JPS6137715A - Makeup cosmetic - Google Patents

Abstract

PURPOSE:The titled cosmetic, obtained by incorporating a regenerated fine fibroin powder, dyed with an acid dye, and having a specific crystallinity as a coloring pigment with other components, and having a low crystallinity and improved touch, dyeability and light resistance, etc. due to the porous structure of fine pores. CONSTITUTION:The titled cosmetic obtained by incorporating regenerated fine fibroin powder, dyed with an acid dye, and having 10-40% crystallintity as a coloring pigment with other components. The regenerated fine fibroin powder having 10-40% crystallinity is obtained by, e.g. dissolving silk (fibroin) in 20- 70wt% aqueous solution of a metal salt, e.g. copper-ethylenediamine or copper hydroxide-ammonia, at 70-85 deg.C, dialyzing the resultant solution, mixing a coagulating salt, blowing air, etc. to the resultant aqueous fibroin solution to coagulate and deposit the fibroin, and drying the resultant fibroin. The makeup cosmetic has better touch to the skin, dyeability, light resistance, bleeding resistance, humectant property and perfurm fixation property.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a makeup cosmetic containing fine powder of regenerated fibroin dyed with an acid dye as a coloring pigment. More specifically, the present invention relates to a makeup cosmetic that does not cause skin irritation, has excellent light resistance, bleed resistance, moisturizing properties, and fragrance retention, and is capable of imparting a silk-like luster and feel.

(Prior technology) Conventionally, acid dyes have been made water-insoluble using precipitants such as aluminum sulfate or zirconium sulfate, and have been incorporated into makeup cosmetics as dye lakes that have been adsorbed onto alumina. It was inferior in properties such as elasticity, moisture retention, fragrance retention, and adhesion, and also had problems in terms of feel.

Silk powder is a fine silk powder obtained by crushing silk fibers, and has a high degree of crystallinity (approximately 50 to 60%).
Relatively low dyeability. Make-up cosmetics containing silk powder dyed with acid dyes have low light resistance and have the disadvantage of giving the skin a hard, strange feel.
- (Problems to be Solved by the Invention) The object of the present invention is to create a makeup that does not irritate the skin, has excellent light fastness, bleed resistance, moisturizing properties, and fragrance retention, and can impart a silky luster and feel. Our goal is to provide cosmetics.

(Means for solving the problem) The first method is to use makeup cosmetics that are colored with a coloring pigment obtained by dyeing fine powder of regenerated fibroin having a crystallinity of 10 to 40% with an acid dye. achieved.

Regenerated fibroin as used herein refers to fibroin that is regenerated (precipitated) by coagulating the water-soluble edge of silk (ibroin), and fine powder of regenerated fibroin refers to regenerated fibroin in fine powder form. It is fibroin.

Examples of fine powder of regenerated fibroin include copper-ethylenediamine aqueous solution, copper hydroxide, ammonia aqueous solution, and copper hydroxide-alkali-glycerin aqueous solution.

Silk (fibroin) is obtained by dissolving silk (fibroin) in at least one solvent selected from the group consisting of an aqueous solution of lithium bromide, an aqueous solution of calcium, magnesium or zinc chloride or nitrate or thiocyanate, and an aqueous solution of sodium thiocyanate, and then dialyzing the solution. Fibroin is prepared by at least one of the methods described above, such as mixing a coagulating salt into a 3 to 20% by weight aqueous fibroin solution, blowing air, isoelectric focusing, ultrasonication, and stirring at a high shear deformation rate. Solidification and precipitation followed by dehydration 1. It is obtained by grinding after drying.

゛Preferable conditions for producing fine powder of regenerated fibroin with a crystallinity of 10 to 40% for use in the present invention are as follows.

First, the concentration of the aqueous solution of the metal salt as a solvent for dissolving fibroin is 20 to 700 to 70% by weight.

The temperature when dissolving the refined silk in the solvent is 70 to 85°C.
is preferred. The fibroin solution obtained by dissolution as described above is subjected to dialysis using a dialysis membrane such as a cellophane membrane or a dialysis machine using hollow fibers to almost completely remove the salts and the like. Concentration 3-20 obtained by dialysis
The aqueous fibroin solution containing 1% by weight causes fibroin to be coagulated and precipitated by the above-mentioned coagulation means.

