JPS62250056A - Regenerated protein fine powder capable of occluding oily material and production thereof - Google Patents

Abstract

PURPOSE:To provide the titled fine powder composed of regenerated protein fine powder containing an oily material dispersed and occluded therein as minute liquid droplets, containing an oily material having high functionality at a high rate, having excellent adhesivity, spreadability, masking power, dispersibility, etc., and useful for cosmetic, food, paint, etc. CONSTITUTION:An aqueous solution of a regenerated protein (e.g. silk fibroin, casein, collagen, etc.) having a concentration of 2-20(wt)%, especially 5-10% is mixed with an oily material or an oily material and an extender pigment and the resultant emulsified suspension liquid is subjected to isoelectric point coagulation, mixing with protein coagulant or agitation at high rate of shear strain (>=50sec<-1>, especially >=100sec<-1>) or their combination. The regenerated protein coagulated and precipitated by this procedure is washed with water, dried and pulverized to obtain the objective regenerated protein fine powder (preferably having maximum particle diameter of 3-30mu) containing an oily material and optionally an extender pigment dispersed and included in the powder as minute liquid droplets. The amount of the oily material included in the powder is 0.5-50%, preferably 1-20% of the powder and <=25 times, especially <=10 times weight of the regenerated protein.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a fine oily body occluding and regenerating protein powder and a method for producing the same.

(Prior Art) Regenerated protein fine powder, especially regenerated silk fibroin powder, has properties such as moderate 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 makeup cosmetic bases (Japanese Patent Publication No. 58-88449).

In addition, the present invention ij etc. takes advantage of the above-mentioned preferable properties of silk fibroin to substantially cover the surface of particles of general pigments with a regenerated fibroin film.
Pigments for paints and cosmetics that have outstanding properties such as flexibility, extensibility, dispersibility, miscibility, coating properties, oil absorption, balance between hydrophilicity and lipophilicity, sweat resistance, feel, skin protection, dyeability, etc. and its manufacturing method were provided as Japanese Patent Publication No. 5)-115) 7.

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 this is no longer satisfactory.

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 conventional method for treating pigments with oily substances is to dilute the oily substance with an appropriate solvent to about the same amount as the treated pigment, mix and suspend the pigment therein, and then stir and distill off the solvent. 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.

That is, in the case of a method in which 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 final product has a large amount of oily substance,
The pigment is in a state where it hardens into lumps or is very prone to caking. For this reason, in conventional methods, the oil content is at most 1 to 2 times the pigment! The reality is that it is limited to 1% or less.

In addition, the conventional method requires explosion-proof equipment because it uses a solvent, and requires equipment for recovering and purifying the solvent, which has the disadvantage that the equipment is too large for the amount of indigo produced.

In addition, even when the amount of oily substance is limited to 1 to 2% by weight or less relative to the pigment, the resulting product often has poor adhesion, spreadability, dispersibility, and miscibility, for example as a base for cosmetics. There were various problems in use, such as the inability to mix in large amounts due to inferior functions.

(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 bodies,
In addition, it has excellent adhesion, spreadability, concealment, dispersibility, miscibility, balance between hydrophilicity and lipophilicity, anti-perspirant properties, feel, and skin protection properties, and is extremely useful for cosmetics, food, general materials, etc. The object of the present invention is to provide a fine powder and to provide an industrially advantageous method for manufacturing the same.

(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 subjecting an emulsified suspension of an aqueous protein solution to an oily substance, or an oily substance and a base pigment, to subjecting it to f&electric point coagulation, and/or mixing a protein coagulant. ,as well as/
Alternatively, the oily body is stirred at a high shear deformation speed to solidify and precipitate the regenerated protein containing fine droplets or the droplets and the base pigment dispersed therein, and then washed with water and dried to form a powder P?
It is characterized by

The oily body-occluding regenerated protein fine powder of the present invention has a structure in which a regenerated protein or a complex of a base pigment and a regenerated protein stores an oily body dispersedly in the form of minute droplets, and the oily body The weight of the powder is preferably 0.5 to 60 times the amount of regenerated protein, and more preferably 25 times (weight) or less of the amount of regenerated protein, and more preferably 1 to 20 times the amount of regenerated protein. 10
It is less than twice (weight).

