JPS62415A - Make-up cosmetic - Google Patents

Abstract

PURPOSE:To obtain the titled cosmetic having excellent color, feeling and durability, etc., by dyeing specific modified porous silk fibroin powder with an acid dye, and using the dyed powder as a color pigment. CONSTITUTION:The objective cosmetic is colored with a color pigment produced by dyeing modified porous silk fibroin powder with an acid dye. The modified porous silk fibroin powder contains >=300mul/g of pores having pore diameter of <=1mu and is composed of a regenerated silk fibroin attached with a polymer composed mainly of N,N-dialkylaminoethyl methacrylate (preferably N,N- dimethylaminoethyl methacrylate or N,N-diethylaminoethyl methacrylate) wherein at least 50wt% of said silk fibroin is composed of a beta-type fibroin insoluble in hot water.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a make-up cosmetic comprising a specific modified porous silk fibroin powder dyed with an acid dye as a coloring pigment.

(Prior art) JP-A-57-191315 discloses a method in which a polymer containing N,N-dialkylaminoethyl methacrylate as a main component is fixed to silk fibroin powder (silk fiber powder, etc.) or regenerated silk fibroin powder. , a dark blue fibroin powder with improved dyeability, etc., and a method for producing the same have been proposed.

However, in the case of this invention, although conventional silk powder (silk fiber powder) or regenerated silk fibroin powder is modified in dyeability, fragrance retention, etc., this modified regenerated silk fibroin The powder was still impractical to be dyed with an acid dye and applied as a colored pigment to make-up cosmetics.

In the above publication, the amount of acid dye (red No. 2) dyed on simple regenerated silk fibroin powder was 0.2% by weight at most, but the amount of dyeing of a polymer of N, N-dialkylaminoethyl methacrylate was 2 to 105% by weight. It is described that the amount of dyeing (red No. 2) of the regenerated silk fibroin powder that has been fixed is increased to 1.7 to 27% by weight.

However, makeup cosmetics containing colored pigments made from these modified regenerated silk fibroin powders have not always been satisfactory in terms of color tone, feel, makeup wear, etc., which will be described later. That is, in order to satisfy the color tone of makeup cosmetics, it is necessary to sufficiently increase the dyeing amount of acid dye in the coloring pigment. If the amount of polymer adhesion is increased, there is a risk that the original characteristics of silk fibroin powder, such as smoothness (smoothness), extensibility (stretchability), and moisture retention (moist feeling) when applied to the skin, may be impaired. However, the conventional colored pigments based on modified silk live broin powder have the disadvantage that when trying to simultaneously satisfy both color tone, feel, and makeup durability, there is a certain limitation in the range of applicability.

(Disclosure of the Invention) Therefore, as a result of intensive research to solve the above problems, the present inventors found that (1) the specific modified porous silk fibroin powder described below, which forms the base of the colored pigment according to the present invention, has the following properties: The starting materials, silk and regenerated silk fibroin, are chemically and physically significantly different in form and properties, and have higher affinity and dyeability with acid dyes, and the colored pigments obtained by dyeing them are To be vividly colored and exhibit a good color tone.

(2) Moreover, this modified porous silk fibroin powder is
Compared to conventional modified silk fibroin powder, it maintains the original properties of silk fibroin powder, such as smoothness, extensibility, and moisture retention, even in areas where a large amount of N,N-dialkylaminoethyl methacrylate polymer is adhered. .

(3) In addition, the makeup cosmetics containing the color pigments of the present invention have improved light resistance, heat resistance, and bleed resistance as described below, and in practical tests have been shown to have improved color tone, feel, makeup durability, etc. To be able to impart and express an excellent, beautiful and stable cosmetic effect (make-up effect).

They discovered these and completed the present invention.

(Objective of the Invention) That is, the object of the present invention is to improve the color tone (color, brightness), feel (smoothness, spreadability, moisturizing properties), and long-lasting makeup (water resistance, sweat resistance, adhesion to the skin). Our aim is to provide excellent makeup cosmetics for various purposes.

