JPH0579260B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a fine powder of oily body occluding and regenerating protein and a method for producing the same. (Prior Art) Regenerated protein fine powder, especially regenerated silk fibroin powder, has properties such as appropriate hygroscopicity and moisture retention, excellent affinity for the skin, good hydrophilicity-lipophilic balance, and ultraviolet absorption. It has been used mainly as an additive to make-up cosmetic bases (Japanese Patent Publication No. 38449/1983). In addition, the present inventors utilized the above-mentioned favorable properties of silk fibroin to improve adhesion, spreadability, dispersibility, and miscibility by substantially covering the particle surface of common pigments with a regenerated silk fibroin film. , Pigments for paints and cosmetics with outstanding coating properties, oil absorption properties, balance between hydrophilicity and lipophilicity, anti-perspirant properties, texture, skin protection properties, dyeing properties, etc., and a method for producing the same, as Japanese Patent Publication No. 57-11577. provided. In recent years, as paints and cosmetics have become more sophisticated, the conventional general functions of pigments are no longer sufficient, and a wider range of sophisticated so-called high functions are required.
The reality is that the above-mentioned functions alone are no longer sufficient for silk fibroin skin pigments. One way to improve the functionality of pigments is to combine them with highly functional ingredients.In this case, if the pigment is intended to be used as a base for paints or cosmetics, it may be difficult to dissolve it in water or sweat. In order to avoid caking and caking, the highly functional ingredients are preferably oil-based. Conventionally, the method for treating oily pigments is to dilute the oily body with an appropriate solvent to about the same amount as the treated pigment, mix and suspend the pigment therein, and then distill off the solvent while stirring. It is true. However, in this method, since the oily substance is merely attached to the surface of the pigment particles, there is a problem that only a very small amount of the oily substance can be mixed with the pigment. In other words, in the case of a method that involves simply adhering to the pigment surface, the oily substance on the pigment surface acts as a binder as the solvent is distilled off, and if the amount of oily substance is large, the final product obtained is a pigment in the form of lumps. It is in a state where it hardens and is extremely prone to caking. For this reason, in conventional methods, the amount of oily material is limited to at most 1 to 2% by weight based on the pigment. In addition, the conventional method requires explosion-proof equipment because it uses a solvent, and also requires equipment for recovering and purifying the solvent, which has the disadvantage that the equipment is too large for the amount of production. Furthermore, even when the amount of oily substance is limited to 1 to 2% by weight or less based on the pigment, the resulting product often has poor adhesion, spreadability, dispersibility, and miscibility, for example as a base for cosmetics. It had various problems in use, such as the inability to mix it in large quantities. (Problems to be Solved by the Invention) The present invention improves the drawbacks of the prior art, and its purpose is to incorporate a high percentage of highly functional oily material, and to have good adhesion and extensibility. , Concealability,
To provide a fine powder that has excellent dispersibility, miscibility, balance between hydrophilicity and lipophilicity, anti-perspirant properties, feel, and skin protection properties and is extremely useful for cosmetics, food, paints, etc., and to use it industrially. An object of the present invention is to provide an advantageous manufacturing method. (Means for Solving the Problems) That is, the present invention provides an oil-based protein which is made of a regenerated protein in the form of a fine powder or a regenerated protein containing a base pigment, and in which an oil-based body is dispersed and built into the fine powder in the form of minute droplets. The method of the present invention involves isoelectric point coagulation, isoelectric focusing, and emulsion suspension of a protein aqueous solution mixed with an oily body, or an oily body and a base pigment.
and/or mixing a protein coagulant and/or stirring at a high shear deformation rate to coagulate and precipitate the regenerated protein containing minute droplets of the oily body or the droplets and a base pigment dispersed therein; It is then washed with water, dried and pulverized. The oil-based occluded and regenerated protein fine powder of the present invention has a regenerated protein or a complex of a base pigment and a regenerated protein,
It has a structure in which oily material is dispersed and occluded in the form of minute droplets, and the amount of oily material is 0.5 to 0.5 of the powder.
