JPH0676293B2 - Makeup cosmetics - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a makeup cosmetic prepared by blending a specific modified porous silk fibroin powder described below dyed with an acid dye as a color pigment.

(Prior Art) Japanese Unexamined Patent Publication (Kokai) No. 57-191315 discloses that silk fibroin powder (silk fiber powder or the like) or regenerated silk fibroin powder has N, N-
There has been proposed a silk fibroin powder in which a polymer mainly containing dialkylaminoethyl methacrylate is fixed and which has improved dyeability and a method for producing the same.

However, in the case of the present invention, although the conventional silk powder (silk fiber powder) or regenerated silk fibroin powder is modified in dyeability, aroma retention, etc., this modified regenerated silk fibroin is used. The powder was still poor in practicability when it was dyed with an acid dye and applied as a coloring pigment to makeup cosmetics.

In the above-mentioned publication, the dyeing amount of the acid dye (Red No. 2) with respect to the mere recycled silk fibroin powder was at most 0.2% by weight, but 2 to 105% by weight of the N, N-dialkylaminoethyl methacrylate polymer was fixed. It is described that the amount of dyed regenerated silk fibroin powder (Red No. 2) is increased to 1.7 to 27% by weight.

However, the makeup cosmetics containing these modified regenerated silk fibroin powder coloring pigments are not always satisfactory in all of the color tone, feel, makeup lasting, etc. described later. That is, in order to satisfy the color tone of makeup cosmetics, it is necessary to increase the dyeing amount of the acid dye in the color pigment sufficiently, and therefore N, N-dialkylaminoethylmethacrylate based on the silk fibroin powder is required. Increasing the amount of polymer adhered may impair the feel of the silk fibroin powder when applied to the skin, such as smoothness (smoothness), extensibility (elongation), and moisturizing (moisturizing). However, the conventional colored pigments based on modified silk fibroin powder have a problem in that, when trying to satisfy both the color tone, the feel and the makeup lasting at the same time, the applicable range is limited.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, (1) the specific modified porous silk fibroin powder described below, which forms the base of the colored pigment according to the present invention, The starting material silk and regenerated silk fibroin are significantly different in morphology and properties chemically and physically, the acid dye has higher affinity and dyeing property, and the coloring pigment obtained by dyeing this is Vivid colors and good color tone.

(2) Moreover, the modified porous silk fibroin powder is
Compared with the conventional modified silk fibroin powder, it has the original characteristics of silk fibroin powder such as smoothness, extensibility, and moisturizing property even in a region where a large amount of N, N-dialkylaminoethyl methacrylate polymer is fixed. .

(3) Further, the makeup cosmetics containing the color pigment according to the present invention have improved light resistance, heat resistance, and bleeding resistance described below, and have been tested in practical use to obtain color tone, touch, makeup lasting, etc. The ability to impart and develop a beautiful, stable cosmetic effect (make-up effect) that is excellent in

The present invention was completed by finding the above.

(Object of the Invention) That is, the object of the present invention is tones (color, vividness), feel (smoothness, spreadability, moisturizing property), makeup sticky (water resistance, sweat resistance, adhesion to skin). To provide excellent makeup cosmetics.

(Structure of the Invention) The present invention comprises regenerated silk fibroin to which a polymer having N, N-dialkylaminoethyl methacrylate as a main component is fixed, and at least 50% by weight of the silk fibroin.
Is composed of hot water-insoluble fibroin (β type), and is colored with a colored pigment obtained by dyeing modified porous silk fibroin powder containing 300 μl / g or more of pores with a pore size of 1 μm or less with an acid dye. Make-up cosmetics.