As the coagulating salt, sodium chloride, sodium sulfate, aqueous ammonia sulfate, etc. are preferable.

The concentration of the coagulating salt when coagulating the fibroin aqueous solution is 5 to 1 as the concentration of the mixed solution with the fibroin aqueous solution.
0% by weight is preferred.

In the coagulation process, air is blown into the fibroin aqueous solution 1
0.11 per 1. It is desirable to blow an air amount of /; or more for 10 minutes or more.

Isoelectric point coagulation in the coagulation process is performed by adding an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid or citric acid to the fibroin aqueous solution while stirring to adjust the pH to 4.5, and then stirring the fibroin aqueous solution at room temperature. This is done by leaving it for 10 minutes or more.

The ultrasonic treatment in the coagulation treatment is performed by placing the fibroin aqueous solution in an ultrasonic generator, passing ultrasonic waves of 30 KHz or higher while stirring, and performing the ultrasonic treatment at room temperature for 1 hour or more.

Stirring at high shear deformation speed during solidification process is 100/
Stir for 1 hour or more at a shear deformation rate of 1 second or more.

When the coagulated products produced by the above-mentioned various coagulation means are centrifugally dehydrated to separate the liquid (water, etc.) and dried, a fine powder of regenerated fibroin having a crystallinity of 10 to 40% is obtained.

The crystallinity of the present invention thus obtained is 10 to 40.
% recycled fibroin fine powder has a lower crystallinity than the normal silk powder and forms a porous structure with fine pores, so it is flexible and absorbs moisture, acid dyes and fragrances well. .

It has the property of absorbing and therefore feels against the skin.

Excellent acid dye staining properties, light fastness, bleed resistance, inertia retention, and fragrance retention.

It is undesirable because it gives a feeling of tightness, and when it is higher than 40%, the light resistance decreases and it gives a hard and strange feeling to the skin, which is undesirable.

The acidic dye used in dyeing the regenerated fibroin fine powder of the present invention is a water-soluble acidic dye, such as Red No. 2 (CI Mu 16185), Red No. 3 (CI Mu 4
5430), Red No. 102 (CI A'16255)
, Red No. 104 (CIA'45410), Red No. 227 (CI Constitution 17200), Red No. 401 (C1 Constitution 451)
90), Red No. 504 (CIA14700), Yellow 4
No. (CI Mu 19140), Yellow No. 5 (CI A 15)
985), Yellow No. 203 (CIA4/7005), Yellow No. 403 (CIA10316), Blue No. 1 (CIA42
090).

Blue No. 2 (CIMU73015), Green No. 3 (CIA'
42053), Green No. 2-01 (CI Muro 1570
), Green No. 205 (C1142085), Green 40
No. 2 (C1142085), brown No. 201 (CI Ken 20
170) etc. are exemplified as preferred.

In the present invention, the fine powder of regenerated fibroin is dyed with an acid dye by dispersing the fine powder of regenerated fibroin in an aqueous acid dye solution, and adding an acid (hydrochloric acid, acetic acid, etc.) to
After adjusting it to acidic, it is heated to 70-100℃ and dyed,
Then dehydrate and wash.

This is done by drying.

In this case, the regenerated fibroin of the present invention with a crystallinity of 10 to 40% dyes evenly and clearly even if the dyeing rate is less than Remarkably superior.

The content of the coloring pigment (fine powder of regenerated fibroin dyed with an acid dye) in the makeup cosmetic of the present invention is 1 to 50% by weight, preferably 5 to 30% by weight based on the total weight of the prescription ingredients. Weight%.

The makeup cosmetics of the present invention can be colored to a desired hue with the coloring pigments, but if necessary, a small amount of coloring inorganic pigments or organic pigments can also be added.

The base used in the make-up cosmetic composition of the present invention is not particularly limited, and may be a well-known and commonly used base for make-up cosmetics, such as an inorganic pigment, an oily substance, or a perfume. The makeup cosmetics of the present invention are extremely useful as, for example, lipsticks, eye shadows, rouges, foundations, and the like.

