JPH0678212B2 - Makeup cosmetics - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to the use of a colored pigment (colorant) obtained by mordanting porous silk fibroin powder with a specific natural dye using a water-soluble aluminum salt as a mordant. The present invention relates to makeup cosmetics improved by.

(Prior Art) Coal tar-based dyes that have been widely used in cosmetics are
Since the carcinogenicity, mutagenicity, and other harmful effects on the human body have become a problem, the amount of legal dyes permitted for use in cosmetics tends to decrease year by year. Natural pigments are a highly safe pigment (coloring agent) that can replace coal tar pigments.
Natural dyes are inferior in light resistance and heat resistance, have a large variation in hue depending on pH, and cannot be used in makeup cosmetics because they bleed.

JP-B-55-46367 discloses dyeing by immersing silk powder (silk powder) in an alkaline aqueous solution in which the natural dye cursamine (safflower dye) is dissolved in order to improve the drawbacks of the natural dye. After that, it is disclosed that a pigment in which carsamine is fixed and insolubilized is formed with an organic acid, and the pigment is mixed with an oily cream.

However, the silk powder that forms the base of this pigment has a very high crystallization rate of 50 to 60%, so that it is difficult to dye it in dark color even with cursamine, and the cursamine itself has poor light resistance and heat resistance. In addition to being sufficient, it has a low affinity with silk and is likely to fall off due to friction in the coexistence of an oily substance or during application of a mixed cosmetic composition. This tendency is found not only in carsamine but also in other natural pigments as described below, and it is difficult to dye in a dark color and to sufficiently improve light resistance, heat resistance, bleed resistance, color tone, etc. there were.

Silk fibroin powder, especially regenerated silk fibroin powder,
Its moderate hygroscopicity and moisturizing properties, excellent affinity for skin, good hydrophilic-lipophilic balance, and further UV absorption properties, etc., have been conventionally used mainly as makeup cosmetic bases. (Japanese Patent Publication No. 58-38449).

Further, by utilizing the above-mentioned preferable properties of silk fibroin as a raw material for cosmetics, the adhesiveness, extensibility, and dispersion formed by substantially covering the particle surface of a general cosmetic pigment with a regenerated silk fibroin film. Properties, miscibility, coating properties, oil absorption, balance of hydrophilicity and lipophilicity, antiperspirant properties, touch,
Japanese Patent Publication No. 57-11577 proposes a pigment for cosmetics which is remarkably excellent in skin protection and dyeability and a method for producing the same.

However, although these regenerated silk fibroin pigments are excellent in dyeability and aroma retention compared with conventional general pigments, practically, these regenerated silk fibroin pigments are dyed with a natural dye. The make-up cosmetics colored with the coloring pigment to be applied were not satisfactory in light resistance, heat resistance, bleed resistance and color tone.

In addition, in JP-A-59-10507, there is described a cosmetic composition containing a pigmented powder of Sikon extract dye as a method related to a method of pigmentizing a dye using silk powder. This method is nothing more than an application of the mordant dyeing method with natural pigments of silk fiber, which has been used since ancient times, to powders. It dyes only a little, at most, in a pale color, and the pigment content generally required as a coloring pigment is 5% or more, preferably 10%.
As mentioned above, more preferably, only those far from the level of 20% or more can be obtained.

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies as an ameliorator for ameliorating the drawbacks of the prior art, and as a result, (1) the porous silk fibroin forming the base of the coloring pigment of the present invention is the starting material silk or ordinary silk. It is significantly different chemically and physically from regenerated silk fibroin in terms of morphology and physical properties. For example, the affinity and adsorption (dyeability) of the specific natural pigments described below are higher, and it develops more vivid colors and is good. It should give a color tone and be superior in gloss, feel and moisturizing property to that of silk itself.

(2) The specific natural pigment described below dyed on porous silk fibroin is well adapted to the water-soluble aluminum salt, chelates by its mordant effect (effect), chemically stabilizes, and has better light resistance. Being able to impart heat resistance, bleed resistance, and color tone.

(3) Since the porous silk fibroin of the substrate and the dye constituting the color pigment of the present invention are both natural products, the color pigment is harmless to the human body and safe.

(4) Make-up cosmetics containing the coloring pigment of the present invention are extremely excellent in light resistance, heat resistance, bleed resistance, and color tone, and also have makeup lasting properties (water resistance, sweat resistance, adhesion to the skin),
It should have a good feel (extendability, moisture retention), etc., and be able to impart and develop a beautiful and stable cosmetic effect (make-up effect).

As a result, the present invention has been completed.

(Object of the invention) That is, the object of the present invention, the human body is safe and without skin irritation,
Excellent in light resistance, heat resistance, bleed resistance, and color tone.
An object of the present invention is to provide a makeup cosmetic having improved makeup stickiness (water resistance, sweat resistance, adhesion to skin), touch (extendability, moisture retention) and the like.

(Structure of the Invention) The present invention comprises regenerated silk fibroin in the form of fine powder or regenerated silk fibroin containing a base pigment, and at least 50% by weight of the silk fibroin is hydrothermally insoluble (β
Type) and has pores with a diameter of 1μ or less 300μ /
Porous silk fibroin powder containing more than g, using water-soluble aluminum salt as a mordant, Suho pigment, gardenia pigment, saffron pigment, madder pigment, cacao pigment, yellowfin pigment, cochineal pigment, lac pigment, purple root pigment, ende pigment, monascus pigment A makeup cosmetic that is colored with a coloring pigment obtained by mordanting with a natural pigment selected from the group consisting of pigments and dyes.