(Specific Description of Structure) The modified porous silk fibroin powder according to the present invention is described in (1) a porous silk fibroin powder obtained by the method described below, which is described in JP-A-57-191315. According to the method described in (1), a polymer containing N, N-dialkylaminoethyl methacrylate as a main component is fixed, followed by washing with water and drying (solid-liquid reaction), and (2) the same as JP-A-57-191315. According to the method described in the publication, after the silk fibroin aqueous solution was reacted with N, N-dialkylaminoethyl methacrylate, this was further
Similar to the method for producing porous silk fibroin powder described below, a suspension is prepared by mixing fine crystal precipitates or fine powder of a water-insoluble carbonate (such as calcium carbonate), and then a high shear deformation rate. The modified regenerated silk fibroin coarse particles are generated by performing a treatment such as stirring with. The coarse particles are treated with an acid to decompose and elute the water-insoluble carbonate, generate carbon dioxide, and then washed with water, dried, and then pulverized (liquid-liquid reaction).

The so-called porous silk fibroin powder according to the present invention is produced, for example, as follows. First, as the silk fibroin raw material, eyebrows, raw silk, eyebrows scraps, raw silk scraps, screws, fried cotton, silk cloth scraps, burettes, etc. are used in the presence of an activator, in warm water or in the presence of an enzyme according to a conventional method, if necessary. For this, scoured silk which has been dried by removing sericin in warm water is used.
Although it is dissolved by the method described in JP-A-38449, the solvent is preferably an aqueous solution of calcium or magnesium or zinc hydrochloride or nitrate in terms of cost and use. The concentration of these aqueous solutions depends on the type of solvent used,
Although it varies depending on the temperature and the like, the concentration of the metal salt etc. is usually 10 to 80% by weight, preferably 20 to 70% by weight, particularly preferably 25 to 60% by weight.
% By weight.

The concentration of fibroin in the aqueous fibroin solution 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 regenerated fibroin powder in the washing and drying steps. Further, outside the both ranges, the proportion of hot water-insoluble fibroin (β structuring rate) is small, and regenerated fibroin, which easily sticks in sweat or an aqueous dispersion medium and easily causes secondary particle formation, is easily produced. The suspension containing the water-insoluble carbonate is prepared by dissolving at least one of calcium, magnesium or zinc hydrochloride or nitrate in an aqueous silk fibroin solution, adding a water-soluble carbonate to the solution, and adding calcium or magnesium. Alternatively, zinc carbonate may be precipitated as water-insoluble fine particles, and since the dissolving salt preferable as the solvent for the silk fibroin raw material happens to be the raw material of the water-insoluble carbonate, it is included in the intermediate coarse particles. Even if the silk fibroin raw material is dissolved in an amount calculated from a predetermined amount (approximately equivalent amount) of the water-insoluble carbonate to be added (approximately equivalent amount), calcium, magnesium or zinc hydrochloride or nitrate, and this is used in the next step as it is without desalting. Good. 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. The low molecular weight silk fibroin, which is originally contained in dialysis or is formed when dissolved, reduces the performance of the product as a base material for cosmetics, or becomes an obstacle to color development during dyeing, and iron ions mixed from raw materials or reaction systems Can be completely removed. In this case, when the water-insoluble carbonate is produced in the reaction system, it is necessary to add a predetermined amount of the hydrochloride or nitrate again.

As the above-mentioned water-soluble carbonate, the reaction of the above-mentioned hydrochloride or nitrate such as sodium carbonate, ammonium carbonate and the water-soluble carbonate occurs instantly under stirring, and water-insoluble carbonate fine particles are precipitated.

At least one treatment such as mixing of a 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 are suspended to regenerate the silk fibroin. The regenerated silk fibroin coarse particles are coarse particle gel bodies which coat and enclose water-insoluble carbonate fine particles. The coarse particle gel body is regenerated by the same method from a silk fibroin aqueous solution in which light calcium carbonate having an average particle size of 1 μm or less, preferably 0.1 μm or less is suspended in the dialysis desalted and purified silk fibroin aqueous solution. You can also

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

Silk fibroin precipitates only by stirring, but in this case it must be carried out at a high shear deformation rate, usually 50 / Sec. Or more,
The shear deformation rate is 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 silk fibroin coarse particles as an intermediate are filtered, washed with 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 be slightly excessive, but if the pH is set to 1 or less, the silk fibroin may become brittle and must be avoided. Completion of acid decomposition can be confirmed by the end of generation of carbon dioxide gas, and then the obtained porous silk fibroin powder is washed with water and dehydrated. For the dehydration, it is preferable to use a centrifugal dehydrator, and by this dehydration, the porous silk fibroin powder is usually dehydrated up 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.

