JPS6270308A - Cosmetic for skin cleaning - Google Patents

Abstract

PURPOSE:To obtain a cosmetic for skin cleaning, having excellent massaging effect, cleaning effect, skin-beautifying effect and feeling to the skin, by compounding porous small spheres composed of regenerated silk fibroin or regenerated silk fibroin containing a base pigment. CONSTITUTION:A skin-cleaning cosmetic such as cleansing cream, massage cream, creamy facial wash, etc., is compounded with porous small spheres having an outer diameter of 0.14-0.9mm, an apparent specific gravity of 0.3-0.9g/ml and a hardness of 0.3-1.0kg/cm<2> and composed of a regenerated silk fibroin containing 0-4pts.wt., preferably 0-2pts.wt. of a base pigment (white pigment, extender pigment, pearl pigment, etc., for cosmetic) based on 1pt.wt. of the regenerated silk fibroin. The amount of the spheres is preferably 5-45wt% based on the whole cosmetic. The cosmetic produced by this process can be used as a massaging cosmetic without giving unagreeable feeling nor pain to the skin and has excellent applicability and improved massaging effect, cleaning effect and skin-beautifying effect.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field) The present invention provides a method comprising porous spherules made of regenerated recombinant fibroin or regenerated silk fibroin containing a base pigment.
This invention relates to a skin cleansing cosmetic with excellent pine surge effect, cleansing effect, skin conditioning effect, and ease of use.

(Prior art) In order to enhance the pine surge effect or cleaning effect on the skin, small particles of crushed fruit branches, synthetic resin particles (for example,
Pulverized core of apricot, polyethylene m-J″-)3
Skin cleansing cosmetics such as pine surge cream, cleansing cream, and creamy face wash containing pine surge cream are commercially available.

However, JP-A-51-121530 discloses that synthetic resins such as 1-polyethylene, polypropylene, and polystyrene, foams, sintered bodies, hollow bodies thereof, or spherical objects such as light metals such as aluminum are used. Cosmetics to be blended. ”
is proposed.

However, since these pulverized products and small spherical products are made of hard materials (hardness of 2.Oky/d or more, hardness is measured by the method described in the Examples section), cosmetics containing them cannot be used. When applying it to the skin and massaging it with your fingers, you may experience an uncomfortable sensation such as rumbling or roughness, and aggressive massage may result in skin cancer, which may not give you a favorable feeling of use. It has the disadvantage that it cannot be
child.

(Disclosure of the Invention) In view of the above-mentioned circumstances, the present inventor has conducted extensive research and has developed a skin cleansing cosmetic composition containing a specific porous spherical substance described below. A part of the porous small spherical material has a hardness (collapse pressure) suitable for disintegration by slight pine surge or finger pressure, so that it does not cause discomfort or discomfort to the skin due to pine surge as in the past. The present invention was completed based on the discovery that it does not cause pain, has an excellent feeling of use, and enhances the pine surge effect, cleansing effect, and skin conditioning effect.

(Object of the Invention) The object of the present invention is to provide a skin cleansing cosmetic that has excellent pine surge effect, cleansing effect, skin conditioning effect, and feeling of use.

(Structure of the Invention) The present invention is a skin cleansing cosmetic characterized by containing porous small spherules made of regenerated silk fibroin or regenerated silk fibroin containing a base pigment. □ (Description of specific structure) The porous small spherules used in the present invention are coagulated into a suspension of water-insoluble carbonate particles or the particles and a black pigment suspended in an aqueous silk fibroin solution. After mixing with a synthetic salt and/or stirring at a high shear deformation rate to produce regenerated silk fibroin coarse particles that cover and encapsulate the fine particles or the base pigment, the water-insoluble carbonate is decomposed and eluted by an acid treatment. It is obtained by generating carbon dioxide gas, then washing with water, drying, and then pulverizing.

This porous spherule-like material has a structure in which the regenerated silk buproin, or the composite of the base pigment and the regenerated silk buproin, has numerous pores.