(Detailed Description of Configuration) The porous silk fibroin powder according to the present invention is prepared by mixing a water-insoluble carbonate fine particle in a silk fibroin aqueous solution or a suspension of the fine particle and a base pigment with a coagulating salt. And / or a regenerated silk fibroin coarse particle covering the fine particles or the base pigment with the fine particle or the base pigment is formed by performing a stirring treatment at a high shear deformation rate, and then a water-insoluble carbonate is decomposed and eluted by an acid treatment to generate carbon dioxide gas. Then, it is obtained by washing with water, drying and pulverizing.

The porous silk fibroin powder has a structure in which regenerated silk fibroin or a complex of a base pigment and regenerated silk fibroin has innumerable fine pores, the amount of which is 300 μ / g in pores having a pore diameter of 1 μm or less. Or more, preferably 400μ
/ g or more, more preferably 600 μ / g or more.

Normal powdered regenerated silk fibroin or silk thread that is embrittled by chemical treatment is crushed, but the mere fibrous silk fibroin powder has a void (Void: micropore) amount of 200 μ / g at most. Then, in the case of the porous silk fibroin pigment according to the present invention, the amount of fine pores is remarkably large, and therefore, for example, in a mordant dyeing of a natural dye or the like, a colored silk fibroin pigment having a very dark color, water resistance, and light fastness is good. Can be obtained.

The reason why the porous silk fibroin powder of the present invention significantly increases and improves the dyeing amount and the fastness of the dye with the increase in the amount of fine pores is not clearly understood, but probably the high adsorption performance of activated carbon is
It is considered that the same principle is caused by the large amount of fine pores.

The porous silk fibroin powder of the present invention is at least 50% by weight, preferably 80% by weight or more of the regenerated silk fibroin,
More preferably, at least 90% by weight is composed of hot water-insoluble fibroin (β type structure). If the amount is less than 50% by weight, the hydrophilicity of fibroin becomes extremely strong, and the particles become secondary particles (particles agglomerate into huge particles) by sticking or caking with water or sweat, and water. The detachment of the film is likely to occur in the dispersion medium (water-based cosmetics), and the dispersibility is likely to be reduced in the oil dispersion medium (oil-based cosmetics). In addition, the elongation and feel during application become poor.

In the present invention, the hot water-insoluble fibroin is a so-called fibroin that does not dissolve even if it is boiled in hot water at 100 ° C. for 15 minutes.

The hot water-insoluble fibroin has an intermolecular hydrogen bond of fibroin substantially having a β structure.

Although the crystallinity of regenerated fibroin varies slightly depending on the conditions of the manufacturing process, it is usually 10% or more, preferably 20%.
It will not exceed 43%. This is considerably lower than the crystallinity of silk fibers (50% or more), and the degree of molecular orientation is also less than half that of silk fibers. This point is considered to be the reason why regenerated silk fibroin gives a more preferable effect as a cosmetic base rather than simply modified silk fibroin.

The base pigment in the porous silk fibroin powder of the present invention is a general term for white pigments for cosmetics, extender pigments, pearl pigments, etc., for example, talc, kaolin, mica, titanium oxide, zinc oxide, titanium mica, or Those compounds may be mentioned, and one kind or a combination of two or more kinds is applied. The maximum particle size of the base pigment is usually 0.03 to 20μ.

In the present invention, the base pigment is 0 for regenerated silk fibroin.
Is 4 times (weight), preferably 0 to 2 times (weight), and more preferably 0 to 1 times (weight).

The maximum particle size of the porous silk fibroin powder of the present invention is usually 0.
5-100μ, preferably 1-60μ, particularly preferably 3-30
is μ. If the maximum particle size is larger than 100 μ, the adhesion to skin, affinity, extensibility, etc. tend to deteriorate.

As the silk fibroin raw material applied to the present invention, eyebrows, raw silk, eyebrows scraps, raw silk scraps, screws, fried cotton, silk cloth scraps, burettes, etc., in the presence of an active agent, if necessary, according to a conventional method, in warm water or with an enzyme. Using refined silk obtained by removing sericin in warm water in the presence of water and dissolving it, for example, it is dissolved by the method described in JP-B-58-38449, but as a solvent, cost, and calcium or magnesium or zinc from the viewpoint of use. Aqueous solutions of hydrochlorides or nitrates are preferred. The concentration of these aqueous solutions varies depending on the type of solvent used, temperature, etc., but the concentration of metal salts and the like is usually 10 to 80% by weight, preferably 20 to 70% by weight, and particularly preferably 25 to 60% by weight.

The fibroin concentration of the aqueous fibroin solution used in the present invention is usually 2 to 20% by weight, preferably 4 to 15% by weight, particularly preferably 5 to 10% by weight.

If it is less than 2% by weight, the regeneration time of the aqueous fibroin solution is long, which is uneconomical. On the other hand, if it exceeds 20% by weight, it may be difficult to dehydrate the porous fibroin powder in the washing and drying steps. Further, in both of the above ranges, regenerated fibroin having a low proportion of hot water-insoluble fibroin (β structuring rate), sticking in sweat or a water dispersion medium, or easily forming secondary particles is likely to be produced.

