, and extensibility, and have a silky luster and feel (moist feeling, Silky touch), also gives a sense of transparency,
A stable makeup effect can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takamasa Hirai 335 Karuku, Nakahara-ku, Kawasaki-shi, Kanagawa Pref.

Claims (2)

[Claims] 1. A Monascus pigment which is obtained by culturing a Monascus pigment-producing bacterium belonging to the genus Monascus and dissolving a slightly water-insoluble or water-insoluble Monascus pigment in an alcohol and adding a regenerated fibroin powder under alkaline conditions of pH 8 or more. And a regenerated fibroin powder. 2. A makeup cosmetic containing the fibroin pigment according to claim 1.