If the maximum particle size is larger than 100 μ, the adhesion to skin, affinity, extensibility, etc. are likely to deteriorate.

In the thus obtained porous silk fibroin powder according to the present invention, at least 50% by weight, preferably at least 80% by weight of the regenerated silk fibroin 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 (aggregate into huge particles) due to sticking or caking with water or sweat, or water dispersion. Desorption of the film is likely to occur in a medium (water-based cosmetics), and dispersibility is likely to be reduced in an oil dispersion medium (oil-based cosmetics). In addition, the elongation and feel during application become poor.

In the present invention, hot water-insoluble fibroin is 100 ° C.
Fibroin that does not dissolve even if it is boiled in hot water 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.

Further, here, during the production process, before or after the drying of the regenerated fibroin powder, after drying or after pulverization, hot water insolubilization of fibroin (in the case of hot water insoluble fibroin, β structuring rate) is further promoted ( Can be increased) and the above characteristics can be further improved.

As the wet temperature treatment, 50% of the powder after drying or crushing is used.
℃ or more, especially heat treatment with saturated steam of 80 ~ 120 ℃, or before drying sodium chloride, potassium chloride,
It is carried out by heat treatment in an aqueous solution of a neutral salt such as sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate or in an organic solvent such as acetone or alcohol.
When these moist heat treatments are performed, it is possible to further increase the crystallinity of fibroin while promoting the insolubilization of regenerated fibroin in hot water (increasing the β structuring rate) as described above, and it is possible to obtain excellent moderate hydrophilicity. It is easy to obtain a good fibroin-coated pigment having a balance of lipophilicity, antiperspirant property, dispersibility in a dispersion medium, and dyeing fastness.

Further, the porous silk fibroin powder according to the present invention has a structure in which regenerated silk fibroin has innumerable fine pores, and the amount thereof is 300 μl / g or more, preferably 400 μl / g or more in pores having a pore diameter of 1 μ or less. is there.

Normal fibrous regenerated silk fibroin or silk thread that has been embrittled by chemical treatment or ground and crushed is simply fibrous silk powder with a void content of at most 200.
Compared with μl / g, in the case of the porous silk fibroin powder according to the present invention, the amount of fine pores is remarkably large, and for this reason, for example, even when dyeing with an acid dye as described below, it is very dark and water resistant. -A colored pigment having good light fastness can be obtained.

The reason why the porous silk fibroin powder according to the present invention significantly increases 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 due to the large amount of fine pores. It is considered that the same principle as that caused by.

Next, in order to obtain a modified porous silk fibroin powder (solid-liquid reaction) by reacting this porous silk fibroin powder with N, N-dialkylaminoethyl methacrylate, a suspension of the porous silk fibroin powder in water is obtained. 3 to 50% by weight of N, N-dialkylaminoethyl methacrylate is added to and mixed with fibroin (pure content), and 0.5 to 5% by weight of radical polymerization catalyst (for example, peroxide) with respect to N, N-dialkylaminoethyl methacrylate. The reaction may be performed at a temperature of 40 to 80 ° C. for 2 to 6 hours in the presence of ammonium sulfate and the like.
Then, the silk fibroin powder is filtered, washed with water, dehydrated and dried, and re-ground if necessary, to obtain the target modified porous silk fibroin powder.

When the modified porous silk fibroin powder of the present invention is produced by the liquid-liquid reaction, an aqueous silk fibroin solution is used instead of the porous silk fibroin powder suspension in the solid-liquid reaction. Under the same conditions as above, N, N
After reacting with dialkylaminoethyl methacrylate, the reaction solution may be mixed with a water-insoluble carbonate microcrystalline precipitate or fine powder, and a method similar to the method for producing the porous silk fibroin powder may be applied. In the same manner, the target modified porous silk fibroin powder can be obtained.

As the alkyl group of N, N-dialkylaminoethyl methacrylate, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl groups can be applied, but the reactivity with silk fibroin and the dyeability of acid dyes Further, methyl group and ethyl group are particularly preferable in order to obtain good results in properties as a cosmetic base.