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

(Specific description of the structure) The modified porous silk fibroin powder according to the present invention is as follows: (1) The porous silk fibroin powder produced as described below is added to the porous silk fibroin powder described in JP-A-57-191315. (2) A method of fixing a polymer containing N,N-dialkylaminoethyl methacrylate as a main component, followed by washing with water and drying (solid-liquid reaction) according to the method of JP-A-57-191315. After reacting an aqueous silk fibroin solution with N,N-dialkylaminoethyl methacrylate according to the method described in the publication, a water-insoluble A suspension is prepared by mixing microcrystalline precipitates or fine powders of carbonate (calcium carbonate, etc.), and then subjected to a treatment such as stirring at a high deformation speed to obtain coarse particles of modified regenerated silk fibroin. is generated.

These coarse particles are obtained by acid treatment to decompose and elute water-insoluble carbonates and generate carbon dioxide gas, followed by washing with water, drying, and pulverization (liquid-liquid reaction).

The porous silk fibroin powder according to the present invention is produced, for example, as follows. First, raw materials for silk fibroin include cocoon, raw silk, cocoon waste, raw silk waste, bis, fried cotton,
A silk cloth layer, a boulet, etc. are prepared by removing sericin in hot water in the presence of an activator or in the presence of an enzyme according to a conventional method, if necessary, and drying the scouring silk. The solvent is preferably an aqueous solution of calcium, magnesium, or zinc hydrochloride or nitrate from the viewpoint of cost and usage, and the concentration of these aqueous solutions depends on the type of solvent used, Although it varies depending on the temperature etc., the concentration of metal salts etc. is usually 10
~80% by weight, preferably 20-70% by weight, particularly preferably 25-60% 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 fibroin aqueous solution becomes long and uneconomical, while if it exceeds 20% by weight,
It may be difficult to dehydrate the recycled fibroin powder during the water washing and drying steps. Further, outside both of the above ranges, the proportion of hot water-insoluble fibroin (β-structuring rate) is small, and regenerated fibroin tends to stick in sweat or an aqueous dispersion medium, or to easily form into secondary particles. The suspension containing a water-insoluble carbonate includes at least one of calcium, magnesium, or zinc hydrochloride or nitrate in an aqueous silk fibroin solution.
A carbonate of calcium, magnesium or zinc may be precipitated as water-insoluble fine particles by dissolving the seeds and adding a readily water-soluble carbonate to the solution. , which also happens to be the raw material for the water-insoluble carbonate, is a hydrochloride or nitrate of calcium, magnesium, or zinc in an amount calculated from a predetermined amount (approximately equivalent amount) of the water-insoluble carbonate to be encapsulated in the intermediate coarse particles. The silk fibroin raw material may be dissolved and used as it is in the next step without desalting. However, it is more preferable that the silk fibroin aqueous solution is subjected to dialysis desalination to completely remove the hydrochloride or nitrate used to dissolve the silk fibroin raw material. Low-molecular-weight silk fibroin that is naturally present or generated during dissolution during dialysis and reduces the product's performance as a cosmetic base, and iron ions that interfere with color development during dyeing and are mixed in from raw materials or reaction systems. can be completely removed. In this case, when producing a water-insoluble carbonate in the reaction system, it is necessary to add a predetermined amount of the hydrochloride or nitrate again.

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

The silk fibroin aqueous solution in which the fine particles are suspended is subjected to at least one type of treatment, such as mixing a coagulating salt or stirring at a high sliding deformation speed of 50/sec or more, to regenerate silk fibroin. The regenerated string fibroin coarse particles are coarse gel bodies that coat and encapsulate water-cooling carbonate fine particles.

The coarse particulate gel body is added to the silk fibroin aqueous solution purified by dialysis and desalting, with an average particle size of Iμ or less, preferably 0.1 μm.
It can also be regenerated in a similar manner from an aqueous silk fibroin solution in which light calcium carbonate with a particle size of less than μ is suspended.

The amount of carbonate fine particles in the coarse particles is 20 to 8
0% by weight is preferred, and 30-70% by weight is more preferred. If it is less than 20% by weight, the amount of micropores decreases, while 80%
If the weight percentage is exceeded, the amount of micropores of 1 μ or less will freeze,
There is a tendency for the amount of micropores of 1μ or more to increase.