If the amount of oily material is less than 0.5% by weight, the product becomes a powder in which the function of the oily material is hardly recognized.
If the amount exceeds - or exceeds 26 times the amount of regenerated protein, the oil-based material cannot be completely absorbed and oozes out to the outer surface of the powder, causing the powder to harden into lumps and affecting its smoothness as a cosmetic base. Shows a tendency for performance such as dispersibility to deteriorate.

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, combinations of animal and vegetable oils such as safflower oil, wheat germ oil, olive oil and lanolin, waxes such as ceresin, higher aliphatic carbonization such as vitamin E1 squalane, hydrogen, lylunic acid, etc. , higher fatty acids such as myristic acid, higher alcohols such as oleyl alcohol, ester oils such as dimethylaminobenzoic acid ester, stearic acid ester, oleic acid ester, type 8 silicone oil, and benzene-based synthetic fragrances such as coumarin and heliotropine. Examples include musk-based synthetic fragrances such as cyclic musk, 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, or collagen as raw materials, make an aqueous solution by a known conventional method, and regenerate the resulting protein.

The fibroin material used in the present invention includes cocoons, raw silk, cocoon scraps, raw silk scraps, bis, fried cotton, silk cloth scraps, boulet, etc. in hot water or fermentation in the presence of an activator as necessary according to a conventional method. Refined silk that has been dried after removing sericin in warm water in the presence of a molten silk is used, and is dissolved using the method described in Japanese Patent Publication No. 58-88449. Alternatively, a water bath solution of zinc hydrochloride or nitrate is preferred. The salt concentration of these saliva fluids varies depending on the type of solvent used, temperature, etc., but the concentration of metal salts, etc. is usually 10 to 80 x 1i-1, preferably 20 to 70 xitl, and particularly preferably 25 to 60 M. It is. Further, it is more preferable that the silk fibroin aqueous solution is subjected to dialysis desalination to completely remove the hydrochloride or nitrate used for dissolving the silk fibroin raw material.

The casein to be 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% (weight t), and separating the insoluble matter by F. Look at it.

Collagen applied to the present invention, especially atelocollagen, can be obtained by crushing young cow skin, for example, and dispersing it in water to obtain a pH of 1.
．． After adjusting to 5 to 4.0, acid-resistant protease (eg pepsin) is added thereto, stirring is continued for 2 to 8 days, and insoluble matter is removed by filtration to obtain an aqueous solution.

The protein concentration of the protein aqueous solution used in the present invention is usually 2.
It is preferably 4 to 16% by weight, particularly preferably 5 to 10% by weight.

If the concentration is less than 2 mm %, the regeneration time of the aqueous protein solution becomes long, which is uneconomical. On the other hand, if the concentration exceeds 20 mm, dehydration in the washing and drying steps may be difficult. When the protein is silk fibroin, the regenerated silk fibroin is composed of at least 6 oats, preferably at least 90 weight, of hot water-insoluble fibroin (β-type structure).

At less than 60 fIkqb, 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 dispersing in water. Dispersibility tends to decrease in media (water-based veins and cosmetics) and oil dispersion media (oil-based paints and cosmetics). Also, the spreadability and feel during application become worse.

The above-mentioned hot water-insoluble fibroin refers to buproin that does not dissolve even when boiled in hot water at 100° C. for 16 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 conditions of the manufacturing process, it is usually 1096 or higher, preferably 2.
096 or higher and never exceeds 48-. This has a considerably low crystallinity (6016 or more) of silk fibers, and also has a low degree of molecular orientation, which is 1/2 or less of 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 fine oil-based occluded and regenerated protein powder of the present invention is a general term for white pigments for paints or cosmetics, extender pigments, pearl pigments, etc., such as talc, kaolin, mica, titanium oxide, zinc oxide, etc. , titanium mica, calcium carbonate, magnesium carbonate, zinc stearate, magnesium stearate, magnesium silicate, organic pigments, or composites thereof, and may be applied singly or in combination of two or more. The maximum particle size of the base pigment is usually 0.
It is 08-20μ.

In the present invention, the base pigment is 0 to 49 times (Nk), more preferably 0 to 20 times (weight) relative to the regenerated protein.
It is.