In addition, in the skeleton porous spherules, at least 50% by weight (hereinafter abbreviated as wt%) of the regenerated silk fibroin is composed of hot water-insoluble fibroin (β-type structure), preferably 3Qwt% or more. If it is less than 5 Qwt%, the hydrophilicity of the fibroin becomes extremely strong, and the porous spherules tend to swell in the aqueous dispersion medium or the fibroin film tends to come off.

Furthermore, although the degree of crystallinity of regenerated silk fibroin varies slightly depending on the conditions of the manufacturing process, it is usually 10% or more, preferably 20% or more, and does not exceed 43%, and the crystallinity of silk fiber (50% or more). 2) It shows a lower value.

The base pigment according to the present invention is a general term for white pigments, extender pigments, pearl pigments, etc. for cosmetics, and includes, for example, talc, kaolin, mica, titanium oxide, zinc oxide, titanium mica,
Or a combination thereof can be applied either singly or in combination. The maximum particle size of the base pigment is usually 0.03-20p.

In the present invention, the base pigment is 0% for regenerated silk fibroin.
~4 times (weight 1.t), preferably 0 to 2 times (weight 1.t)
weight).

Silk fibroin raw materials applicable to the production of porous small spherules of the present invention include cocoon, raw silk, cocoon waste, raw silk waste, bis, fried cotton, silk cloth waste, boulet, etc. according to the conventional method.
Using scouring silk that has been dried after removing sericin in warm water in the presence of a surfactant or in the presence of an enzyme, it is dissolved, for example, by the method described in Japanese Patent Publication No. 58-38449, but as a solvent. From the viewpoint of cost and use, an aqueous solution of calcium, magnesium, or zinc hydrochloride or nitrate is preferred. The concentration of these aqueous solutions varies depending on the type of solvent used and the temperature, but the concentration of metal salts, etc. is usually 1.
It is 0 to 80% by weight, preferably 20 to 70% by weight, particularly preferably 25 to 60% by weight.

The concentration of fibroin in the aqueous fibroin solution used for producing the porous spherules of the present invention is usually 2 to 20% by weight.
, preferably 4 to 15% by weight, particularly preferably 5 to 10%
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 remove water from porous spherules during washing and drying processes. Further, outside both of the above ranges, the proportion of hot water-insoluble fibroin (β-structuring rate) is low, and regenerated fibroin that tends to stick or form secondary particles in an aqueous dispersion medium is likely to be produced.

The suspension applied to the method of the present invention is prepared by dissolving at least one hydrochloride or nitrate of calcium, magnesium, or zinc in an aqueous solution of silk fibroin, adding a readily water-soluble carbonate to the suspension, and adding the calcium, magnesium, or nitrate to the silk fibroin aqueous solution. Zinc carbonate may be precipitated as water-insoluble fine particles,
In addition, the preferable dissolving salt as a solvent for silk fibroin raw material is calculated from the predetermined amount (approximately equivalent amount) of water-insoluble carbonate to be encapsulated in the intermediate coarse particles, which also happens to be the raw material for the water-insoluble carbonate. The silk fibroin raw material may be dissolved in a hydrochloride or nitrate of calcium, 7gnesium, or zinc 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. Due to dialysis, it is either naturally present or formed during dissolution,
It is possible to completely remove low-molecular-weight silk fibroin, which degrades the performance of products as cosmetic bases, and iron ions mixed in from raw materials and reaction systems. In this case, when producing a water-insoluble carbonate in the reaction system, it is necessary to add the hydrochloride or nitrate in a predetermined manner again.

When a base pigment is used in combination, the base pigment is suspended in a suspension and a predetermined process is performed to obtain porous spherules coated with the base pigment.

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

A coagulating salt is mixed into an aqueous silk fibroin solution in which both the fine particles or the fine particles and the base pigment are suspended, or! 'i 0
/ SeC [Perform at least 11 times of treatment, such as stirring with the above-mentioned rhythmic deformation speed, to regenerate silk fibroin. The regenerated silk fibroin coarse particles are water-insoluble carbonate fine particles or both the fine particles and the base pigment. (2) It is a coarse particulate gel body that covers and encapsulates. The coarse particulate gel body has an average particle size of 1 μm in the aqueous fibroin solution purified by dialysis and desalination.
It can also be regenerated in a similar manner from an aqueous silk fibroin solution in which light calcium carbonate (1,1p J::J, -) or both this and the base pigment are suspended.