The amount is preferably in the range of 50% by weight, and 25 times (by weight) or less the amount of regenerated protein, and more preferably 1 to 20% by weight of the powder and not more than 10 times (by weight) the amount of regenerated protein. If the amount of oily material is less than 0.5% by weight, it tends to become a powder in which the function of the oily material is hardly recognized, and if it exceeds 50% by weight of the powder or exceeds 25 times the amount of regenerated protein, the oily material may occlude. It tends to seep out onto the outer surface of the powder, causing the powder to harden into lumps, and resulting in poor performance as a cosmetic base, such as smoothness and dispersibility. The oily substances applicable to the present invention include animal and vegetable oils, waxes, higher aliphatic hydrocarbons, higher fatty acids, higher alcohols, ester oils, silicone oils, benzene-based synthetic fragrances, terpene-based synthetic fragrances, musk-based synthetic fragrances, and the like. For example, animal and vegetable oils such as safflower oil, wheat germ oil, olive oil and lanolin, waxes such as ceresin, vitamin E, higher aliphatic hydrocarbons such as squalane, linolenic acid, myristic acid, etc. higher fatty acids such as oleyl alcohol, higher alcohols such as oleyl alcohol, ester oils such as dimethylaminobenzoic acid ester, stearic acid ester, oleic acid ester, various silicone oils, benzene-based synthetic fragrances such as coumarin and heliotropin, macrocyclic musk, etc. Examples include musk-based synthetic fragrances and terpene-based synthetic fragrances such as citronellol and ionone. Various proteins can be used as raw materials for the regenerated protein applied to the present invention, but it is particularly preferable to use silk fibroin, casein, and collagen as raw materials and make an aqueous solution by a known conventional method, and then regenerate the resulting protein. Silk fibroin raw materials to be applied to the present invention include cocoons, raw silk, cocoon scraps, raw silk scraps, bis, fried cotton, silk cloth scraps, boulettes, etc., in hot water or enzymatically in the presence of an activator as necessary according to a conventional method. Refined silk, which has been dried after removing sericin in hot water, is used for dissolution, for example, by the method described in Japanese Patent Publication No. 58-38449. Aqueous solutions of hydrochloride or nitrate are preferred. The salt concentration of these aqueous solutions varies depending on the type of solvent used, temperature, etc., but the concentration of metal salts etc. is usually 10 to 80% by weight, preferably 20 to 70% by weight, particularly preferably 25 to 60% by weight. . Further, 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. The casein used in the present invention is generally prepared by dissolving commercially available milk casein or soybean casein in a dilute aqueous sodium hydroxide solution of 0.1 to 1.0% (by weight), and separating the insoluble matter before use. Collagen applied to the present invention, especially atelocollagen, can be obtained by, for example, crushing young cow skin, dispersing it in water, adjusting the pH to 1.5 to 4.0, and adding acid-resistant protease (e.g. pepsin) to it. Continue stirring for several days, and remove insoluble matter by filtration to obtain an aqueous solution. The protein concentration of the aqueous protein 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 the concentration is less than 2% by weight, the regeneration time of the aqueous protein solution becomes long and uneconomical, while if it exceeds 20% by weight, dehydration during washing and drying steps may be difficult. When the protein is silk fibroin, the regenerated silk fibroin is composed of at least 50% by weight, preferably at least 90% by weight of hot water-insoluble fibroin (β-type structure). If it is less than 50% by weight, the hydrophilicity of fibroin becomes extremely strong, causing adhesion and caking with water and sweat, resulting in powder particles becoming secondary particles (particles aggregate to form giant particles) and becoming dispersible in water. Dispersibility tends to decrease in media (water-based paints and cosmetics) and oil dispersion media (oil-based paints and cosmetics). Also, the spreadability and feel during application become worse. The aforementioned hot water-insoluble fibroin refers to fibroin that does not dissolve even when boiled in hot water at 100°C for 15 minutes. In the hot water-insoluble silk fibroin, the intermolecular hydrogen bonds of the fibroin are substantially in the β structure. Although the degree of crystallinity of regenerated silk fibroin varies slightly depending on the various conditions of the manufacturing process, it is usually 10% or more, preferably 20% or more, and does not exceed 43%. This is considerably lower than the crystallinity of silk fibers (more than 50%), and the degree of molecular orientation is also low, less than half that of silk fibers. The proportion of hot water insolubility, degree of crystallinity, etc. of regenerated silk fibroin can be controlled within a predetermined range by selecting the regeneration method from an aqueous solution. The base pigment in the oil-based occluded and regenerated protein fine powder of the present invention is a white pigment for paints or cosmetics,
A general term for extender pigments, pearl pigments, etc., such as talc, kaolin, mica, titanium oxide, zinc oxide, titanium mica, calcium carbonate, magnesium carbonate, zinc stearate, magnesium stearate, magnesium silicate, organic pigments, Compounds thereof can be mentioned, and they can be applied singly or in combination of two or more. The maximum particle size of the base pigment is usually 0.03-20μ. In the present invention, the base pigment is 0% for regenerated protein.
~49 times (weight), more preferably 0 to 20
It is twice (weight). The maximum particle size of the oil-based occluded and regenerated protein fine powder of the present invention is usually 0.5-100μ, preferably 1-60μ, particularly preferably 3-30μ. When the maximum particle size is larger than 100μ, adhesion to the skin, affinity, spreadability, etc. tend to deteriorate. The method of the present invention involves isoelectric point coagulation and/or mixing of a protein coagulant into an emulsion obtained by mixing and stirring an oily substance in an aqueous protein solution, and/or a high shear deformation rate which is particularly useful when the regenerated protein is silk fibroin. The protein is coagulated and regenerated by stirring, etc., and at the same time, the oily substance that has been emulsified is dispersed and occluded in the form of minute droplets inside the coagulated body. When a base pigment is used in combination, a predetermined amount of the base pigment is suspended in an emulsion, and a fine powder containing the base pigment can be obtained through the same regeneration process as described above. When the protein regeneration method is isoelectric point coagulation, when the protein is silk fibroin or casein, the pH is 4.0~
5.0, when the protein is collagen, pH = 7-8
Stir for at least 10 minutes. When a coagulating salt is used, for example, a concentrated aqueous solution of sodium chloride, ammonium sulfate, sodium sulfate, potassium sulfate, etc. is mixed and stirred to regenerate and precipitate the protein. The amount of coagulating salt is usually such that the concentration of the mixture with the aqueous solution is 5~
Adjust to 10% by weight. When the protein aqueous solution is silk fibroin aqueous solution,
Silk fibroin can be regenerated into gel powder by isoelectric point coagulation or by mixing with coagulating salts, but preferably at 50/sec.