Further, N, N-
It is also possible to fix a copolymer of dialkylaminoethyl methacrylate and another acrylic monomer or an ethylenically unsaturated compound such as a vinyl compound to silk fibroin.

The amount of N, N-dialkylaminoethyl methacrylate added to silk fibroin is preferably 3 to 50% by weight,
If it is less than 3% by weight, the desired dyeing amount of the acidic dye cannot be obtained sufficiently, and if it exceeds 50% by weight, the inherent characteristics of the silk of the obtained color pigment may be impaired. That is, in the present invention, the amount of N, N-dialkylaminoethyl methacrylate added may be an amount suitable for keeping the amount of the polymer fixed to 3 to 35% by weight. The modified porous silk fibroin powder according to the present invention can be produced by appropriately adjusting it according to the description of JP-A-57-191315 within a range that achieves the object of the present invention.

(1) As described above, the modified porous silk fibroin powder has (1) at least 50% by weight of the regenerated silk fibroin that is composed of hydrothermally insoluble fibroin, has a crystallinity of 10% to 43%, and a pore diameter of 1 μm. It must be porous containing the following pores at 300 μl / g or more.

(2) Further, the polymer containing N, N-dialkylaminoethyl methacrylate as the main component is fixed to the extent that the original properties of the silk fibroin powder are not impaired, and the number of amino groups is increased.

Due to, for example, the adsorption activity of the acid dye is dramatically increased, and the color development (color tone and sharpness) of the obtained color pigment is unprecedented, and the smoothness, extensibility, and characteristics of the silk fibroin powder are excellent. It has moisturizing properties. Furthermore, the makeup cosmetics containing this coloring pigment exhibit remarkably excellent properties as described above.

The acid dye according to the present invention is a water-soluble acid dye,
For example, Red No. 2 (CI No. 16185), Red No. 3 (CI No. 4543)
0), Red No. 102 (CINo.16255), Red No. 104 (CINo.4541)
0), Red No. 227 (CINo.17200), Red No. 401 (CINo.4519)
0), Red No. 504 (CINo.14700), Yellow No. 4 (CINo.1914)
0), Yellow No. 5 (CINo.15985), Yellow No. 203 (CINo.4700)
5), Yellow No. 403 (CI No. 10316), Blue No. 1 (CI No. 4209)
0), Blue No. 2 (CINo.73015), Green No. 3 (CINo.4205)
3), Green No. 201 (CINo.61570), Green No. 205 (CINo.4209)
5), Green No. 402 (CINo.42085), Brown No. 201 (CINo.2017)
0) and the like are exemplified as preferable ones. The acid dyeing method is to disperse the modified porous silk fibroin powder in an acid dye aqueous solution, add acid (hydrochloric acid, acetic acid, etc.), and add PH.
Is adjusted to acidity, heated to 70 to 100 ° C. for dyeing, and then dehydrated, washed with water and dried to obtain the color pigment according to the present invention.

The content 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 with the above-mentioned coloring pigment, but if necessary, a small amount of a coloring inorganic pigment or an organic pigment can be blended.

The base used in the makeup cosmetics of the present invention is a well-known base for makeup cosmetics, such as an inorganic pigment, an extender pigment, an oily substance, and a fragrance, and is not particularly limited. The makeup cosmetics of the present invention are extremely useful as lipsticks, eye shadows, blushers, foundations and the like.

(Effects of the Invention) The makeup cosmetic of the present invention has excellent light-coloring properties, and by incorporating the modified porous silk fibroin powder dyed with an acid dye having the original characteristics of silk fibroin, Excellent in heat resistance, heat resistance, bleeding resistance, color tone (color, vividness), touch (smoothness, extensibility, moisture retention), makeup lasting (water resistance, sweat resistance, adhesion to skin), etc. It has a beautiful and stable cosmetic effect, 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.
The samples were stored for a week and 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 was stored for 3 months in a thermostat whose internal temperature was adjusted to 50 ° C, and one was stored in a cool dark place (5 ° C) for 3 months. The heat resistance was judged from the degree of color change by visually comparing the colors of the above.