The carbonate fine particles in the coarse particles are 50 to 95% of the coarse particles.
]i amount% is preferable, and 60 to 90% by weight is more preferable. When it is less than 50% by weight, the pore density decreases, while when it exceeds 95% by weight, the hardness decreases and the characteristics of porous spherules as described below cannot be obtained.

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

Silk fibroin can be precipitated by stirring alone, but in this case, the deformation must be carried out at a fast rate of deformation, usually at least 5 Q/sec, preferably at least 100/sec. 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.

Silk fibroin coarse particles, which are intermediates, are filtered, washed with water, optionally dried, and coarsely pulverized, followed by acid treatment to decompose carbonate fine particles. Hydrochloric acid, citric acid, or citric acid is suitable as the acid, but care must be taken when using sulfuric acid, as sulfate, which is poorly soluble in water, may be produced. The amount of acid is preferably equivalent to or slightly in excess of the carbonate included in the coating, but P If is 1
The following should be avoided as there is a risk that the silk fibroin will become brittle. Completion of the acid decomposition can be confirmed by the end of the generation of carbon dioxide gas, and then the obtained porous fibroin powder is washed with water and dehydrated. For dehydration, it is preferable to use a centrifugal dehydrator, and by this dehydration, porous silk fibroin coarse particles are usually reduced to 100 to 500% by weight based on the dry matter.
dehydrated to some degree. 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 or reduced pressure.

The dried product thus obtained is easily pulverized by using a pulverizer such as a hammer mill or jet mill. Subsequently, the particle size of the spherical material may be separated using a sieve (20 to 100 mesh 1). For example, if it passes through a 20 mesh sieve and does not pass through a 100 mesh sieve, the outer diameter is 0.14 to 1.
Porous spherules of 0.9 fl can be produced.

The characteristics of the porous small spheres produced as described above include an outer diameter of 0.14 to 0.9 m, and an apparent specific gravity (measurement method described later) of 0.1 m.
3-0.9 g/ml, hardness Q, 3-1.0
kg/cd (7) range is preferred. If the outer diameter is less than 0.14 ff, it is difficult to obtain a sufficient pine surge effect and cleaning effect (and if it exceeds 0.9 wm, it is difficult to obtain a favorable feeling of use because the skin feels strange when pine surge is applied.

In addition, if the apparent specific gravity is less than 0.39/me or exceeds 0.99/l, it will be 0, 3 to 1 as described below.
Hardness in the range of 0 kg/d is difficult to obtain. Furthermore, the hardness is 0
．． If it is less than 3 kQ/cd, the porous spherules will easily crumble when pressed by fingers, making it difficult to obtain sufficient pine surge effect and cleansing effect, and if it is less than 1.0 kQ/cd, the porous spherules will easily break down when pressed with fingers, and if it is less than 1.0 kQ/cd, it will not be possible to touch the skin during pine surgery. It causes pain and does not provide a favorable feeling of use.

In order to obtain the skin cleansing cosmetic of the present invention, the above-mentioned porous small spherules may be blended into known cleansing gels, cleansing creams, pine surge creams, creamy facial cleansers, etc. in a conventional manner. is preferably 5 to 45 wt% based on the total amount of the skin cleansing cosmetic.

If it is less than 5 wt%, sufficient pine surge effect and cleansing effect cannot be obtained, and if it exceeds 45 wt%, it is not only difficult to prepare the dosage form of the cosmetic, but also cause discomfort or pain to the skin during pine surge. If it occurs and is used favorably (it will not become a rice cake).

(Examples) Hereinafter, experimental examples regarding various porous spherules and examples of the present invention will be described and explained.

The outer diameter described in the experimental example was determined by the average value of the maximum outer diameter of 100 small porous spheres, and the apparent specific gravity was calculated from the wires of 100+7 small porous spheres.