When using a coagulating salt, for example, concentrated aqueous solutions of sodium chloride, potassium chloride, sodium nitrate, potassium nitrate, etc. are mixed and stirred to precipitate silk fibroin. The concentration of the coagulating salt is adjusted so that the concentration of the mixed solution with the aqueous silk fibroin solution is usually 5 to 10% by weight.

Silk fibroin can be precipitated by stirring alone, but in this case it must be carried out at a fast deformation rate, usually 50/Sec.
, preferably 100/See.

It is carried out at the above sliding deformation speed. The stirring time varies depending on the concentration of the aqueous solution, the rate of sliding deformation, etc., but gelation is usually achieved in one hour or more.

It is an intermediate (■ Fibroin coarse particles are filtered, washed with water, dried in some cases, and then coarsely pulverized and then treated with an acid to decompose the carbonate fine particles. Hydrochloric acid, acetic acid, or citric acid is suitable as the acid. However, care must be taken when using sulfuric acid as it may generate sulfates that are poorly soluble in water.The amount of acid should preferably be equivalent to or slightly in excess of the carbonate contained in the coating, but
The following should be avoided as there is a risk that the silk fibroin will become brittle. Completion of acid decomposition can be confirmed by the termination of carbon dioxide gas generation, and then the obtained porous silk fibroin powder is washed with water and dehydrated. It is preferable to use a centrifugal dehydrator for dehydration, and by this dehydration, the porous silk fibroin powder is usually dehydrated to about 100 to 500% by weight based on the dry product. After dehydration, it can be easily dried to an absolutely dry state. Drying is carried out at a temperature of 60 to 60℃ under normal pressure or reduced pressure.
It is carried out at 120°C.

The dried product thus obtained is easily pulverized by using a pulverizer such as a hammer mill or jet mill. The particle size (maximum particle size) is usually 0.5 to 100μ,
It is preferably adjusted to 1 to 60μ, particularly preferably 3 to 30μ.

When the maximum particle size is larger than 100μ, adhesion to the skin, affinity, extensibility, etc. change (easily).

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 constituted by hot water-insoluble fibroin (β-type structure). 50% by weight
If the hydrophilicity of fibroin is extremely strong, water or sweat may cause adhesion and caking, causing the pigment particles to become secondary particles (particles aggregate to form giant particles), or the water dispersion medium ( In water-based cosmetics, the film tends to be detached, and in oil dispersion media (oil-based cosmetics), the dispersibility tends to decrease.Furthermore, the spreadability and feel during application become poor.

In the present invention, hot water-insoluble fibroin means 100%
This refers to fibroin that does not dissolve even when boiled in hot water at ℃ for 15 minutes.

In the hot water-insoluble fibroin, the intermolecular hydrogen bonds of the fibroin are substantially in the β structure.

Although the crystallinity of the regenerated fibroin varies slightly depending on the conditions of the manufacturing process, it is usually 10% or more, preferably 2.
It is 0% or more and does not exceed 43%. This is considerably lower than the crystallinity of silk fibers (50% or more), and the degree of molecular orientation is also low, at 1/2 or less of that of silk fibers. This point is considered to be the reason why regenerated fibroin has a more favorable effect as a cosmetic base than simply modified fibroin.

In addition, during the manufacturing process, by performing heat recording treatment before drying, after drying, or after pulverizing the regenerated fibroin powder, p-water insolubilization of fibroin (proportion of hot water-insoluble fibroin, β-structuring rate) is further promoted ( ), and the above-mentioned properties can be further improved.

As for the wet temperature treatment, the powder after drying or pulverization is
Heat treatment with saturated steam at 0°C or above, especially 80-120°C, or before drying, add sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium nitrate,
This is carried out by heat treatment in a neutral salt aqueous solution such as potassium nitrate or an organic solvent such as acetone or alcohol. When performing these thermal treatments, it is possible to promote the hot water insolubilization of the regenerated fibroin (increase in the β-structuring rate) as described above, and further increase the crystallinity of the fibroin, resulting in excellent and moderate hydrophilicity. It is easy to obtain a fibroin-coated pigment that has a good balance between oil and lipophilicity, antiperspirant properties, dispersibility in a dispersion medium, and color fastness.