In the light resistance test (1) and this heat resistance test, the L value of the Hunter colorimetric system for each of two samples, a
The values and b values were measured with a spectrophotometer (Murakami Color Research Laboratory), and 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 the sample was put in 150cc of boiling water and boiled for 2.5 hours, and the degree of elution of the acid dye into the aqueous layer (to the extent that water is colored)
The bleeding resistance was judged by observing the sample with the naked eye. Then, the absorbance of the dye eluted in the aqueous layer was measured to quantify the amount of the dye, and the residual ratio of the dye was determined from the following formula to be used as a measure of bleed resistance.

(4) Practical test (sensory test) Using a sample of makeup cosmetics for 2 months, color tone (color, vividness), touch (smoothness, extensibility, moisture retention), makeup lasting (water resistance, A sensory test was conducted by 30 female panelists on sweat resistance and adhesion to the skin), and the results were displayed as sensory evaluation points. Regarding the sensory evaluation score, for each questionnaire item (test item), 5 people answered that it was good, 3 people answered that it was normal, and 1 person answered that it was poor.
It is the average score of 30 people when it is set as a point.

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

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, a hollow fiber type dialysis device was used in which 2000 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. Each of the solutions was allowed to flow at a rate of 0.11 / hour and dialyzed with deionized water to obtain an aqueous silk fibroin solution. The silk fibroin concentration of the silk fibroin aqueous solution was 6.5% by weight, and the residual calcium chloride was 0.001% by weight.

200 parts of this silk fibroin aqueous solution was stirred at a high speed so as to give a shear deformation rate of 100 / Sec. Or more. Stir 2-3
As time continued, silk fibroin gradually precipitated, and finally the whole solidified as an aggregate of small gels. The gel aggregate was separated by filtration, washed with water and dried, and then pulverized with a jet mill to obtain 15 parts of regenerated silk fibroin powder according to the description in Japanese Patent Publication No. 58-38449. (Production Example 1) Furthermore, 30 parts of calcium chloride dihydrate was stirred and mixed with 200 parts of the silk fibroin aqueous solution obtained above, and after confirming that the solution was completely dissolved, 200 wt of a 10 wt% sodium carbonate aqueous solution was added thereto. Was gradually added to precipitate fine crystals of calcium carbonate. Since the reaction was quantitatively completed at the same time as the addition of sodium carbonate was completed, the silk fibroin aqueous solution in which the carbonate fine particles were suspended was subsequently stirred at a high speed so as to give a shear deformation rate of 100 / Sec.

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 by filtration, washed with water, dried and then pulverized with a hammer mill to obtain about 33 parts of 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 completion of the reaction, the precipitate was filtered off, 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 this result, it can be seen that the amount of calcium carbonate fine particles in the coarse particles was about 60% by weight. The average particle sizes of the silk fibroin powders of Production Examples 1 and 2 were 13.0μ and 12.5μ, respectively, as measured by a Coulter counter. Also, in the case of Production Example 2, the amount of fine pores measured by mercury porosimetry was 630 μl / g and the porosity of 1 μm or less was porous, but the regenerated silk fibroin powder of Production Example 1 or simply the fiber was crushed. The porosity of the silk fibroin powder of 1 μm or less was 200 μl / g or less.

The crystallinity of the porous silk fibroin powder of Production Example 2 was X.
The result of line measurement was 18%, and the proportion of hot water-insoluble fibroin (β structuring rate) was 80% by weight.

Next, 100 parts of each of the powders of Production Example 1 and Production Example 2, and N, N-
15 parts of dimethylaminoethyl methacrylate (monomer / fibroin = 0.15) and 2 parts of a catalyst ammonium persulfate (catalyst / monomer = 0.02) were reacted in 1000 parts of water at a temperature of 60 ° C. for 4 hours, respectively.

The amount of the N, N-dimethylaminoethyl methacrylate polymer fixed was calculated by the rate of increase with respect to each powder.
The regenerated silk fibroin powder in Example 2 was 6.0% by weight, and the porous silk fibroin powder in Production Example 2 was 12% by weight.