The cirrhosis measurement test, pine surge effect, cleaning effect, and skin conditioning effect evaluation tests are as follows.

(1) Hardness measurement test The hardness of 100 small porous spheres measured with a push-pull gauge (manufactured by Aiko Engineering Co., Ltd.)
The average value of the collapse pressure) was defined as the hardness.

(2) Evaluation test of pine surge effect, cleansing effect, and skin conditioning effect Twenty female test subjects who use make-up after-effects applied the example on the left and right sides of their faces once in the morning and once in the evening for one month. Approximately 0.5 coat of comparative sample was applied.
Pine surgery and face washing were performed in the usual manner. Then, using the paired comparison method, the test subject himself/herself asked, ``The feel of pine surge,'' ``
Evaluation items such as "cleansing effect" and "skin conditioning effect" were evaluated.

The evaluation results showed that, regarding each of the above evaluation items, the example had better pine surge than the comparative example. ”, “The makeup was good and my skin felt refreshed after washing it off.”, “My skin became smoother and its firmness and luster improved.” ” as the number of people who responded.

(Experimental example) Various porous small spherical parts were produced according to the above production method by suspending water-insoluble carbonate particles or the particles and a base pigment in an aqueous silk fibroin solution obtained from silk spinning waste. The properties of the spherules were then measured.

Experimental example-1 Using silk spinning waste as a raw material for silk fibroin, one of these
00 parts was stirred and refined with a solution of 30 parts of Marcel soap and 3000 parts of water at 95 to 98°C for 3 hours to remove the remaining glue.
%, washed with water and dried with hot air at 80°C.

Calcium chloride ((3a(J?2-2H20) 200
and 200 parts of water to prepare 400 parts of a 38% by weight calcium chloride aqueous solution and heated to 110°C.

80 parts of scoured silk fabric was added to this mixture using a kneader while stirring for 5 minutes, and the mixture was further stirred for 30 minutes to completely dissolve it.

Next, the inner diameter is 200μ, the film thickness is 20μ, and the quality is 500III.
Using a hollow fiber type dialysis device in which 200n of regenerated cellulose-based hollow fibers were bundled and both ends of the bundles were fixed (sealed) without clogging the hollow holes, each of the above-mentioned solutions was mixed for 0.11 parts per hour. A fibroin/aqueous solution was obtained by dialysis using deionized water. The fibroin concentration of the fibroin aqueous solution was 6.5% by weight, and the residual calcium chloride was 0.001% by weight.

60 parts of calcium chloride dihydrate was stirred and mixed with 200 parts of the fibroin aqueous solution obtained above, and after confirming that it was completely dissolved, 10% by weight of sodium carbonate was added to 400 parts of sodium carbonate.
c 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, the silk fibroin aqueous solution in which the carbonate fine particles are suspended is subsequently stirred at high speed so as to give a shear deformation rate of 100/sec or more. did.

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 aggregates were separated, washed with water, dried, and then ground in a hammer mill to obtain about 52 parts of coarse powder.

The obtained pulverized material was suspended in 200 parts of water, and 80 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 separated in a furnace, washed with water, dried, and then pulverized and passed through a sieve to obtain 13 parts of porous small spherules made of regenerated fibroin according to the present invention. This result shows that the amount of calcium carbonate fine particles in the Af coarse particles was about 80 wt%.

The outer diameter of the obtained porous small spheres was 0.43 fl, and the apparent specific gravity was (1509/*t, hardness 1; 10.7 kg/#
C”l:.

Ivy.

Experimental Example-2 Next, 20 parts of talc (pigment) was further added to 200 parts of the fibroin aqueous solution obtained above.
30 parts of porous small spheres made of regenerated silk fibroin containing a base pigment were obtained in the same manner as in Example 1. From this result, the content of calcium carbonate fine particles in the coarse particles is approximately 55 wt%.
It turns out that there was. The outer diameter of the porous small spheres is Q,
8ml/g, brushed specific gravity is 0.75L! /ml, and the hardness was 0.8 kq/cd.