Stirring treatment at a high shear deformation rate of 100/sec. or more allows regeneration in particularly favorable conditions. The stirring time varies depending on the concentration of the aqueous solution, shear deformation rate, etc., but gelation is usually achieved in one hour or more. The regenerated coarse protein powder or the regenerated coarse protein powder containing the base pigment is a gel body in which an oily body is dispersed and occluded in the form of minute droplets. Here, if the amount of oily body mixed with the protein aqueous solution exceeds 50% by weight of the regenerated gel body (dry weight) or exceeds 25 times the amount of regenerated protein, the mother liquor synergized by the regeneration treatment should be On the other hand, a large number of droplets of oily material are separated and suspended, and it is clearly recognized visually and tactilely that oily material is also attached to the surface of the generated gel powder, but the amount of oily material is is less than 50% by weight of the gel body, and 25% of the amount of regenerated protein is
When the amount is less than 2 times, the presence of oily substances can hardly be recognized on the surface of the mother liquor and the gel body. In particular, when the amount of oily material is less than 20% by weight of the gel material and is less than 10 times the amount of regenerated protein, no oily material is observed on the surface of the mother liquor and gel powder. That is, in the case of the present invention, when the amount of the oily substance is within this range, surprisingly, it is almost quantitatively occluded into the regenerated protein powder containing the regenerated protein and the base pigment, and the oily substance is absorbed even after washing with water in the post-process. It does not separate from the powder at all. For comparison, when an oily substance is later mixed into an aqueous suspension of gel-like regenerated protein powder that is regenerated without mixing an oily substance, the amount of oily substance adsorbed to the gel body is at most 1% by weight or less. Below, it can be clearly determined by the visual and tactile sense of the mother liquor and gel powder that it is simply adhering to the surface, and that the adhesion is not complete when 1% by weight or more is mixed. The obtained crude oily body occluded and regenerated protein powder is subsequently washed with water and dehydrated. It is preferable to use a centrifugal dehydrator for dehydration, and by this dehydration, the coarse powder usually has a dry content of 100 to 100%
It is dehydrated to about 500% by weight. After dehydration, it can be easily dried to an absolutely dry state. Drying is
It is carried out at a temperature of 60 to 120°C under normal pressure or reduced pressure. The dried product thus obtained is easily pulverized by using a pulverizer such as a hammer mill or a jet mill. The particle size (maximum particle size) is usually adjusted to 0.5-100μ, preferably 1-60μ, particularly preferably 3-30μ. When the protein component of the thus obtained oily body occlusion regeneration protein fine powder of the present invention is silk fibroin,
At least 50% by weight of the regenerated fibroin is composed of hot water-insoluble fibroin, but it is possible to make the fibroin hot water insolubilized (hot water-insoluble fibroin , β-structuring rate) can be further promoted (increased), and the above-mentioned properties can be further improved. As for the β-ization treatment, the powder after drying or pulverization is heat-treated with saturated steam at 50°C or higher, especially 80 to 120°C, or sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, This is carried out by treatment in a neutral salt aqueous solution such as ammonium sulfate or an organic solvent such as acetone or alcohol. When these β-forming treatments are carried out, 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 adhesion and spreadability. nature, concealability, dispersibility, miscibility,
A fine oily body occluded and regenerated protein powder having a good texture is obtained. (Effects of the Invention) The oily body occluding and regenerating protein fine powder of the present invention is capable of occluding a large amount of functional oils and is extremely useful for cosmetics, food, paints, etc. Various animal and vegetable oils, oily vitamins, ultraviolet absorbers, etc. It has built-in functions such as oil, skin-protecting oil, and various natural and synthetic fragrances, and is itself a regenerated protein pigment in the form of a fine powder, so it has excellent adhesion to the skin, spreadability, feel, moisturizing property, concealing property, and dispersion. It has outstanding properties desirable for cosmetic bases, such as flexibility, miscibility, balance between hydrophilicity and lipophilicity, ultraviolet absorption, and skin protection. In particular, when the regenerated protein is regenerated fibroin, more than 50% by weight of the regenerated fibroin is composed of hot water-insoluble fibroin (β-type structure), which has a high β-structured rate and the molecules are appropriately oriented. Uniform dispersibility in paints and cosmetics using oil as a dispersion medium,
Antiperspirant properties, film stability, miscibility with inorganic powders,