The maximum particle size of the oily body occluding and regenerating protein fine powder of the present invention is usually 0.5 to 100μ, preferably 1 to 60μ, particularly preferably 8 to 80μ. 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 coagulating an emulsion obtained by mixing and stirring an aqueous protein solution with an oily substance at a constant dew point, and/or mixing a protein coagulant, and/or applying a high abrasion 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 coexisted with the emulsion 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 fibrolin or casein, PH = 4.0 to 5.0,
When the protein is collagen, stir for 10 minutes or more at pH=7-8. 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 mixed solution with the aqueous solution is 5 to 10.
Adjust so that it becomes m1k'1.

When the protein aqueous solution is a silk fibroin aqueous solution, the silk fibroin is regenerated into a gel powder by isoelectric point coagulation or the mixing of a coagulating salt, but at a rate of 50/sec>preferably 100/5 ec.
Stirring treatment at a high shear deformation rate of 1 or more allows regeneration in particularly favorable conditions. 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.

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 weight JI% of the regenerated gel body (dry weight) or exceeds 26 times the amount of regenerated protein, the mother liquor synergized by the regeneration treatment should be It is clearly recognized visually and tactilely that many oily droplets are separated and suspended on the surface of the gel powder produced, but the oily droplets are clearly visible and tactile. If the amount of the gel is less than 50 times and the amount of regenerated protein is less than 25 times, the presence of oily substances on the mother liquor and the surface of the gel cannot be recognized.

In particular, when the amount of oily material is less than 20% by weight of the gel material and 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 occluded in the regenerated protein powder and the base pigment-containing regenerated protein powder almost at a constant temperature, and the oily substance is absorbed even in the post-process water washing. It does not separate from the powder at all.

For comparison, when an oily substance was later mixed into an aqueous suspension of gel-like regenerated protein powder that was regenerated without mixing an oily substance,
The adsorption of the oily substance to the gel body is at most 1 weight or less, and it is simply adhering to the surface, and if more than 1 weight of oil is mixed, the adsorption will not be complete due to the visual appearance of the mother liquor and gel powder. This can be clearly determined by the sense of touch.

The obtained oily body occluded and regenerated protein coarse powder is washed with water,
Dehydrate.

It is preferable to use a centrifugal dehydrator for dehydration, and this dehydration usually yields a coarse powder of 100 to 600 weight ff based on the dry matter.
It is dehydrated to about 1-. After dehydration, it can be easily dried to an absolutely dry state. Drying 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 0.5 to 100μ,
The thickness is preferably adjusted to 1 to 60μ, particularly preferably 8 to 80μ.

When the protein component of the thus obtained fine powder of oil-based occluded and regenerated protein of the present invention is silk fibroin, at least 60% by weight of the regenerated fibroin is composed of hot water-insoluble fibroin. By subsequently subjecting the protein to β-ization treatment, it is possible to further promote (increase) the hot water insolubilization of fibroin (the proportion of hot water-insoluble fibroin, the β-structured rate), and to further improve the above-mentioned properties. can.

As for the β-ization treatment, the powder after drying or pulverization is
Heat treatment with saturated steam at 0°C or above, especially 80 to 120°C, or in a neutral salt aqueous solution such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, etc. or an organic solvent such as acetone or alcohol before drying. This is done by processing. These β
When carrying out the oxidation treatment, it is possible to promote the insolubilization of regenerated fibroin in hot water (increase in β-structuring rate) as described above, and further increase the degree of crystallinity of fibroin, resulting in excellent adhesion, extensibility, and concealment. A fine oily body occluded and regenerated protein powder having good properties, dispersibility, miscibility, and texture can be obtained.

(Effects of the Invention) The oily body occluding and regenerating protein fine powder of the present invention is capable of occluding a large number of functional oils and is extremely useful for cosmetics, food, paints, etc. Various animal and vegetable oils, oily vitamins, ultraviolet rays, etc. It has built-in functions such as oil-absorbing agents, skin-protecting oils, and various natural and synthetic fragrances, and is itself a regenerated protein pigment in the form of a powder, so it has excellent adhesion to the skin, spreadability, feel, moisturizing properties, concealing properties, etc. It has outstanding properties that are desirable for cosmetic bases, such as dispersibility, miscibility, balance between hydrophilicity and lipophilicity, ultraviolet absorption, and skin protection properties.