Further, 30 parts each of the modified powders of Production Example 1 and Production Example 2 and 10 parts of Red No. 2 (CI No. 16185) were dissolved in 1000 parts of water, and the mixture was added to an aqueous solution prepared by adjusting pH to 1.5 with hydrochloric acid and dispersed. Let, 80
Dye at -100 ° C for 1 hour, wash with water, dry,
A red colored pigment was obtained. The dyeing amount was calculated from the amount of the dye remaining in the dyeing solution. The powder of Production Example 1 was 5.0% by weight based on the weight of the powder, and the powder of Production Example 2 was 16.5% by weight.

Production Examples 3 to 7 Dissolution and dialysis were performed according to Production Example 2 to prepare an aqueous silk fibroin solution, to which calcium chloride, sodium carbonate,
And all of hydrochloric acid were increased / decreased at the same rate to prepare various modified porous silk fibroin powders in the same manner as in Production Example 2 except that the amount of calcium carbonate in the intermediate coarse particles shown in Table 1 was adjusted. The obtained pigment was dyed with an acid dye (Red No. 2) to produce various colored pigments. 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 dyeing amount of Red No. 2, and if it deviates from this range, the amount of fine pores becomes 300 μl / g or less, which is inappropriate.

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 (1-1) to (1-6), (2-1) to (2-
6) The ratio of N, N-dimethylaminoethyl methacrylate (monomer) to 100 parts of each of the powders of Production Example 1 and Production Example 2 was changed to 3.5 to 50% by weight, and ammonium persulfate as a catalyst was added to 2 parts of the monomer. Various powders having different amounts of N, N-dimethylaminoethyl methacrylate polymer fixed were made to react separately in 1000 parts of water at a temperature of 60 ° C. for 4 hours, respectively. I got it.

Then 30 parts of each of these powders and yellow No. 4 (CI No. 1914
0) Each colored pigment was obtained in the same manner as in the dyeing process of Production Example 1 except that 15 parts of water was dissolved in 1000 parts of water, and the dyeing amount is shown in Table 2 (4th and 8th steps).

As shown in Table 2, the modified regenerated silk fibroin powder of Production Example 1 (pore volume 150 μl / g) was compared with the modified porous silk fibroin powder of Production Example 2 according to the present invention (pore volume 630 μl / g). , The reaction sticking rate of the monomer is low, and the sticking amount is 11 ~
Even at 35% by weight, the dyeing amount is as low as 8.0 to 16% by weight, and the monomer fixing amount is 26% by weight as described later.
The above shows a tendency that the original properties of the silk fibroin powder are impaired. In the case of the powder of Production Example 2, the amount of adhered monomer was 3.0% by weight and the amount of dyed was 7.0% by weight, which is excellent in the amount of dyed yellow # 4.

Further, as will be described later, it was a phenomenon to be noted in the present invention that the original characteristics of the silk fibroin powder were not impaired even when the amount of the fixed monomers reached 35% by weight,
This is considered to be due to the characteristics of the porous powder.

Production Examples 8 to 9 In Production Examples 1 and 2, 200 parts of an aqueous silk fibroin solution (6.5% by weight of silk fibroin), 1.3 parts of N, N-diethylaminoethyl methacrylate (monomer / fibroin = 0.1), and a nonionic surfactant were used. 0.2 part and 0.026 part of hydrogen peroxide which is a catalyst and 0.026 part of acidic sodium sulfite are added and reacted for 4 hours at a temperature of 60 ° C. to preliminarily fix the polymer of N, N-diethylaminoethyl methacrylate to silk fibroin ( Liquid-liquid reaction) Others were the same as in Production Example 1 or Production Example 2 (excluding the step of reacting N, N-diethylaminoethyl methacrylate), but each powder was obtained. The characteristics are shown in Table 3.

Then, in the dyeing process of Production Example 1, these powders were respectively obtained in the same manner except that Red No. 2 was replaced with Blue No. 1 (CI No. 42090) to obtain blue color pigments.

The dyeing results are shown in Table 3.