It also has an excellent skin humidity control effect, and does not cause phenomena such as adhesion, caking, secondary particle formation, and film peeling due to water and sweat. (Example) Examples of the present invention will be described below. The parts shown in Examples mean parts by weight, and the percentages other than crystallinity mean percentages by weight. Example 1 Using silk spinning waste as a raw material for silk fibroin,
100 parts of this was stirred and refined in a solution of 30 parts of Marcel soap and 3000 parts of water at 95 to 98°C for 3 hours to reduce the residual glue to 0.1% or less, washed with water, and then dried with hot air at 80°C. 100 parts of calcium chloride (CaCl ₂ 2H ₂ O) and water
38% by weight calcium chloride aqueous solution by mixing 100 parts
200 parts were prepared and heated to 110°C. 40 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 hollow fibers with an inner diameter of 200μ, a membrane thickness of 20μ, and a length of 500mm were bundled together, and a hollow fiber-type dialysis device was used in which both ends of the fibers were bundled and fixed (sealed) without blocking the hollow holes. The solution was dialyzed against deionized water at a rate of 0.1/hour to obtain a fibroin aqueous solution. The fibroin concentration of the fibroin aqueous solution is
6.5% by weight, residual calcium chloride 0.001% by weight
It was hot. To 200 parts of the obtained fibroin aqueous solution, 4.3 parts of octyl paradimethylaminobenzoate (trade name: Escarol 507, manufactured by Van Dyk) as an oily substance was mixed and vigorously stirred. Although the oily substance is water-insoluble, since the aqueous fibroin solution has surface-active properties, it is easily emulsified to form an emulsion. Subsequently, the oily body-fibroin emulsion was stirred at high speed so as to give a shear deformation rate of 100/sec. or more. When stirring is continued for 2 to 3 hours, silk fibroin gradually precipitates, and finally solidifies as an aggregate of small gel particles (crystallinity 11%, β structure ratio 54%) and separates from water. At this time, no oil droplets were observed floating in the synercised mother liquor (water), and the gel particles did not feel oily, and no oily substances were observed to adhere to the fingertips even if they were strongly pinched with the fingertips. Nakatsuta. Further high-speed stirring was continued, and then about 40 c.c. of a 30% concentrated ammonium sulfate aqueous solution was mixed, and the mixture was further stirred for 1 hour to carry out β-ization treatment of the protein, and as a result, the gel body was broken into small particles. Next, the gel body was separated, washed with water, and dried at 105° C. for 2 hours to obtain 17.3 parts of coarse powder. This shows that the oily body is almost quantitatively occluded in the regenerated silk fibroin. The obtained coarse particles were then ground in a jet mill to obtain a fine powder with an average particle size of 8.5μ. The crystallinity of this fine powder is 23% as a result of X-ray measurement, and the proportion of hot water-insoluble fibroin (β structure ratio) is 98%, making it a powder with extremely good adhesion, spreadability, and feel on the skin. Therefore, it was suitable as a cosmetic pigment. Next, octyl paradimethylaminobenzoate is
This is an ultraviolet absorber with an absorption peak at 3200 Å, and the absorption rate of the oil-based material was measured using the ultraviolet absorption spectrum of the obtained fine powder. As a result, the proportion of oily bodies in the fine powder was 25%, and this result also shows that the regenerated silk fibroin fine powder occludes oily bodies at a yield of almost 100%. As a measurement medium, so as not to affect the occlusion state of the oily body,
It was measured by a calibration curve method using propylene glycol, which is a non-solvent for oily substances. In the case of this medium, fine powder forms a stable suspension due to its viscosity and is therefore preferred as a measuring medium. At the same time, the ultraviolet absorption spectra of the mother liquor synercised from the gel body and the washing waste solution were also measured, but no absorption was observed here. Comparative Example 1 Stirring, gelling, and β-forming were carried out in the same manner as in Example 1, except that no oily substance was mixed, to produce 13.0 parts of fine powder of recycled silk powder with an average particle size of 8.7 μm. The fine powder was freshly mixed with 200 parts of distilled water,
While vigorously stirring, 4.3 parts of octyl paradimethylaminobenzoate and a nonionic emulsifier were mixed therein, and stirring was continued for an additional 3 to 4 hours. Stirring was stopped, and the powder was separated and dried at 105°C for 2 hours, yielding 13.5 parts of powder. This is a weight increase of about 3.8%, but it is thought that this is due to the fact that the separated powder picks up about 200% of the mother liquor and is simply due to adhesion. That is, although it is also a silk fibroin powder, it can be seen that the regenerated protein that has been coagulated and regenerated has almost no ability to absorb oily substances. In addition, measurement of the ultraviolet absorption spectrum of the separate mother liquor revealed that this one had a concentration of approximately 3.8
The presence of an oily substance was confirmed. The obtained oil-based regenerated silk fibroin was ground again in a jet mill to obtain a fine powder with an average particle size of 6.5 μm. The crystallinity of the fine powder is 23%, and the β structure ratio is 99.