In particular, when the regenerated protein is regenerated fibroin, more than 60% of its weight is composed of hot water-insoluble fibroin (β-type structure), which has a high β-structured rate and whose molecules are appropriately oriented. Uniform dispersion in paints and cosmetics that use oil as a dispersion medium, anti-perspirant properties, film stability, miscibility with inorganic powders, and extremely excellent skin humidity control effect, with no adhesion caused by water or sweat. , does not cause phenomena such as caking, secondary particle formation, and film peeling.

(Example) The present invention will be explained in detail below.

The parts shown in the Examples mean parts by weight, and the terms other than crystallinity mean % by weight.

Example 1 Using silk spinning waste as a raw material for phase fibroin, one of these
00 parts was stirred and refined with a solution of 30 parts of Marcel soap and 8000 parts of water at 95 to 98°C for 8 hours to reduce the remaining glue to 0.1 parts.
%, washed with water and dried with hot air at 80°C.

100 parts of calcium chloride CCaC12e (2 parts gO) were mixed with 100 parts of water to prepare 200 parts of an 88 Jusha calcium chloride aqueous solution and heated to 110°C. 40 parts of refined silk waste was added to this mixture using a kneader while stirring for 6 minutes, and the mixture was further stirred for 80 minutes to completely dissolve it.

Next, 2000 regenerated cellulose-based hollow fibers with an inner diameter of 200μ, a membrane thickness of 20μ, and a length of 600mm 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 lysate was OA
The fibroin solution was dialyzed using deionized water at a rate of 1/hour to obtain a fibroin aqueous solution. The fibroin concentration of the buproin aqueous solution was 6.5% by weight, and the residual calcium chloride was 0.001% by weight.

To 200 parts of the obtained aqueous fibroin solution, 4.8 parts of octyl baladimethylaminobenzoate (trade name: Escarol 507, manufactured by Van Dyk) was mixed with oily 19 and stirred vigorously. Although the oily substance is water-insoluble, since the aqueous fibroin solution has surfactant ability, it is easily emulsified to form an emulsion. Subsequently, the oily body-fibroin emulsion was applied for 1007 seconds.

Stirring was performed at high speed to give the above shear deformation rate.

When the stirring is continued for 2 to 8 hours, silk fibroin gradually precipitates, and finally the whole becomes small gel particles (crystallinity 11%).
, β structure ratio: 54 h) and solidifies as an aggregate 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 at all, and no oily substances were observed to adhere to the fingertips even if they were strongly pinched with the fingertips. There wasn't.

Further high-speed stirring was continued, and then approximately 40 cc of a concentrated ammonium sulfate aqueous solution of aO* was mixed, and the mixture was further stirred for 1 hour to carry out β-ization treatment of the protein. As a result, the gel body was crushed into small particles. Next, the gel body was separated by F, washed with water, and then dried at 105° C. for 2 hours. As a result, 17.8 parts of coarse powder was obtained. This shows that the oily body is almost quantitatively occluded in the regenerated silk fibroin.

The obtained coarse particles were then pulverized with a jet mill to obtain a fine powder with an average particle size of 8.5 μm. The crystallinity of the fine powder is 28 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 is suitable as a cosmetic pigment.

Next, octyl baradimethylaminobenzoate is 8200
Although it is an ultraviolet absorber with an absorption peak at ^, the absorption yield of the oil-based material was measured based on the ultraviolet absorption spectrum of the obtained fine powder. As a result, the proportion of oily substances in the fine powder was 25
%, and this result also shows that the regenerated silk fibroin fine powder occludes oily bodies with a yield of almost 100%. Propylene glycol, which is a non-solvent for the oily substance, was used as the measurement medium so as not to affect the occlusion state of the oily body, and the measurement was performed using a calibration curve method. In the case of this medium, fine powder forms a stable suspension due to its viscosity and is therefore preferred as a measuring medium. In addition, the ultraviolet absorption spectra of the mother liquor synercised from the gel body and the washing waste solution were also measured, but no total absorption was observed.

Comparative Example 1 Stirring was carried out according to Example 1 except that the oily body was not mixed.
After gelation and beta treatment, the average particle size of 18.0 parts s, y
A fine powder of μ recycled silk powder was produced. The fine powder was newly mixed with 200 parts of distilled water, and while stirring vigorously, 4.8 parts of octyl valadimethylaminobenzoate and a nonionic emulsifier were mixed therein, and stirring was continued for an additional 8 to 4 hours. .