Furthermore, the porous silk fibroin powder according to the present invention has a structure in which the regenerated silk fibroin has countless fine pores, and the amount of pores with a pore diameter of 1 μ or less is 300 μI/g or more, preferably 4° OμI/g. That's all.

Compared to ordinary powdered regenerated silk fibroin or silk thread, which is simply pulverized as it is or which has been embrittled through chemical treatment, the amount of voids (Void: micropores) is at most 200μI/g. Therefore, in the case of the porous silk fibroin powder according to the present invention, the amount of micropores is extremely large, and therefore, as described later, the color is very deep even when dyed with acid dyes, etc., and has good water and light fastness. pigments can be obtained.

The reason why the porous silk fibroin powder according to the present invention noticeably increases and improves the dyeing amount and fastness of the dye due to the increase in the amount of fine pores is not clear, but it is probably due to the high adsorption performance of activated carbon. This is thought to be caused by the same principle.

Next, add N to this porous silk fibroin powder.

To react with N-dialkylaminoethyl methacrylate to obtain modified porous silk fibroin powder (solid-reaction), add 3 to 50% by weight of fibroin (purity) to a suspension of porous silk fibroin powder in water. % weight, N-dialkylaminoethyl methacrylate added and mixed, N
.

0 for N-dialkylaminoethyl methacrylate
．． The reaction may be carried out at a temperature of 40 to 80° C. for 2 to 6 hours in the presence of 5 to 5% by weight of a radical polymerization catalyst (for example, ammonium persulfate, etc.).

Next, the silk fibroin powder is collected by filtration, washed with water, dehydrated and dried, and re-pulverized if necessary to obtain the desired modified porous 1) fibroin powder.

In addition, when producing the modified porous silk fibroin powder of the present invention by the liquid-reacting method described above, an aqueous silk fibroin solution is used in place of the porous silk fibroin powder Qifi solution in the solid-reacting method, and the above-mentioned After reacting N,N-dialkylaminoethyl methacrylate under the same conditions as above, a microcrystalline precipitate or fine powder of water-insoluble carbonate is mixed with the reaction solution, and further the method for producing the porous composite fibroin powder. A method similar to that described above can be used, and the same desired modified porous fibroin powder can be obtained.

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

In addition, within the limits that do not impair the essence of the present invention, N, N
It is also possible to fix a copolymer of dialkylaminoethyl methacrylate and other acrylic monomers, ethylenically unsaturated compounds such as vinyl compounds to silk fibroin.

The amount of N,N-dialkylaminoethyl methacrylate added to the string fibroin is preferably 3 to 50% by weight, and if it is less than 3% by weight, the desired amount of acid dye cannot be sufficiently dyed, and if it is 50% by weight. If it exceeds this amount, there is a risk that the inherent characteristics of silk in the resulting colored pigment may be impaired. That is,
In the present invention, the amount of N,N-dialkylaminoethyl methacrylate added is such that the amount of the polymer fixed is 3 to 3.
Any amount suitable for 5% by weight may be used. The modified porous silk fibroin powder according to the present invention can be manufactured by appropriately adjusting the powder according to the description in JP-A-57-191315, within a range that achieves the object of the present invention.

This modified porous silk fibroin powder has (1) as described above, at least 50% by weight of the constituent regenerated silk fibroin is hot water-insoluble fibroin, the degree of crystallinity is 10% to 43%, and the pore size is 1 μm. 300 or less pores
Be porous with a content of μl/g or more.

(2) In addition, the polymer containing N,N-dialkylaminoethyl methacrylate as a main component is fixed to a degree that does not impair the inherent properties of the silk fibroin powder, and the number of amino groups is increased.

Due to these factors, the adsorption activity of acid dyes increases dramatically, and the coloring properties (color tone and clarity) of the resulting colored pigments are better than ever, and the characteristics of silk fibroin powder, such as smoothness, extensibility, It has moisturizing properties. Furthermore, makeup cosmetics containing this colored pigment exhibit significantly excellent properties as described above.