However, it was considerably inferior to that obtained in Example 1 in terms of adhesion, spreadability, and feel on the skin. Example 2 According to Example 1, oily body occlusion regenerated fibroin was produced in which the occlusion amount was changed by increasing or decreasing the amount of octyl paradimethylaminobenzoate mixed, and the degree of expression of oily body function (ultraviolet absorption ability) was determined. , crystallinity, β structure ratio, and evaluation as a cosmetic base were conducted by 10 specialized inspectors. The results are shown in Table 1. From this result, it was found that the oil-based material can be occluded at a high yield up to about 50% by weight of the powder, and is also suitable as a cosmetic base. Powder has oil absorption capacity.
When it exceeds 50% by weight, it tends to rapidly caking, the average particle size becomes coarse, and the degree of expression of oily body functions and performance as a cosmetic base decrease. Also, crystallinity, β
The structural fraction also decreases as the amount of oily body occlusion increases.

【table】

[Table] (Note) The above ◎ means very good, ○ means good, △ means slightly poor, and × means poor. Comparative Example 2 According to Comparative Example 1, the amount of oily material to be mixed and the amount of pick-up at different times were determined. Powders were prepared with varying amounts of adhesion, and the degree of expression of the oily body function and their use as cosmetic bases were evaluated. The results are shown in Table 2.

[Table] Example 3 A fibroin aqueous solution was prepared by dissolving and dialysis according to Example 1. The aqueous solution contains squalane as an oily substance and titanium oxide as a base pigment (average particle size 3μ).
Mix and add dilute hydrochloric acid dropwise under vigorous stirring to bring the pH to 4.0.
And so. When the stirring is continued for 2 to 3 hours, silk fibroin is gradually precipitated with titanium oxide as the core, and finally the entire product solidifies as an aggregate of small gel particles and is separated from water. At this time, squalane is coagulated (after drying)
0.5-50% by weight of silk fibroin, and 25% of the amount of silk fibroin
When the amount is less than twice that, there are almost no oil droplets floating in the synercised mother liquor (water), and the gel particles do not feel oily, and even if you pinch them tightly with your fingertips, no squalane is observed to adhere to your fingertips. I couldn't help it. The gel body was separated, dried at 105°C for 2 hours, and then subjected to moist heat treatment in saturated steam at 110°C to increase the β structure ratio. The obtained coarse powder was pulverized using a jet mill to form a fine powder. Table 3 shows the proportion of squalane in the fine powder (wt%,
When changing the ratio of squalane to silk fibroin (mixing amount), the respective oily body absorption rates (production amount/mixing amount, gelation yield of fibroin are
(100%), the crystallinity of silk fibroin, the β structure ratio, the average particle size, and the evaluation results as a cosmetic base. As an index of the degree of expression of oily body functions, the lubricity of the pigment on the skin, which is the occlusion property of squalane, was measured.

[Table] Example 4 The hair and meat tissue of the hide of a young cow was removed, crushed, and thoroughly washed with water. Suspend 100 parts of the insoluble collagen in 1000 parts of water, mix with 0.2 parts of pepsin (acid-resistant protease), and PH with dilute hydrochloric acid.