Stirring was stopped, and the powder was separated and dried at 106° C. for 2 hours, yielding 18.6 parts of powder. This is an increase in N of about 8.8 -, but it is thought that the weight increase is due to the fact that the powder collected from each house picks up the mother liquor of about 20 (1) and is simply due to adhesion. Although it is a powder of silk fibroin, it is clear that the regenerated protein that has been coagulated and regenerated has almost no occlusion ability of oily substances.In addition, measurements using the ultraviolet absorption spectrum of the mother liquor that were collected separately showed that The presence of approximately 8.8 parts of oily material was confirmed in this case.

The obtained oil-based regenerated silk fibroin was pulverized again using a jet mill to obtain a fine powder with an average particle size of 6.5 μm. The crystallinity of the fine powder was 28 and the β structure ratio was 99.
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 the range of octyl baladimethylaminobenzoate to be mixed, and the degree of expression of oily body function (ultraviolet absorption ability ), 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 in a high yield up to about 50% of the powder, and is also suitable as a cosmetic base. When the amount of oily absorbent exceeds 50% by weight, the powder rapidly becomes difficult to caking and has a coarse average particle size, resulting in a decrease in the degree of expression of the oily body function and performance as a cosmetic base.

In addition, crystallinity, Comparative Example 2 According to Comparative Example 1, by adjusting the odor of the oily substance to be mixed and the pick-up force when F is opened, powders with varying amounts of adhesion were produced. The degree of functional expression and its use as a cosmetic base were evaluated.

=28-Example 8 According to Example 1, a fibroin aqueous solution was prepared by dissolving and dialyzing. Squalane as an oily substance and titanium oxide (average particle size 8 μm) as a base pigment were mixed into the aqueous solution, and dilute hydrochloric acid was added dropwise with a vigorous stirrer to adjust the pH to 4.0.

When stirring is continued for 2 to 8 hours, silk fibroin is gradually precipitated with titanium oxide as the core, and finally the entire product solidifies as a combination of small gel particles and separates from water. At this time, squalane is coagulated (after drying) at 0°5~50! t% and less than 26 times the amount of silk fibroin, there are almost no oil droplets floating in the synergized mother liquid, and the gel particles do not feel oily, even if you pinch them strongly with your fingertips. No squalane adhesion to the fingertips was observed.

The gel bodies were separated, dried at 106°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.

Squalane proportion in powder (heavy ore, mixed amount) according to No. 8
, the respective oily body occlusion rates (produced amount/mixed amount, gelation yield of fibroin is 100%), crystallinity of silk fibroin, β structure rate, when the squalane magnification relative to silk fibroin is changed, The measurement results for average particle size and evaluation as a cosmetic base are shown.

As an indicator of the degree of expression of the oily body function, measure the lubricity of the pigment on the skin, which is the occlusion property of squalane (Note) Fibroin: Titanium oxide: Oily body is the mixing ratio (weight it) Example 4 Young cow The hair and flesh of the skin were removed, crushed, and thoroughly washed with water. 100 parts of the insoluble collagen was suspended in 1000 parts of water, 0.2 parts of pepsin (acid-resistant proteolytic enzyme) was mixed therein, the pH was adjusted to 2 to 8 with dilute hydrochloric acid, and stirring was continued. When the enzymatic reaction was continued for 72 hours, the bond between telopeptide and atelocollagen was broken down and the insoluble collagen was dissolved in water. Next, the dissolved solution was filtered and undissolved matter was separated by a furnace, and then the dissolved solution was adjusted to pH=7 to 8 with diluted sodium hydroxide solution to precipitate only atelocollagen. This was separated, mixed with 1000 parts of water, adjusted to pH 8 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 stir vigorously for 20 to 80 minutes with or without suspending 14 parts of various base pigments in the emulsion. Lasted for a minute. Next, a dilute aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7 to 8, and atelocollagen absorbed the oily body or the oily body and the base pigment, solidified and regenerated, and separated from water. At this time, no floating oil droplets were observed in the seminal plasma mother liquor (7jO), and the gel particles did not feel oily, and even when pinched with the fingertips, no oily substance was observed to adhere to the fingertips. .