The suspension applied to the method of the present invention is prepared by dissolving at least one of calcium, magnesium or zinc hydrochloride or nitrate in an aqueous silk fibroin solution, and adding a water-soluble carbonate to the solution to obtain calcium, magnesium or zinc. The carbonate may be precipitated as water-insoluble fine particles, and a preferable dissolving salt as a solvent for the silk fibroin raw material is
Since it happens to be a raw material of the water-insoluble carbonate, the amount of the calcium-, magnesium-, or zinc-hydrochloride or nitrate calculated from the predetermined amount (approximately equivalent amount) of the water-insoluble carbonate to be included in the coarse particles as the intermediate is used for silk. The fibroin raw material may be dissolved and used as it is in the next step without desalting. However, it is more preferable that the aqueous solution of silk fibroin is dialyzed and desalted to completely remove the hydrochloride or nitrate used for dissolving the silk fibroin raw material. By dialysis, low molecular weight silk fibroin, which is originally contained or generated when dissolved, reduces the performance of the product as a base material for cosmetics, or when dyeing, especially when dyeing with a natural quinone pigment Therefore, it is possible to completely remove the iron ions and the like mixed from the raw materials and the reaction system. In this case, when the water-insoluble carbonate is produced in the reaction system, it is necessary to add a predetermined amount of the above-mentioned hydrochloride or nitrate.

When a base pigment is also used in combination, the base pigment can be suspended in a suspension to undergo a predetermined process to obtain a porous silk fibroin pigment including the coating.

Examples of the above-mentioned water-soluble carbonate include sodium carbonate and ammonium carbonate. The reaction between the hydrochloride or nitrate and the readily water-soluble carbonate occurs instantaneously under stirring, and water-insoluble carbonate fine particles are precipitated.

At least one kind of treatment such as mixing of the coagulating salt or stirring at a high shear deformation rate of 50 / sec or more is performed on the silk fibroin aqueous solution in which the fine particles or both the fine particles and the base pigment are suspended, To play. The regenerated coarse particles of silk fibroin are fine particles of water-insoluble carbonate or a coarse-particle gel body containing both the fine particles and the base pigment as a coating. The coarse-grained gel body is the same as the silk fibroin aqueous solution in which the dialysis desalted and purified silk fibroin aqueous solution has an average particle size of 1 μm or less, preferably 0.1 μm or less, or light calcium carbonate or both thereof and a base pigment are suspended. It can also be reproduced by the method.

The amount of fine carbonate particles in the coarse particles is preferably 20 to 80% by weight of the coarse particles, and more preferably 30 to 70% by weight. 20% by weight
When it is less than 1, the micropore amount tends to decrease, while when it exceeds 80% by weight, the micropore amount of 1 μ or less tends to decrease and the micropore amount of 1 μ or more tends to increase.

When a coagulating salt is used, silk fibroin is precipitated by mixing and stirring concentrated aqueous solutions of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate and the like. The concentration of the coagulable salt is adjusted so that the concentration of the mixed solution with the silk fibroin aqueous solution is usually 5 to 10% by weight.

Although silk fibroin is precipitated only by stirring, in this case, it should be performed at a high shear deformation rate and usually at a shear deformation rate of 50 / sec or more, preferably 100 / sec or more. The stirring time varies depending on the concentration of the aqueous solution, the shear deformation rate, etc., but the gelation is usually performed for 1 hour or more.

The intermediate silk fibroin coarse particles are washed with excess water, dried in some cases, coarsely pulverized and then acid-treated to decompose the carbonate fine particles. Although hydrochloric acid, acetic acid or citric acid is suitable as the acid, it should be noted that sulfuric acid may form a sparingly water-soluble sulfate. It is desirable that the amount of the acid is equivalent to the amount of the carbonate contained in the coating to a slight excess, but if the pH is set to 1 or less, the silk fibroin may become brittle and must be avoided. The completion of acid decomposition can be confirmed by the end of the generation of carbon dioxide, and then the obtained porous silk fibroin powder is washed with water and dehydrated. For dehydration, it is preferable to use a centrifugal dehydrator, and this dehydration usually dehydrates the porous silk fibroin powder to about 100 to 500% by weight based on the dried product. After dehydration, it can be easily dried to an absolutely dry state. Drying is performed at a temperature of 60 to 120 ° C. under normal pressure or reduced pressure.

The dried product thus obtained is easily made into fine powder by using a crusher such as a hammer mill or a jet mill. The particle size (maximum particle size) is usually adjusted to 0.5 to 100 µ, preferably 1 to 60 µ, and particularly preferably 3 to 30 µ.

The thus obtained porous silk fibroin powder of the present invention is such that at least 50% by weight of the regenerated fibroin is composed of hot water-insoluble fibroin. Hot water insolubilization (ratio of hot water insoluble fibroin,
The β structuring rate) can be further promoted (increased), and the above characteristics can be further improved.

As the moist heat treatment, the powder after drying or pulverization is 50
℃ or more, especially heat treatment with saturated steam of 80 ~ 120 ℃, or sodium chloride, potassium chloride before drying,
It is carried out by heating and drying in a neutral salt aqueous solution such as sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate or the like, or an organic solvent such as acetone, alcohol and the like. When these moist heat treatments are performed, promotion of hot water insolubilization of regenerated fibroin as described above (increase in β structuring rate)
Along with this, the crystallinity of fibroin can be further increased, and a good fibroin coating having an excellent balance of hydrophilicity and lipophilicity, antiperspirant properties, dispersibility in a dispersion medium, film stability, and dye fastness. A pigment is easily obtained.