The acidic dye according to the present invention is a water-soluble acidic dye,
For example, Red No. 2 (C1-16185), Red No. 3 (C
1 45430), Red No. 102 (C1) 1h1625
5), Red No. 104 (C1 45410), Red 227
No. (C1 17200), Red No. 401 ((llllh4
5190), red No. 504 (C1 floor 14700), yellow No. 4 (C1 floor 19140), yellow No. 5 (CIIIkL,
15985), yellow number 203 ((l 47005), yellow number 403 (CINafO316), blue number 1 (C1 floor 14700), blue number 2 CC1 case 73015), green 3
No. (CIN [L42053), Green No. 201 CC1 South 61570), Green No. 1205 (CI No. 42095),
Green No. 402 (CI!m42085), Brown No. 201 (
+j 隘20170) etc. are exemplified as preferred. The dyeing method with acid dyes involves dispersing modified porous silk fibroin powder in an aqueous acid dye solution, adding an acid (hydrochloric acid, acetic acid, etc.) to adjust the pH to acidic, and then heating it to 70-100°C. This is carried out by dyeing, followed by dehydration, washing with water, and drying, and thus the colored pigment according to the present invention is obtained.

The content of the colored 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 prescription ingredients. The make-up cosmetic composition of the present invention can be colored to a desired hue with the above-mentioned colored pigments, but if necessary, a small amount of a non-colored Ia pigment or an organic pigment can also be blended.

The bases used in the make-up cosmetics of the present invention are not particularly limited, but are well-known and commonly used bases for make-up cosmetics, such as inorganic pigments, extender pigments, oily substances, fragrances, etc. The make-up cosmetics are extremely useful as, for example, lipsticks, eye shadows, rouges, foundations, and the like.

(Effects of the Invention) The makeup cosmetic of the present invention has excellent color development and is light resistant by incorporating modified porous silk fibroin powder dyed with an acid dye that retains the original characteristics of silk fibroin. properties, heat resistance, bleed resistance, color tone (
color, brightness), texture (smoothness, extensibility, moisture retention)
It has excellent makeup retention (water resistance, sweat resistance, adhesion to the skin), etc., and can provide beautiful and stable cosmetic effects, and its commercial value is extremely high.

Examples will be described below.

In addition, % shown in Examples means % by weight, and parts means parts by weight. In addition, the test methods for light resistance, heat resistance, bleed resistance, and practical tests (sensory tests) of makeup cosmetics are as follows.

(1) Prepare two light resistance test samples, one placed in a sunlight box (glass case) and exposed to sunlight for 3 weeks, and one placed in a cool dark place for 3 weeks.
After storage for a week, the colors of both samples and visual observations were compared, and the light resistance was determined from the degree of color change.

(2) Two heat resistance test samples were prepared; one was kept in a constant temperature bath with the internal temperature adjusted to 50℃ for 3 months, and the other was kept in a cool dark place (5℃) for 3 months.
The samples were stored for several months, and the colors of both samples were compared by visual observation, and the heat resistance was determined from the degree of color change.

In addition, in the light resistance test in 1)) and this heat resistance test, the L value of the Hunter colorimetric system, a
The value and b value were measured using a spectrophotometer (manufactured by Murakami Color Research Co., Ltd.), and the color difference ΔE was calculated from the following formula and displayed.

ΔE (color difference) = (ΔL) “10 (Δa)” + (Δb). If the ΔE value (color difference value) is 5 or less, the colors of both samples appear to be the same to the naked eye and there is no color difference; If it is 10 or less, a slight color difference will be felt, and if it is 10 or more and 20 or less, the color difference can be clearly determined.

Furthermore, when the ΔE value is 20 or more, the color difference becomes even larger.

(3) Bleed resistance test 1 g of the sample was placed in 150 cc of boiling axillary water, boiled for 2.5 hours, and the degree of elution of the acidic dye into the water layer (the extent to which the water was colored) was observed with the naked eye. Bleed resistance was determined.

Next, the amount of dye was determined by measuring the absorbance of the dye eluted into the aqueous layer, and the dye residual rate was determined from the following formula, which was used as a measure of bleed resistance.