The gel body was separated in a furnace, washed with water, freeze-dried, and then pulverized with a jet mill to obtain a fine powder with an average particle size of 5 to 10 μm.

Table 4 shows the yield of gel body (gel amount after drying/total mixture)
Example 5 of Evaluation of Texture as a Cosmetic Base 60 parts of commercially available milk casein were 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 ticcasein aqueous solution, and vigorous stirring was continued for 20 to 8 minutes with or without suspending 80 parts of various base pigments in the emulsion. . Next, dilute hydrochloric acid was added dropwise to adjust P)i to 4.5, and the casein occluded the oily body or the oily body and the base pigment, solidified and regenerated into a gel-like form, and was separated from water. At this time, no oil droplets were observed floating in the synercised mother liquor (T), 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 by ν, washed with water, dried at 105℃ for 2 hours, and pulverized with a jet mill. The result was 5 to 10, depending on the base pigment.
A fine powder with an average particle size of μ was obtained.

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 some differences depending on the type of base pigment and oily body, in any combination, the oily body is occluded in a high yield, and the obtained fine powder is good as a cosmetic base Example 6 Example 1 Similarly, a 6.6 weight aqueous fibroin solution was prepared. 46 parts of various oily substances were mixed and stirred into 200 parts of the aqueous solution, and 160 parts of various base pigments were suspended in the emulsion.
Vigorous stirring was continued for 0-80 minutes. Then 80 weight j71
About 50 parts of concentrated ammonium sulfate aqueous solution was mixed. Gelation of silk fibroin progresses gradually, and finally the entire gel solidifies as an aggregate of small gel particles and separates from water. Another 80 weight j
When about 50 parts of concentrated ammonium sulfate aqueous solution of iq/b was mixed and stirring was continued for β-ization, the gel body was crushed into small particles. Next, the gel body was separated into V-sections, washed with water, dried at 105° C. for 2 hours, and pulverized with a jet mill. As a result, a fine powder with an average particle size of 5 to 10 μm was obtained, although it varied depending on the base pigment. 6th
The table shows the yield of gel body (gel amount after drying/total mixture),
and evaluation of the feel as a cosmetic base.

Claims (1)

[Scope of Claims] (1) A fine powder of regenerated protein containing an oily body, 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 oily substance accounts for 0.5 to 50% by weight of the powder and is 25 times or less the amount of regenerated protein. (3) The fine powder according to claim 1, wherein the oily substance accounts for 1 to 20% by weight of the powder and is 10 times or less the amount of regenerated protein. (4) The oily substance is 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. The fine powder according to claim 1, which is (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) At least 50% by weight of the silk fibroin is hot water-insoluble fibroin (β type) Claim 6
Fine powder as described in section. (8) The fine powder according to claim 6, wherein at least 90% by weight of the silk fibroin is hot water-insoluble fibroin. (9) The fine powder according to claim 5, wherein the collagen is atelocollagen. (10) The fine powder according to claim 1, wherein the crystallinity of the regenerated protein is at least 10%. (11) The fine powder according to claim 1, wherein the crystallinity of the regenerated protein is at least 20%. (2) A patent claim 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. The 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) Treatment of isoelectric focusing and/or mixing of a protein coagulant and/or stirring at a high shear deformation rate on an emulsified suspension obtained by mixing an aqueous protein solution with an oily substance, or an oily substance and a base pigment. to coagulate and precipitate the regenerated protein containing minute droplets of the oily material or the droplets and the base pigment dispersed therein, followed by washing with water, drying and pulverizing. Manufacturing method. (2) The production method according to claim 16, wherein the protein aqueous solution is a silk fibroin aqueous solution obtained by dissolving a refined silk raw material in an aqueous solution of calcium, magnesium, or zinc hydrochloride and/or nitrate. (18) Protein aqueous solution binds 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) The protein is silk fibroin, casein has a pH of 4
~5. The manufacturing method according to claim 19, wherein atelocollagen is subjected to isoelectric point coagulation at pH 7 to 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) Using silk fibroin aqueous solution as the protein aqueous solution, 50/sec. or more, preferably 100/sec
．． 17. The manufacturing method according to claim 16, wherein the protein is coagulated and regenerated by stirring at the above shear deformation speed.