In the present invention, as natural pigments for dyeing porous silk fibroin powder, Suho extract pigments, Suho pigments such as brasilin, gardenia extract pigments, gardenia pigments such as crocin, saffron extract pigments, madder extract pigments, alizarin, etc. Akane dye, cacao extract dye, cacao dye such as polyphenol, yellowfin extract dye, berberine etc. yellowfin dye, cochineal extract dye, carminic acid etc. cochineal dye, lac extract dye, laccaic acid etc. rack dye,
Examples of the dyes include purple root extract pigments, purple root pigments such as shikonin, endhu extract pigments, endu pigments such as rutin, monascus extract pigments, monascus pigments such as monascorpurin, ai extract pigments, and indigo pigments.

The mordant dyeing of the porous silk fibroin powder in the present invention is performed by immersing the porous silk fibroin powder in an aqueous solution of a water-soluble aluminum salt (mordant) and then immersing it in the aqueous solution of the natural pigment to dye it, Alternatively, the porous silk fibroin powder is dyed with an aqueous solution of the natural pigment, and then immersed in an aqueous solution of a water-soluble aluminum salt to carry out mordant treatment.

When dyeing the porous silk fibroin powder, the amount of natural pigment is 0.1 to 3 relative to the weight of the porous silk fibroin powder.
It is within the range of 0% by weight. And the dyeing temperature is usually 60-100
C, dyeing time is 1 to 3 hours. The amount of water-soluble aluminum salt (mordant) when mordanting the porous silk fibroin powder is in the range of 0.1 to 10% by weight with respect to the weight of the powder, and the mordanting temperature is 50 to 80 ° C. The mordant treatment time is 1 to 3 hours.

The amount of each aqueous solution (bath ratio) when dyeing with the above natural pigment aqueous solution and when mordanting with an aqueous solution of a water-soluble aluminum salt is usually 30 to 70 times the weight of the porous silk fibroin powder. .

Preferred examples of the water-soluble aluminum salt include aluminum potassium alum, aluminum sodium alum, aluminum ammonium alum, aluminum sulfate, aluminum acetate, aluminum chloride and the like.

As described above, the colored pigment of the present invention obtained by mordanting the fine powder of porous silk fibroin is dyed without mordanting fine powder of regenerated fibroin or fine powder of silk (silk powder) (normal dyeing). Dyeing property, color developability, color tone, light resistance, heat resistance, bleeding resistance, water resistance, sweat resistance, and adhesion to skin are superior to the above-mentioned coloring pigments.

The blending amount of the color pigment 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 ingredients.

The makeup cosmetic of the present invention can be colored in a desired hue by blending the above-mentioned coloring pigments, but a small amount of a coloring inorganic pigment or an organic pigment can be blended if necessary.

The base used in the makeup cosmetic of the present invention is a well-known and commonly used base for makeup cosmetics, such as an inorganic pigment, an extender oily substance, and a fragrance, and is not particularly limited.

The makeup cosmetics of the present invention are extremely useful as, for example, lipsticks, eye shadows, blushers and foundations.

(Effects of the Invention) The makeup cosmetics of the present invention are safe to the human body, have no skin irritation, and are excellent in light resistance, heat resistance, bleed resistance, and color tone, and also have makeup lasting properties (water resistance, sweat resistance, skin resistance). Adhesiveness), touch (extendability, moisturizing property), etc. are good, and a beautiful and stable cosmetic effect (make-up effect) can be expressed and imparted, and its commercial value is extremely high.

Examples will be described below.

In the examples,% means% by weight, and parts means parts by weight. The test methods for the light resistance, heat resistance, bleed resistance, and practical test (sensory test) of makeup cosmetics are as follows.

(1) Light resistance test Two samples were prepared, one was stored in a sunshine box (glass case) and exposed to sunlight for 3 weeks, and one was placed in a cool and dark place.
After storage for a week, both samples were compared with each other by observing the color and the naked eye, and the light resistance was judged from the degree of color change.

(2) Heat resistance test Two samples were prepared, one of which was stored in a thermostat whose internal temperature was adjusted to 50 ° C for 3 months, and one of which was stored in a cool dark place (5 ° C) for 3 months and then both samples By comparing the colors of the
The heat resistance was judged from the degree of color change.

In the light resistance test (1) and the heat resistance test, the L value, a value, and b value of the Hunter colorimetric system for each of the two samples were measured with a spectrophotometer (Murakami Color Research Laboratory). Then, the color difference ΔE was calculated from the following formula and displayed.

It should be noted that when the ΔE value (color difference value) is 5 or less, the colors of both samples look the same to the naked eye and there is no color difference, and when 5 or more and 10 or less, a slight color difference is felt, and when 10 or more and 20 or less, the color difference is clearly judged. it can. Further, when the ΔE value is 20 or more, the color difference becomes extremely large.

(3) Bleed resistance test 1g of sample was put in 150cc of boiling water and boiled for 2.5 hours, and the degree of elution of natural pigments in the aqueous layer (to the extent that water is colored)
The bleeding resistance was judged by observing the sample with the naked eye.

(4) Practical test (sensory test) Color tone (color tone, brilliance, etc.) when using makeup cosmetic samples for two months, makeup stickiness (water resistance, sweat resistance,
Adhesion to skin), touch (extendability, moisture retention), etc.
A practical test (sensory test) was conducted by 30 female panelists, and the results were displayed as sensory evaluation points. In addition, the sensory evaluation score is an average of 30 people for each questionnaire item (test item), where 5 people answered that it was good, 3 people answered normal, and 1 person answered poor It is a point.