The makeup cosmetic of the present invention has excellent light resistance, bleed resistance, moisture retention, fragrance retention, adhesion, and extensibility, and has a silk-like luster and feel (silky touch and moist, good feel). Furthermore, it can give a transparent feeling and can express and impart a stable cosmetic effect (make-up effect).

(Example) The implementation side will be explained below.

Example 1 (1) Production of colored pigment of the present invention ■ Production of fine powder of regenerated fibroin with 20% crystallinity 50% chlorination A fibroin-calcium chloride solution obtained by adding and dissolving 10 parts of refined silk to 100 parts of a calcium aqueous solution (110° C.) was cooled and desalted by dialysis using a cellulose tube. Next, 50 parts of the obtained fibroin aqueous solution with a fibroin concentration of 5% was added at a shear deformation rate of 10 at room temperature.
The fibroin was solidified by vigorous stirring for 3 hours using a 0/sec stirring device. Water is removed from the coagulated gel using a centrifugal dehydrator, dried at 105°C, and then pulverized using a jet mill to obtain the fibre-filter fine powder (of the present invention) with a crystallinity of 20%.
The particle size was 0.1 to 0.5μ). The degree of crystallinity was measured using a Geigerflex 2027 manufactured by Rigaku Co., Ltd. using a reflection concentration method (X-ray diffraction). '■ Dyeing of recycled buproin fine powder Dissolve 10 parts of acid dye yellow, No. 4 (CI^19140) in 1000 parts of water, adjust the pH to 1°5 with hydrochloric acid, and add fine fibroin powder to this aqueous solution. (Crystallinity 20%) Add 33.3 parts and disperse,
℃ for 1 hour, washed with water, and dried to obtain a colored pigment of the present invention in which fine powder of regenerated fibroin was dyed yellow. In addition, Yellow No. 4 dyed 24% (dyeing rate) of the fine powder of recycled fibroin, and the color tone as a dye (coloring pigment) was good. Its characteristics The colored pigment of the present invention (crystallinity 20% dyed with Yellow No. 4)
After uniformly mixing 5 parts of recycled fibroin fine powder), 50 parts of sericite, 20 parts of kaolin, and 15 parts of titanium oxide, this mixture was added to 10 parts of liquid paraffin and mixed,
Thereafter, it was crushed, sieved, and stamped into a mold to obtain almost rouge.

As a result of testing this almost red color as described below, the color difference value ΔE after 2 weeks of sunlight irradiation was 8.5, indicating good light resistance, and the dye residual rate was 95%, indicating good bleed resistance.

In addition, as a result of a practical test of this Habo Beni by three specialized inspectors, it was found that it had a moist and good feel on the skin,
It was observed that a smooth, natural makeup effect with silk-like luster was imparted.

Prepare two light resistance test samples of O wabo crimson, one placed in a solar box (glass case) and exposed to sunlight for two weeks, and one placed in a cool dark room for 2 weeks.
After 2 weeks of storage, the color difference ΔE was measured using a Hunter colorimeter as described below, and the degree of fading of the dye (coloring pigment) due to sunlight was determined. Hunter colorimetric system L value, a value and b○ Bleed resistance test sample 1y of Haboko was boiled in boiling water for 2 hours, and the amount of pigment was determined by measuring the absorbance of the pigment eluted into the aqueous layer. 1. Then, the dye residual rate was determined from the following formula and used as a measure of bleed resistance.

Comparative Example l Dyeing with Yellow No. 4 was carried out in the same manner as in Example 1, except that silk powder (crystallinity 50%) was used instead of recycled fibroin fine powder with a crystallinity of 20%, and the dyeing rate was as follows. The content was extremely low at 1.5%, and the color tone as a dye (coloring pigment) was also insufficient.

In addition, the color difference value △ after 2 weeks of sunlight irradiation was almost red when silk powder dyed with Yellow No. 4 was mixed in the same manner as in Example 1.
E was 21.5 and light resistance was poor.