(4) Practical test (sensory test) Using samples of makeup cosmetics for two months, color 1)
A sensory test was conducted by 30 female panelists regarding (color, brightness), feel (smoothness, spreadability, moisturizing properties), and makeup retention (water resistance, sweat resistance, adhesion to the skin). The results were displayed as sensory evaluation points. For each questionnaire item (test item), the sensory evaluation score is 5 points for those who answered good, 3 points for those who answered fair, and 1 point for those who answered poor.
This is the average score of 30 people.

Production Examples 1 to 2 Using silk spinning waste as a raw material for silk fibroin, 10 of this
0 parts with a solution of 30 parts of Marcel soap and 3000 parts of water.
Stirring and scouring at 5 to 98°C for 3 hours to reduce residual glue to 0.1%
After washing with water, it was dried with hot air at 80°C.

200 parts of water was mixed with 200 parts of calcium chloride (Ca C 1 g.2 HzO) to prepare 400 parts of a 38% by weight calcium chloride aqueous solution, and 1) it was heated to 0°C. 80 parts of refined silk waste was added to the mixture using a kneader while stirring for 5 minutes, and the mixture was further stirred for 30 minutes to completely dissolve it.

Next, 2,000 regenerated cellulose-based hollow fibers with an inner diameter of 200μ, a membrane thickness of 20μ, and a length of 500m were bundled together, and both ends of the fibers were bundled and fixed (sealed) without blocking the hollow holes using a hollow fiber type dialysis device. , each of the above solutions was added to 0.
1) Dialyzed using deionized water to obtain a string fibroin aqueous 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 added to 100/S e
The mixture was stirred at a high speed so as to give a sliding deformation speed of .c. When stirring was continued for 2 to 3 hours, silk fibroin gradually precipitated and finally solidified as a small gel aggregate. The gel aggregate is filtered, washed with water, dried, and then ground with a jet mill.
15 parts of regenerated silk fibroin powder according to the description in No. 449 was obtained. (Production Example 1) In addition, 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 it had completely dissolved, 1. 200 cc was gradually added to precipitate fine crystals of calcium carbonate. Since the reaction is quantitatively completed at the same time as the addition of sodium carbonate is completed, one portion of the silk fibroin aqueous solution in which the carbonate fine particles are suspended is added.
The mixture was stirred at high speed so as to give a deformation speed of 00/Sec or more.

When the stirring was continued for 2 to 3 hours, silk fibroin containing calcium carbonate gradually precipitated, and finally the entire mixture solidified as a small gel aggregate.

The gel aggregate was filtered, washed with water, dried, and ground in a hammer mill to obtain about 33 parts of coarse powder.

The obtained pulverized material was suspended in 200 parts of water, and 40 parts of concentrated hydrochloric acid was gradually introduced into the suspension. The reaction solution foams violently due to the generated carbon dioxide gas.

After confirming that the generation of carbon dioxide gas had ended, stirring was continued for another 2 to 3 hours. After completion of the reaction, the precipitate was filtered, washed with water, dried, and pulverized with a jet mill to obtain 13 parts of fine particles of porous silk fibroin powder according to the present invention (Production Example 2).
). This result shows that the amount of calcium carbonate fine particles in the coarse particles was about 60% by weight. Production example 1.2
The average particle diameters of the silk fibroin powders were 13.0 μm and 12.5 μm, respectively, as measured by a Colecoo counter.

In addition, in the case of Production Example 2, the amount of micropores measured by mercury porosimetry showed that it was porous with a pore size of 1 μ or less of 630 /Z I / g, but the recycled silk fibroin powder of Production Example I or simply fiber The amount of pores of 1μ or less in each of the silk fibroin powders obtained by pulverizing the powder was 200μI/g or less.

The crystallinity of the porous M'4N fibroin powder of Production Example 2 was 18% as a result of X-ray measurement, and the proportion of hot water-insoluble fibroin (β-structuring rate) was 80% by weight.

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

The amount of N,N-dimethylaminoethyl methacrylate polymer fixed was calculated based on the weight increase rate for each powder, and
The content of the regenerated silk fibroin powder of No. 1 was 6.0% by weight, and the content of the porous set fibroin powder of Production Example 2 was 12% by weight.