Production Examples 1-2 Using silk spinning waste as a raw material for silk fibroin,
0 part with a solution of 30 parts of Marcel soap and 3000 parts of water at 95-98 ° C
Was stirred and scoured for 3 hours, the residual glue was reduced to 0.1% or less, washed with water, and dried at 80 ° C. with hot air.

Mix 200 parts of water with 200 parts of calcium chloride (CaCl ₂ · 2H ₂ O) to prepare 400 parts of 38 wt% calcium chloride aqueous solution and prepare 110 parts.
Heated to ° C. 80 parts of scoured silk spun waste was added to this with stirring with a kneader for 5 minutes, and further stirred for 30 minutes to completely dissolve it.

Next, using a hollow fiber type dialysis device, 200 regenerated cellulose-based hollow fibers with an inner diameter of 200μ, a film thickness of 20μ, and a length of 500mm were bundled, and the ends were fixed and sealed (sealed) without blocking the hollow holes. Then, each of the solutions was allowed to flow at a rate of 0.1 / hour and dialyzed with deionized water to obtain an aqueous fibroin solution. The fibroin concentration of the aqueous fibroin solution was 6.5% by weight, and the residual calcium chloride was 0.001% by weight.
Met.

200 parts of this fibroin aqueous solution is 100 / sec. The stirring was performed at high speed so as to give the above shear deformation speed. When stirring was continued for 2 to 3 hours, silk fibroin was gradually precipitated, and finally the whole solidified as an aggregate of small gels. Separate the gel aggregate, wash with water, dry, crush it with a jet mill,
15 parts of regenerated silk fibroin powder according to the description in Japanese Patent Publication No. 58-38449, which is a conventional technique, was obtained. (Production Example 1) Further, to 200 parts of the fibroin aqueous solution obtained above,
After stirring and mixing 30 parts of calcium chloride dihydrate with stirring and confirming complete dissolution, 200 cc of 10 wt% sodium carbonate was gradually added thereto to precipitate fine crystals of calcium carbonate. Since the reaction is quantitatively completed at the same time when the addition of sodium carbonate is completed, subsequently, the silk fibroin aqueous solution in which the carbonate fine particles are suspended is supplied at 100 / sec. The stirring was performed at high speed so as to give the above shear deformation speed.

When stirring was continued for 2 to 3 hours, silk fibroin covering and encapsulating calcium carbonate gradually precipitated, and finally the whole solidified as an aggregate of small gels.

The gel aggregate was separated, washed with water, dried and then crushed with a hammer mill to obtain about 33 parts of a coarse powder.

The obtained pulverized product was suspended in 200 parts of water, and concentrated hydrochloric acid 4
0 part was gradually introduced. The reaction liquid vigorously foams due to the generated carbon dioxide gas. After confirming that the generation of carbon dioxide gas was completed, the stirring was further continued for 2 to 3 hours. After the reaction was completed, the precipitate was separated, washed with water, dried and then pulverized with a jet mill to obtain 13 parts of fine particles of the porous silk fibroin powder according to the present invention. (Production Example 2) From these results, it can be seen that the amount of calcium carbonate fine particles in the coarse particles was about 60% by weight.

The average particle size of the porous silk fibroin powder of Production Example 2 was 12.5μ as measured by a Coulter counter. In addition, the measurement of micropores by mercury porosimetry showed that the pore volume of 1μ or less was 630μ / g, which was porous, but 1μ or less of the regenerated silk fibroin powder of Production Example 1 or the silk fibroin powder obtained by simply pulverizing fibers. The porosity of each was less than 200 μ / g.

The crystallinity of the porous silk fibroin powder of Preparation Example 2 was 18% as a result of X-ray measurement, and the proportion of hot water-insoluble fibroin (β structure ratio) was 80% by weight.
The powder had a good feel and was suitable as a pigment.

Next, the porous silk fibroin powder of Production Example 2 and the regenerated silk fibroin powder of Production Example 1 were dyed by the usual mordanting method as described below using shikonin as a natural pigment, and the dyeing amount was compared. Production Example 1 from the amount of dye remaining in the
The amount of adsorbed regenerated silk fibroin powder of No. 2 was 1.5%, whereas the amount of the powder of Production Example 2 was about 7.5%, demonstrating that the porous silk fibroin powder has a strong adsorption activity.

Production Examples 3 to 7 Dissolution and dialysis were carried out according to Production Example 2 to prepare an aqueous silk fibroin solution, and calcium chloride, sodium carbonate, and hydrochloric acid were all added and removed at the same rate to give the intermediates shown in Table 1. Various porous silk fibroin powders were obtained by the same treatment as in Production Example 2 except that the amount of calcium carbonate in the coarse particles was adjusted. The results are shown in Table 1.

From this result, the amount of calcium carbonate in the intermediate coarse particles was 20
It is understood that -80% is a desirable range in terms of the amount of dyeing of the natural pigment, and if it deviates from this range, the fine pore amount becomes 300 μ / g or less, which is unsuitable.

The crystallinity of the regenerated silk fibroin in the powders of Production Examples 1 to 7 was in the range of 15 to 30%.