= 2 to 3 and continued stirring. The enzymatic reaction is 72
Over time, the bonds between telopeptide and atelocollagen were broken down and the insoluble collagen was dissolved in water. Next, after filtering the solution and separating undissolved substances, the solution was diluted with dilute sodium hydroxide solution to pH=
It was adjusted to 7 to 8 to precipitate only atelocollagen. This was separated, mixed with 1000 parts of water, adjusted to pH 3 with dilute hydrochloric acid, and stirred to produce a 5.6% by weight aqueous atelocollagen solution. Dissolve 2.8 parts of various oily substances in hexane if necessary in 200 parts of the obtained collagen aqueous solution, mix and stir, and continue to stir vigorously for 20 to 30 minutes with or without suspending 14 parts of various base pigments in the emulsion. Ta. Then, a dilute aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7 to 8. Atelocollagen occluded the oily body or the oily body and the base pigment, solidified and regenerated, and separated from water. At this time, no oil droplets were observed floating in the gelatinized mother liquor (water), the gel particles did not feel oily, and even when pinched with the fingertips, there was no oily substance adhering to the fingertips. Ta. The gel body was separated, washed with water, freeze-dried, and then ground in a jet mill to obtain a fine powder with an average particle size of 5 to 10 μm. Table 4 shows the results of evaluation of the yield of the gel body (gel amount after drying/total mixture) and the feel as a cosmetic base.

[Table] Example 5 60 parts of commercially available milk casein was mixed with a 0.5% aqueous sodium hydroxide solution and dissolved with stirring to make 1000 parts. 4 parts of various oily substances were mixed and stirred into 200 parts of the obtained 6% by weight casein aqueous solution, and 80 parts of various base pigments were added to the emulsion.
Stir vigorously for 20-30 minutes with or without suspending the
Lasted for a minute. Next, add dilute hydrochloric acid dropwise to this and PH=
When adjusted to 4.5, casein occludes the oily body or the oily body and the base pigment, solidifies and regenerates into a gel-like state, and separates from water. At this time, no oil droplets were observed floating in the synercised mother liquor (water), and the gel particles did not feel oily, and even when pinched with fingertips, no oily substances were observed at all. The gel body was separated, washed with water, dried at 105°C for 2 hours, and ground in a jet mill to obtain a fine powder with an average particle size of 5 to 10 μm, depending on the base pigment. Table 5 shows the yield of the gel body (gel amount after drying/total mixture) and the evaluation of the feel as a cosmetic base. Although there are slight differences in the type of base pigment and oily material, it was found that in all combinations, the oily material was occluded at a high yield, and the resulting fine powder had a good feel as a cosmetic base. Ru.

【table】

[Table] Example 6 According to Example 1, a 6.5% by weight aqueous fibroin solution was produced. Add 45 parts of various oils to 200 parts of the aqueous solution.
150 parts of various base pigments were suspended in the emulsion, and vigorous stirring was continued for 20 to 30 minutes. Next, about 50 parts of a 30% by weight concentrated ammonium sulfate aqueous solution was mixed.
Gelation of silk fibroin progresses gradually, and finally the entire gel becomes solid as an aggregate of small gel particles and separates from water. Furthermore, when about 50 parts of a 30% by weight concentrated ammonium sulfate aqueous solution was mixed and stirring was continued for beta conversion, the gel body was crushed into small particles. Next, the gel body was separated, washed with water, dried at 105°C for 2 hours, and pulverized with a jet mill to obtain a fine powder with an average particle size of 5 to 10 μm, depending on the base pigment. Table 6 shows the yield of gel body (gel amount after drying/total mixture),
and evaluation of the feel as a cosmetic base. Although there are slight differences in the type of base pigment and oily material, it was found that in all combinations, the oily material was occluded at a high yield, and the resulting fine powder had a good feel as a cosmetic base. Ru.