From the results shown in Table 3, even when the method for fixing the N, N-dialkylaminoethyl methacrylate polymer was the liquid-liquid reaction described above, the modified porous silk fibroin powder of Production Example 9 according to the present invention was excellent. It is apparent that it has dyeing properties.

Examples 1 to 5, Comparative Examples 1 to 3 [Lipstick] Various color pigments of Production Examples 1 to 9 were blended according to the description in Table 4 to prepare respective lipsticks of Examples or Comparative Examples, Various characteristics tests were conducted. The results are shown in Table 4.

(1) Composition (ingredient components) (blending amount) 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 pigment 10.0 (2) Preparation method Heat the oily ingredients to 90 ° C. After melt-mixing, the 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) Characteristics The results of various characteristics tested according to the above-mentioned test method are shown in Table 4.

As shown in Table 4, the lipsticks of Examples 1 to 5 are Comparative Example 1
It is superior in light resistance, heat resistance, bleed resistance, color tone and makeup lasting to the lipsticks of ~ 3. Further, Comparative Example 3 is a mixture of two colors of red and blue, but one of the colored pigments of Production Example 8 is inferior in light resistance, and therefore ΔE in the light resistance test.
Showed a high number.

Examples 6 to 10 and Comparative Examples 4 to 6 [Blushing] Various coloring pigments were blended in the same manner as in Example 1 to prepare each blushing, and various properties were tested. The result is the fifth
Described in the table.

(1) Composition (2) Preparation method After the component (A) is uniformly mixed, this is added to the dissolution mixture of the component (B) and mixed, and then crushed and sieved, and the resulting product is stamped with a mold. Each cheek red was prepared.

(3) Properties As shown in Table 5, the cheek red of Examples 6 to 10 of the present invention are excellent in various tests. However, the smoothness and wettability were found to be slightly inferior in terms of the feel of the practical test of Example 10, which is considered to be because the amount of the pigment fixed on the monomer exceeded 35%. On the other hand, in the case of the color pigment of the comparative example, when the monomer adhesion amount was 35% (Comparative Example 6), the original characteristics of silk fibroin were already impaired, and the evaluation points were extremely low in each item of the practical test. .

Example 11, Comparative Example 7 [Foundation cream] Various foundation pigments were prepared in the same manner as in Example 1 to prepare respective foundation creams, and various properties were tested. The results are shown in Table 5.

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

(3) Characteristics Comparative Example 7 is a mixture of two color pigments of red and yellow. One of the pigments of Production Example 7 is inferior in light resistance, heat resistance and bleeding resistance, so that ΔE is large. Showed the value.

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Claims (7)

[Claims] 1. A regenerated silk fibroin having a polymer mainly composed of N, N-dialkylaminoethyl methacrylate fixed thereto, wherein at least 50% by weight of the silk fibroin is composed of hot water-insoluble fibroin (β type). And
In addition, a makeup cosmetic in which a modified porous silk fibroin powder containing pores having a pore diameter of 1 μ or less and 300 μl / g or more is dyed with an acid dye to obtain a colored pigment. 2. The method according to claim 1, wherein the amount of the polymer having N, N-dialkylaminoethyl methacrylate as a main component fixed therein is 3 to 35% by weight based on the recycled silk fibroin. Makeup cosmetics. 3. The N, N-dialkylaminoethyl methacrylate is N, N-dimethylaminoethyl methacrylate or N, N-diethylaminoethyl methacrylate, as claimed in claim (1) or (2). Makeup cosmetics listed. 4. The makeup cosmetic composition according to claim 1, wherein the regenerated silk fibroin has a crystallinity of at least 10%. 5. The maximum diameter of the modified porous silk fibroin powder is
The makeup cosmetics according to claim (1), wherein the makeup cosmetic is 0.5 to 100 μm. 6. The makeup cosmetic according to claim 1, wherein the amount of the acid dye dyed is 7 to 30% by weight based on the modified porous silk fibroin powder. 7. A coloring pigment is blended in an amount of 1 to 50% by weight based on the total weight of prescription components.
Makeup cosmetics according to item.