Production Examples 8 to 9 A conventional technique similar to Production Example 1 except that 200 parts of silk fibroin solution dissolved and dialyzed according to Production Example 1 was mixed with 80 parts of titanium oxide having an average particle size of 2μ. Japanese Patent Publication 57-
Regenerated silk fibroin-coated pigment 110 according to 11577
I got a part. (Production Example 8) In addition, in accordance with Production Example 1, silk spun waste was dissolved to produce a solution using silk fibroin as an aqueous calcium chloride solution. 400 parts of 20% sodium carbonate was mixed with 240 parts of the solution with stirring to precipitate fine crystals of calcium carbonate. 80 parts of titanium oxide with an average particle size of 2μ is mixed with this,
A uniform suspension was prepared by adding 0 part of water.

Salt is further added to the suspension to a concentration of 10% by weight, and when stirring is continued for 2 to 3 hours, a silk fibroin gel body encapsulating and encapsulating fine particles of calcium carbonate and titanium oxide is gradually regenerated and precipitated. Separate the gel body and
It was decomposed with 2,000 parts of diluted hydrochloric acid diluted with 0 part of concentrated hydrochloric acid, and then treated according to Production Example 2. The dry coarse powder was pulverized with a jet mill to obtain 115 parts of fine powder. (Production Example 9) The amount of fine particles of calcium carbonate in the intermediate coarse particles of this fine powder was about
It was 36% by weight, and the amount of titanium oxide was twice that of the regenerated silk fibroin. Next, other characteristics are shown in Production Example 2.
Was tested according to.

Production Examples 10 to 14 Titanium oxide was changed to another base pigment having an average particle size of 2 to 6 μ,
This was carried out according to Production Example 8 except that the ratio of the regenerated silk fibroin to the regenerated silk fibroin was changed variously, and then various properties were tested according to Production Example 2.

As shown in Table 2, the powders of Production Examples 9 to 14 according to the present invention have a large amount of pores and exhibit excellent dyeability, as compared with the powder of the prior art of Production Example 8.

((Production Example of Coloring Pigment)) The base powders obtained in Production Examples 1 to 14 were mordanted with the natural dye according to the present invention to produce various coloring pigments.

Production Examples 100 to 103 1 kg of madder stalks were shredded, immersed in 40 water and boiled for 2 hours, and then passed through to obtain a dyeing solution 39.6 containing 12 g of madder pigment (extracted pigment). In this dye liquor, the regenerated silk fibroin of Production Example 1 (30% crystallinity, 160 μm pore volume /
500 g of the powder of g) was dispersed and dyed at 60 to 100 ° C. for 1 hour, and then the free Akane dye which had been washed thoroughly with water was dissolved and removed. Fine powder (502 g) of the obtained Akane dye-stained regenerated fibroin was dispersed in an aqueous solution of 10 g of aluminum potassium alum in 2.5 water, and the temperature was 70-80 ° C.
After heating for 80 minutes for mordant treatment (post mordant),
It was washed with water, dried and dried to obtain a reddish orange colored pigment (Akane dye-Production Example 1). (Production Example 100) Similarly, in Production Example 100, the powder of Production Example 1 is replaced by the regenerated silk fibroin-coated pigment of Production Example 8 (porosity 160
.mu. / g) was applied in the same manner to obtain a color pigment (Akane dye-Production Example 8). (Production Example 101) In the above Production Example 100, the porous silk fibroin powder according to the present invention of Production Example 2 was replaced with the powder of Production Example 1 (pore volume).
630 μ / g) was applied in the same manner as above to obtain a color pigment (Akane dye-Production Example 2). (Production Example 102) In the same manner, the powder of Production Example 9 according to the present invention was applied to obtain a color pigment (Akane dye-Production Example 9). (Production Example 103) Production Examples 104 to 106 Production of the colored pigment of the present invention (Suho dye-mordanting dyed regenerated fibroin fine powder) 1 kg of Suho bark was immersed in water 10 and boiled for 2 hours,
The solution was cooled and passed over to obtain dye solution 9.6 containing 9 g of Suho dye (extracted dye). Disperse 500 g of the powder of Production Example 8 (pore volume: 230 μ / g) in this dye liquor, boil for 1 hour to dye,
After cooling, add 100 m of a saturated aqueous solution of aluminum ammonium alum, perform mordant treatment at 70 to 80 ° C for 30 minutes, and wash with water. After washing with water, water was added to 10 and 50 m of a 5% aqueous solution of aluminum acetate was added, and mordant treatment was carried out at 70 to 80 ° C. for 30 minutes. ) Got. (Production Example 104) In the above Production Example 104, instead of the powder of Production Example 3, the porous silk fibroin powder according to the present invention of Production Example 5 (porosity amount
A colored pigment (Suho dye-Production Example 5) was obtained in the same manner except that 500 μg / g) was applied. (Production Example 105) In the same manner, the powder of Production Example 11 according to the present invention was applied to obtain a color pigment (Suho dye-Production Example 11). (Production Example 106) Production Examples 107 to 109 Production of Coloring Pigment of the Present Invention (Purple Dye-Mordant Regenerated Fibroin Fine Powder) 1 kg of purple root was crushed and immersed in 1 water, and then water at 40 to 60 ° C. 20 Was added to obtain a dye liquor containing 11 g of the purple root dye, 20.9. 500 g of the powder of Production Example 7 (pore volume 240 μ / g) was dispersed in this dye liquor, and dyeing was carried out at 40 to 60 ° C. for 2 hours, and then a fine powder of a purple dye-stained regenerated fibroin was obtained. Disperse in 20% 0.5% aluminum acetate aqueous solution, 1 at 70-80 ℃
A mordanting treatment was carried out with stirring for a period of time, followed by washing with water and drying to obtain a purple coloring pigment (purple root dye-Production Example 7). (Production Example 10
7) In the above Production Example 107, instead of the powder of Production Example 7, the porous silk fibroin powder according to the present invention of Production Example 6 (porosity amount
A coloring pigment (purple dyestuff-Production Example 6) was obtained in the same manner except that 360 μg / g) was applied. (Production Example 108) Similarly, the powder of Production Example 13 according to the present invention was applied to obtain a color pigment (purple dye-Production Example 13). (Production Example 109) Production Example 110 100 g of carminic acid of cochineal dye is dissolved in 20 water,
A dyeing solution was prepared by adding 100 g of a 32% acetic acid aqueous solution to this aqueous solution. 500 g of the porous silk fibroin powder according to the present invention of Production Example 12 was dispersed in this dyeing solution, and dyeing was carried out at 50 to 80 ° C. for 1.5 hours. Then 50 g of aluminum potassium alum 5 g
After adding an aqueous solution dissolved in water to mordant treatment at 80 ° C. for 30 minutes, it was filtered, washed with water and dried to obtain a red color pigment (Cochineal dye-Production Example 12).