【table】

Claims (1)

[Scope of Claims] 1. A fine oily body-occluding regenerated protein powder, which is made of a finely powdered regenerated protein or a base pigment-containing regenerated protein, and in which an oily body is dispersed and occluded in the form of minute droplets inside the fine powder. 2. The fine powder according to claim 1, wherein the oil content is 0.5 to 50% by weight of the powder and is 25 times or less the amount of regenerated protein. 3. Claim 1, in which the oily substance accounts for 1 to 20% by weight of the powder and is 10 times or less the amount of regenerated protein.
Fine powder as described in section. 4 The oily substance is an animal or vegetable oil, wax, higher aliphatic hydrocarbon, higher fatty acid, higher alcohol, ester oil, silicone oil, benzene-based synthetic fragrance, terpene-based synthetic fragrance, musk-based synthetic fragrance, or a combination thereof. Fine powder according to claim 1. 5. The fine powder according to claim 1, wherein the regenerated protein is silk fibroin, casein, or collagen. 6. The fine powder according to claim 1, wherein the regenerated protein is silk fibroin. 7. The fine powder according to claim 6, wherein at least 50% by weight of the silk fibroin is hot water-insoluble fibroin (β type). 8. Claim 6, wherein at least 90% by weight of the silk fibroin is hot water insoluble fibroin.
Fine powder as described in section. 9. The fine powder according to claim 5, wherein the collagen is atelocollagen. 10 The crystallinity of the regenerated protein is at least 10%
The fine powder according to claim 1, which is 11 The crystallinity of the regenerated protein is at least 20%
The fine powder according to claim 1, which is 12. Claims in which the base pigment is talc, kaolin, mica, titanium oxide, zinc oxide, titanium mica, calcium carbonate, magnesium carbonate, zinc stearate, magnesium stearate, magnesium silicate, an organic pigment, or a combination thereof. Fine powder according to item 1. 13. The fine powder according to claim 1, wherein the amount of the base pigment is 0 to 49 times (by weight) the amount of the regenerated protein. 14. The fine powder according to claim 1, wherein the amount of the base pigment is 0 to 20 times (by weight) the amount of the regenerated protein. 15. The fine powder according to claim 1, wherein the maximum particle size of the fine powder is 8 to 80μ. 16 An emulsified suspension obtained by mixing an aqueous protein solution with an oily substance or an oily substance and a base pigment is subjected to isoelectric focusing and/or mixing of a protein coagulant and/or stirring at a high shear deformation rate. A method for producing a fine powder of a regenerated protein occluding an oily body, which comprises coagulating and precipitating the regenerated protein containing minute droplets of the oily body or the droplets and a base pigment dispersed therein, followed by washing with water, drying, and pulverizing. . 17 Protein aqueous solution converts refined silk raw material into calcium,
17. The production method according to claim 16, which is an aqueous solution of silk fibroin obtained by dissolving it in an aqueous solution of magnesium or zinc hydrochloride and/or nitrate. 18 Protein aqueous solution converts natural collagen to pH=1.5
17. The production method according to claim 16, which is an aqueous collagen solution obtained by treating with an acid-resistant protease in water with a pH of 4.0 to 4.0. 19. The production method according to claim 16, wherein the isoelectric point solidification is achieved by stirring at room temperature for 10 minutes or more. 20 Protein is silk fibroin, casein has PH
4-5. The manufacturing method according to claim 19, wherein atelocollagen is subjected to isoelectric point coagulation at pH 7-8. 21. The production method according to claim 16, wherein the protein coagulant is ammonium sulfate, sodium sulfate, sodium chloride, or a combination thereof. 22. The production method according to claim 16, wherein an aqueous silk fibroin solution is used as the aqueous protein solution, and the protein is coagulated and regenerated by stirring at a shear deformation rate of 50/sec. or more, preferably 100/sec. or more.