Furthermore, 30 parts each of the modified powders of Production Examples 1 and 2 and 10 parts of Red No. 2 (Crllh16185) were dissolved in 1000 parts of water, and the solution was added to an aqueous solution whose pH was adjusted to 1°5 with hydrochloric acid and dispersed. The mixture was bundled at 80 to 100°C for 1 hour, washed with water, and dried to obtain a red colored pigment. The amount of dyeing is calculated from the amount of dye remaining in the dyeing solution.Production Examples 3 to 7 A silk fibroin aqueous solution is prepared by dissolving and dialysis according to Production Example 2, and calcium chloride and sodium carbonate are added to the solution. ,
Various modified porous silk fibroin powders were prepared in the same manner as in Production Example 2, except that the amount of calcium carbonate in the intermediate coarse particles was adjusted to the amount shown in Table 1 by increasing and decreasing all of the amount and hydrochloric acid at the same rate. This was further 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 is 2
0 to 80% is a desirable range in terms of the dyeing amount of Red No. 2,
It can be seen that outside this range, the amount of fine pores becomes less than 300 μl/g, which is inappropriate.

In addition, the crystallinity of the regenerated silk fibroin in the powders of Production Examples 1 to 7 was in the range of 15 to 30%.
~(1-6), (2-1) ~(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 3.5.
~50% by weight, and the catalyst, ammonium persulfate, was added to 2% by weight based on 70% of the total amount of N.
, various powders having different adhesion amounts of N-dimethylaminoethyl methacrylate polymer were obtained as shown in Table 2 (3rd and 7th stage).

Next, 30 parts of each of these powders and Yellow No. 4 (CINa
19140) was dissolved in 1000 parts of water, each colored pigment was obtained in the same manner as the dyeing process of Production Example 1, and the dyeing amount was shown in Table 2 (4 or less, the remainder (white in Table 2). As shown, the modified regenerated fibroin powder (pore volume 150 μI/g) of Production Example 1 is different from the modified porous silk fibroin powder according to the present invention (pore volume 630 μI/g) of Production Example 2.
μl/g), the monomer reaction fixation rate is low,
Moreover, even if the amount of fixation is 1) to 35% by weight, the amount of dyeing is 8.
It showed only a low value of 0 to 16% by weight, and furthermore, as described later, when the amount of monomer fixed was 26% by weight or more, the original properties of silk fibroin powder tended to be impaired. In the case of the powder of Production Example 2, the amount of 7-mer fixation was 3.0% by weight and the amount of dyeing was 7.0% by weight, and the dyeing property of Yellow No. 4 was excellent.

In addition, as will be described later, it is a phenomenon that should be noted in the present invention that even when the amount of monomers fixed reaches 35% by weight, the original properties of the silk fibroin powder were not impaired to a large extent, and this is due to the characteristics of the porous powder. considered to be a thing.

Production Examples 8 to 9 In Production Examples 1 and 2, N, N
- 1.3 parts of diethylaminoethyl methacrylate (monomer/fibroin = 0, 1), 0.2 parts of a nonionic surfactant, and 0.026 parts of hydrogen peroxide and 0.026 parts of acidic sodium sulfite as catalysts were added. , temperature 60℃
Silk fibroin was reacted for 4 hours with N,N-
Other than fixing the polymer of diethylaminoethyl methacrylate (liquid-liquid reaction), the procedure was the same as Production Example 1 or Production Example 2 (except for the step of reacting N, N-diethylaminoethyl methacrylate). The properties are shown in Table 3.

Next, blue colored pigments were obtained using these powders in the same manner as in Production Example 1 except that Red No. 2 was replaced with Blue No. 1 (CIN142090).

The dyeing results are shown in Table 3.

From the results in Table 3, even when the method of fixing the N,N-dialkylaminoethyl methacrylate polymer is the aforementioned liquid-liquid reaction, the modified porous silk fibroin powder of Production Example 9 according to the present invention is superior. It is clear that it has dyeing properties.

Examples 1 to 5, Comparative Examples 1 to 3 [Lipstick] The various coloring pigments of Production Examples 1 to 9 were blended according to the description in Table 4 to prepare each lipstick that is an example or a comparative example. , and conducted tests on its properties.

The results are listed in Table 4.