Production Example 111 Mordant dyeing was carried out in the same manner as in Production Example 110 except that laccaic acid as a lac dye was used instead of carminic acid as a cochineal dye to give a reddish brown colored pigment (lac dye-Production Example 1
2) got.

Production Example 112 Dissolve 150 g of water-soluble monascus pigment in water 20, adjust the pH to 11 by adding 30% aqueous sodium hydroxide solution to this aqueous solution,
This was used as a dye liquor. 500 g of the porous silk fibroin powder according to the present invention of Production Example 4 was dispersed in this dye liquor and the mixture was stirred at 60 ° C. for 1
After dyeing for an hour, 50 m of a 10% aqueous solution of aluminum ammonium alum was added and mordanting was performed at 70 ° C. for 30 minutes. After mordanting, 4N hydrochloric acid was added to adjust the pH to 5 and the mixture was washed with water and dried to obtain a reddish brown colored pigment (Monascus dye-Production Example 4).

Production Example 113 1 kg of petals of saffron were washed with water, immersed in 40 of water and boiled for 1 hour to obtain a dye liquor 39.6 containing 220 g of the extracted pigment. 40% of 0.05% aluminum sulfate solution in advance
Production example 5 after mordanting at 70-80 ° C for 1 hour (pre-mordanting)
500 g of the porous fibroin powder according to the present invention was dispersed, dyed at 70 to 80 ° C. for 1 hour, dried, and then pulverized to obtain a yellow coloring pigment (saffron dye-Production Example 5).

Production Example 114 1 kg of cocoa seeds was crushed, soaked in water 40, boiled for 2 hours and then cooled to obtain a dye liquor 39.6 containing 36 g of a cocoa extract pigment. To this dyeing solution, 500 g of the porous fibroin powder according to the present invention of Production Example 10 was dispersed, boiled for 1 hour for dyeing, and after cooling, an aqueous solution in which 10 g of aluminum potassium alum was dissolved was added, and further at 70 to 80 ° C.
A mordanting treatment was carried out for a minute, and after rinsing, washing with water and drying, a brown coloring pigment (cocoa dye-Production Example 10) was obtained.

Production Example 115 1kg of yellowfin trunk endothelium is cut into small pieces and immersed in 40 water for 2 minutes.
Boil for 3 hours and add 3 g of dyeing solution containing 21 g of yellowfin pigment.
I got 9.6. 500 g of the porous silk fibroin powder according to the present invention of Production Example 14 was dispersed in this dye liquor, and dyeing was carried out at 60 to 100 ° C. for 1 hour, followed by washing with water. Next, an aqueous solution prepared by dissolving 10 g of aluminum ammonium alum in 2.5 of water was added, and mordanting treatment was performed at 70 to 80 ° C. for 30 minutes, followed by washing with water, followed by drying, and a yellow coloring pigment (yellowfin dye-Production Example 14).
Got

Production Example 116 1kg of sardines of shrimp was shredded, soaked in 25 of water, boiled for 1 hour, and then passed through to obtain a dyeing solution 24.7 containing 9g of swelling dye
Got To this dyeing solution, 500 g of porous silk fibroin powder according to the present invention of Production Example 9 which had been mordanted (pre-mordanting) with 0.3% aluminum potassium alum aqueous solution 25 at 70 to 80 ° C for 1 hour was dispersed to 70 to 80 ° C. Dye for 1 hour,
It was filtered, washed with water and dried to obtain a yellow color pigment (Enju dye-Production Example 9).

Production Example 117 1 kg of spider powder was crushed and dispersed in 40 water, and then 400 m of a 10% aqueous solution of caustic potash and 400 m of a 10% aqueous solution of hydrosulfite were added and stirred. Got 70% to 80% of 25% of 0.1% aqueous solution of aluminum ammonium alum was previously added to this dyeing solution.
Disperse 500 g of the porous silk fibroin powder according to the present invention of Production Example 2, which has been subjected to a mordant treatment (pre-mordanting) for 1 hour at 50 ° C.,
It was dyed at 70 ° C. for 1 hour, washed with water, washed with water, and dried to obtain a dark blue colored pigment (ai dye-Production Example 2).