Also, as a result of practical testing of this almost red product, it gave a hard and strange feeling to the skin.

Comparative Example 2 Instead of regenerated fibroin fine powder with a crystallinity of 20%, -
The same procedure as in Example 1 was conducted except that recycled fibroin fine powder with a crystallinity of 8% was used.

As a result, the dyeing rate of Yellow No. 4 was 30%, and the residual rate of almost red pigment mixed with this regenerated fibroin fine powder dyed with Yellow No. 4 was 62%, and the bleed resistance was poor. Also, as a result of practical testing of this almost red product, it gave an unpleasant sticky feeling to the skin.

Example 2 The same procedure as in Example 1 was carried out except that regenerated fine fibroin powder with a degree of nodulation of 10% was used instead of fine regenerated fibroin powder with a degree of nodulation of 20%.

As a result, the dyeing rate of Yellow No. 4 was high at 31%, and the bleed resistance of Almost Red, which was formulated with this fine fibroin powder dyed with Yellow No. 4, was confirmed by a practical test with a dye residual rate of 9. As a result, it gave the skin a moist and good feel and a natural makeup effect with a silky shine.

Example 3 The same procedure as in Example 1 was carried out except that regenerated fine fibroin powder with a crystallinity of 27% was used instead of fine regenerated fibroin powder with a crystallinity of 20%. As a result, the dyeing rate of Yellow No. 4 was high at 18%, and the bleeding resistance of Almost Red, which contained recycled fibroin fine powder dyed with Yellow No. 4, was good with a dye residual rate of 98%. Moreover, the light resistance of 6 trout after 2 weeks of sunlight irradiation was 6.3, which was also good. As a result of a practical test of Matato's almost beni, it gave a moist and good feel to the skin and a natural makeup effect with a silky shine.

Example 4 The same procedure as in Example 1 was carried out except that regenerated fine fibroin powder with a crystallinity of 40% was used instead of fine regenerated fibroin powder with a crystallinity of 20%. As a result, the dyeing rate of Yellow No. 4 was high at 8%, and the light resistance of the dye containing recycled fibroin fine powder dyed with Yellow No. 4 was 11.8, which was good. In addition, as a result of practical tests on this almost red,
It gave the skin a moist and good feel and a natural makeup effect with a silky shine.

Example 5 +11 Staining of recycled fibroin fine powder A recycled fibroin fine powder with a crystallinity of 30% was used as the recycled fibroin fine powder, and red 3 was used as the acid dye.
A colored pigment of the present invention was obtained by carrying out dyeing in the same manner as in Example 1, except that No. (CIA45430) was used. Note that Red No. 3 was dyed by 19% (dying rate) of the recycled fibroin fine powder, and the color tone as a pigment was good.

(2) Lipstick of the present invention and its characteristics 9 parts candelilla wax, 8 parts solid paraffin.

5 parts of beeswax, 5 parts of carnauba wax, 1 part of lanolin, 7 parts of the colored pigment of the present invention (regenerated fibroin fine powder with a crystallinity of 30% dyed with Red No. 3) are added, put on a roller, melted again, and molded. The lipstick of the present invention was obtained by pouring the lipstick into a container and cooling and molding it.

The light fastness of this lipstick, as determined by the test method described below, was 80% as a pigment residual rate, and the bleed resistance was 99% as a pigment residual rate, both of which were high and good.

Further, as a result of practical tests of this lipstick, it was confirmed that it gave a moist and good feel to the lips and could impart a good makeup effect with natural coloring and transparency.

O Lipstick light resistance test method Two lipsticks were prepared, one was placed in a sunlight box (glass case) without a cap and exposed to sunlight for two weeks, and the other one was kept blank and kept indoors (10 (1) After boiling for 1 hour, it separates into a water layer and an oil layer.
The measurement was performed using a spectrophotometer using a 1-thickness quartz cell at 30 nm (480 nm for yellow No. 5 + 635 nm for blue No. 1). In addition, the dye residual rate was quantified as the dye residual rate with respect to the blank.