(1) &II composition (raw ingredients) (compounding amount parts) Candelilla wax 4.0 Solid paraffin 8.0 Beeswax
5.0 carnauba wax
5.0 lanolin
1). 0 isopropyl myrite) 15.
0 Castor oil 42. .

Colored pigment 10.0 (2) Preparation method After heating the oily raw materials to a temperature of 90°C and dissolving and mixing,
Colored pigments were added to the mixture and kneaded by rollers, then melted again, poured into molds, and cooled to prepare each lipstick.

(3) Properties The results of various properties tested according to the above test method are listed in Table 4.

As shown in Table 4, the lipsticks of Examples 1 to 5 are the same as Comparative Example 1.
It has better light resistance, heat resistance, bleed resistance, color tone, and makeup retention than the lipsticks No. 3 to 3. Further, Comparative Example 3 is a mixture of two colors, red and blue, but one of them, the colored pigment of Production Example 8, had poor light resistance, so the 8E of the light resistance test showed a high value.

Examples 6 to 10, Comparative Examples 4 to 6 [Ha Red] In the same manner as in Example 1, various color pigments were blended to prepare each almost red color, and tests on various properties were conducted. The result is the fifth
Record in the table.

(1) Mi composition (raw ingredients) (compounding amount parts) 17 care 1, 7 1. .

(2) Preparation method After uniformly mixing the (A) component, this is added to the dissolved mixture of the (B) component, mixed, and then pulverized and sieved, and then molded. Each almost red was prepared.

(3) Characteristics As shown in Table 5, almost all of Examples 6 to 10 of the present invention were excellent in various tests.

However, in the feel section of the practical test of Example 10, it was observed that the smoothness and wettability were slightly inferior, but this is thought to be due to the amount of fixed monomer of the color pigment exceeding 35%.

On the other hand, in the case of the colored pigment of the comparative example, the monomer adhesion amount was 3.
At 5% (Comparative Example 6), the original properties of silk fibroin were already impaired, and the evaluation scores were extremely low in each item of the practical test.

Example 1), Comparative Example 7 [Foundation Cream] In the same manner as in Example 1, various colored pigments were blended to prepare foundation creams, and tests on various properties were conducted. The results are listed in Table 5. (1) Composition (raw materials) (Amount: parts) 1 stearic acid 8.0 (2) Preparation method Components (A) and (B) were heated, mixed and melted at a temperature of 80°C. Component (A) was mixed into component (B) to emulsify and disperse the mixture, and the mixture was cooled to 30° C. with stirring to prepare each foundation cream.

(3) Characteristics Comparative Example 7 is a mixture of two colored pigments, red and yellow, but one of the pigments in Production Example 7 is inferior in light resistance, heat resistance, and bleed resistance, so 8E is showed a large value.

Claims (7)

[Claims] (1) Consisting of regenerated silk fibroin to which a polymer containing N,N-dialkylaminoethyl methacrylate as a main component is fixed, at least 50% by weight of the silk fibroin
Modified porous silk fibroin powder, which is composed of hot water-insoluble fibroin (β type) and contains 300 μl/g or more of pores with a pore size of 1 μ or less, is colored with a colored pigment obtained by dyeing with an acid dye. make-up cosmetics. (2) Claim No. 1, wherein the amount of the polymer mainly composed of N,N-dialkylaminoethyl methacrylate is 3 to 35% by weight based on the regenerated silk fibroin.
Make-up cosmetics described in section. (3) Claims (1) or (2), wherein the N,N-dialkylaminoethyl methacrylate is N,N-dimethylaminoethyl methacrylate or N,N-diethylaminoethyl methacrylate. Make-up cosmetics. (4) The crystallinity of the regenerated silk fibroin is at least 10
% of the makeup cosmetic according to claim (1). (5) The maximum diameter of modified porous silk fibroin powder is 0.5
The makeup cosmetic according to claim (1), which has a particle size of 100μ. (6) The amount of dyed acid dye is 7 to 30% by weight based on the modified porous silk fibroin powder.
The makeup cosmetics described in item 1). (7) The coloring pigment is 1 to 1 based on the total weight of the prescription ingredients.
The makeup cosmetic according to claim (1), which contains 50% by weight.