Production Example 118 1 kg of gardenia seeds is immersed in 40 water and boiled for 1 hour,
The dye solution containing 380 g of gardenia extract dye.
Obtained. In this dyeing liquor, 500 g of porous silk fibroin powder according to the present invention of Production Example 13, which had been mordanted in advance with 0.05% ammonium sulfate aqueous solution 40 at 70 to 80 ° C. (pre-mordanting), was dispersed at 70 to 80 ° C. After dyeing for 1 hour, an aqueous solution of malic acid was added to adjust the pH to 4, then dried and dried to obtain a yellow coloring pigment (gardenia dye-Production Example 13).

Examples 1 to 8 and Comparative Examples 1 to 4 [Lipstick] Various color pigments of Production Examples 100 to 118 were blended according to the description in Table 3 to prepare respective lipsticks which are Examples or Comparative Examples. Then, various characteristics tests were conducted. The results are shown in Table 3.

(1) Composition (ingredient components) (blending amount part) Candelilla wax 4.0 Solid paraffin 8.0 Beeswax 5.0 Carnauba wax 5.0 Lanolin 11.0 Isopropyl myristate 15.0 Castor oil 42.0 Coloring pigments listed in Table 3 (2) Preparation method Oil-based ingredients After heating to a temperature of 80 ° C. for dissolution and mixing, a color pigment was added thereto, and the mixture was kneaded by applying it to a roller, then melted again, poured into a mold and cooled to prepare each lipstick.

(3) Properties Table 3 shows the results of various properties tested in accordance with the test method described above.

Examples 9 to 12 and Comparative Examples 5 to 6 [Blusher] Each of the blushers was prepared by blending various coloring pigments in the same manner as in Example 1 and various properties were tested. The result is the fourth
Described in the table.

(1) Composition (2) Preparation method After uniformly mixing the component (A), this is added to the dissolved mixture of the component (B) and mixed, and then crushed and sieved, and a die is cast. Each cheek red was prepared.

Examples 13 to 14 and Comparative Example 7 [Foundation cream] Various foundation pigments were mixed in the same manner as in Example 1 to prepare respective foundation creams, and various properties were tested. The results are shown in Table 4.

(1) Composition (2) Preparation method The components (A) and (B) are heated and mixed at a temperature of 80 ° C to dissolve them,
The component (A) was mixed into the component (B), emulsified and dispersed, and cooled to 30 ° C. with stirring to prepare each foundation cream.

As shown in Tables 3 and 4, Examples 1 to 14, which are makeup cosmetics of the present invention, are superior in various characteristics in comparison with Comparative Examples 1 to 7, respectively. it is obvious.

Claims (13)

[Claims] 1. A regenerated silk fibroin in the form of fine powder or a regenerated silk fibroin containing a base pigment, at least 50% by weight of which is hydrothermally insoluble fibroin (β).
Type) and has pores with a diameter of 1μ or less 300μ /
Porous silk fibroin powder containing more than g, using water-soluble aluminum salt as a mordant, Suho pigment, gardenia pigment, saffron pigment, madder pigment, cacao pigment, yellowfin pigment, cochineal pigment, lac pigment, purple root pigment, ende pigment, monascus pigment A makeup cosmetic that is colored with a coloring pigment obtained by mordanting with a natural pigment selected from the group consisting of pigments and dyes. 2. The makeup cosmetic composition according to claim 1, wherein the regenerated silk fibroin or the regenerated silk fibroin containing a base pigment contains 400 μg / g or more of pores having a pore diameter of 1 μm or less. 3. The makeup cosmetic according to claim 1, wherein the regenerated silk fibroin or the regenerated silk fibroin containing a base pigment contains 600 μg / g or more of pores having a pore diameter of 1 μm or less. 4. At least 80% by weight of regenerated silk fibroin.
Is a hot water-insoluble fibroin, The makeup cosmetics according to claim 1. 5. The makeup cosmetic according to claim 1, wherein the regenerated silk fibroin has a crystallinity of at least 10%. 6. The makeup cosmetic composition according to claim 1, wherein the regenerated silk fibroin has a crystallinity of at least 20%. 7. The maximum particle size of the porous silk fibroin powder is 0.
The makeup cosmetic according to claim 1, which has a size of 5 to 100 µ. 8. The base pigment is 0 for regenerated silk fibroin.
The make-up cosmetics according to claim 1, which is 4 times (weight). 9. The makeup cosmetic composition according to claim 1, wherein the base pigment is talc, kaolin, mica, titanium oxide, zinc oxide, titanium mica, or a combination thereof or a combination thereof. 10. The makeup cosmetic according to claim 1, wherein the water-soluble aluminum salt is aluminum potassium alum, aluminum sodium alum, aluminum ammonium alum, aluminum sulfate, aluminum acetate, aluminum chloride or a combination thereof. . 11. The make-up cosmetic composition according to claim 1, wherein mordant dyeing is carried out by mordant treatment of porous silk fibroin powder with an aqueous solution of a water-soluble aluminum salt and then dyeing with an aqueous solution of a natural pigment. . 12. The make-up cosmetic composition according to claim 1, wherein mordant dyeing is performed by dyeing porous silk fibroin powder with an aqueous solution of a natural pigment and then mordant treatment with an aqueous solution of a water-soluble aluminum salt. . 13. A color pigment in an amount of 1 to 50% by weight based on the total weight of prescription components.
Makeup cosmetics described in the item.