Q Lipstick bleed resistance test method Boil the sample in boiling water for 2 hours, measure the absorbance of the pigment eluted into the water layer in the same manner as in the light resistance test above, quantify the amount of pigment, and determine the pigment residual rate. was searched and displayed.

Comparative Example 3 The same procedure as in Example 5 was carried out, except that silk powder (crystallinity 50%) was used instead of the regenerated fibroin fine powder with a crystallinity of 30%. As a result, the dyeing rate of Red No. 3 was extremely low at 1.6%, and the color tone as a dye (coloring pigment) was also insufficient. Furthermore, the light resistance (dye retention rate) of the lipstick containing dyed silk powder was poor at 42%. Also, in a practical test of this lipstick, it gave a hard and strange feeling to the lips.

Comparative Example 4 The same procedure as in Example 5 was carried out, except that instead of the recycled fine fibroin powder with a crystallinity of 30%, a fine recycled fibroin powder with 8% crystal dust was used. As a result, the bleed resistance of a lipstick containing regenerated fibroin fine powder dyed with Red No. 3 was poor at a pigment residual rate of 71%. In addition, when we tested this lipstick, it gave an unpleasant, sticky feeling to the lips.

Example 6 The same procedure as in Example 5 was carried out except that regenerated fine fibroin powder with a crystallinity of 10% was used instead of fine regenerated fibroin powder with a crystallinity of 30%. As a result, the regenerated fibroin fine powder dyed with Red No. 3 had a good and sufficient color tone as a coloring pigment, and the dyeing rate was high at 32%. In addition, the light resistance of the lipstick containing this colored pigment (dyed regenerated fibroin fine powder) is 9 as a pigment residual rate.
4%, and the bleed resistance was 92% as a dye residual rate, both of which were good. A practical test of this lipstick revealed that it gave a moist and pleasant feel to the lips, and provided a good make-up effect with natural coloring and transparency.

Example 7 Regeneration with 30% crystallinity? The same procedure as in Example 5 was conducted except that regenerated fine fibroin powder with a crystallinity of 20% was used instead of fine ibroin powder. As a result, the regenerated fibroin fine powder dyed with Red No. 3 had a good and sufficient color tone as a coloring pigment, and the dyeing rate was high at 25%.

Furthermore, the light resistance of the lipstick containing this colored pigment was 81% as a dye residual rate, and the bleed resistance was 99% as a pigment residual rate, both of which were good. A practical test of this lipstick revealed that it gave a moist and good feel to the lips, and gave a good make-up effect with natural coloring and transparency.

Example 8 The same procedure as in Example 5 was carried out except that regenerated fine fibroin powder with a crystallinity of 40% was used instead of fine regenerated fibroin powder with a crystallinity of 30%. As a result, the regenerated fibroin fine powder dyed with Red No. 3 had a good and sufficient color tone as a coloring pigment, and the dyeing rate was high at 20%. Furthermore, the light resistance of the lipstick containing this colored pigment was 74% as a dye residual rate, and the bleed resistance was 99% as a pigment residual rate, both of which were good. A practical test of this lipstick revealed that it gave a moist and good feel to the lips, and gave a good make-up effect with natural coloring and transparency.

Example 9 4 parts of regenerated fibroin fine powder (crystallinity 20%, dyeing rate 15%) dyed with Blue No. 1 (CI 142090) and regenerated fibroin fine powder dyed with Yellow No. 4 (crystallinity 20%, 2 parts (dyeing rate 24%) and yellow No. 5 (CIA159)
Regenerated fibroin fine powder (crystallinity 2) stained with
0%, dyeing rate 27%) 3.3 parts, 30 parts of mica, and 47.7 parts of sericite were mixed into a molten mixture of 6 parts of squalane, 3 parts of lanolin, and 4 parts of myristic acid. After adding carbon, stirring and pulverizing, the mixture was cast into a mold to obtain an eye shadow of the present invention.

A practical test of this eyeshadow revealed that it had good adhesion to the eyelids and provided a good makeup effect with a natural finish.

Claims (1)

[Claims] A makeup cosmetic colored with a colored pigment obtained by dyeing fine powder of recycled fibroin with an acid dye having a crystallinity of 10 to 40%.