Furthermore, the crystallinity of the silk fibroin constituting the porous spherules in Examples 1 and 2 was 20% and 19%, respectively, and the degree of crystallinity of the silk fibroin insoluble in hot water (β structure ratio) was 83% by weight, respectively.
, 82 wt%.

Experimental Example-3 to Experimental Example 10 20 of the fibroin aqueous solution obtained in Experimental Example-1 above
The fi-formation process after suspending finely powdered calcium carbonate (average particle size 0.2 μm) dispersed in 200 parts of water and various base pigments was carried out in accordance with Experimental Example-1. Table 1 shows the results of manufacturing various porous spherules and measuring the characteristics of the porous spherules.

The amount of concentrated hydrochloric acid added to decompose and elute calcium carbonate was adjusted as appropriate depending on the amount of calcium carbonate added. Furthermore, the crystallinity of silk fibroin, which constitutes the porous spherules, is 17.
~23%, β structure rate is 78 Table 1 Examples 1 to 3. Comparative Examples 1 to 2 [Cleansing Gel] Each cleansing gel was prepared by applying the small spherules of the experimental examples and crushed apricot cores as shown in Table 2 to the small spherules in the basic composition below. did.

(1) Basic composition (raw material components) (mixed weight%) ■Small spherules
Listed in Table 2 ■ Polyvinyl alcohol 0.2 ■ Glycerin 5
, 0 ■ Methylparaben o, 1 ■ Diisopropanolamine 0.7 ■ Water
Remaining amount with the total amount being 100% (2) Preparation method After sequentially dissolving ingredients ■ to ■ in the water of raw material ingredient ■, mix the small spherules of ingredient ■ uniformly while stirring to prepare each cleansing gel. Prepared.

The crushed apricot kernels were commercially available as raw materials for cosmetics and had an average outer diameter of 0.5 ff.

(3) Characteristic Comparative Example 1 and Examples 1 and 2, as well as Comparative Example 2 and Example 3, were compared in pairs, and the results of C evaluation for each evaluation item as described above are shown in Table 2. Described.

In contrast to Comparative Example 1, Example 1.2 is clearly superior in the feel of pine surge and skin conditioning effect, and is clearly recognized to have a high pine surge effect and a high cleaning effect. In addition, the conventional crushed apricot kernels of Comparative Example 2 caused tingling and pain on the skin during pine surge, making it impossible to actively pine surge, whereas Example 3 showed a significantly better effect. In particular, Example 3 is a cleansing gel with a beautiful appearance in which small red spherules are dispersed in a transparent gel.

Examples 4-6. Comparative Example 3 [Cream Facial Cleanser] In the same manner as in Example 1, each cream facial cleanser was prepared by applying the small spheres of the experimental example as shown in Table 2.

(1) Basic recipe (raw material ingredients) (Blend ants wt%) 0 Small spherules Listed in Table 2 (2) Preparation method Ingredients (A) and (■) are each heated and dissolved to bring the temperature to 80°C. Ingredient (A) is gradually poured into component (1) while stirring, and the mixture is stirred for 15 minutes. Cool with stirring and when the temperature reaches 40°C add the pellets for a further 30°C.
Cool to °C.

(3) Properties Comparative Example 3 and Examples 4 to 6 were compared in pairs, and the results of evaluation regarding each evaluation item are listed in Table 2.

Example 4 to Comparative Example 3 which did not contain small spherules
No. 6 showed better results regarding each evaluation item. In addition, in Example 4, in which porous small spheres with an outer diameter of 0.15 y were applied in Experimental Example 3, the outer diameter of the porous small spheres was small, and it was observed that the effect of pine surge was slightly lower. Ta.

In particular, Examples 5 and 6 are creams with a beautiful appearance in which yellow, blue, or red porous spherules are uniformly dispersed, and a pleasant pine serge can be made by breaking up the spherules with the pine serge. This further enhanced the pine surge effect.

Example 7. Comparative Example 4 Pine Surge Cream Each pine surge cream was prepared by applying the small spheres and polyethylene particles of the experimental example as shown in Table 2.

(1) Basic recipe (raw material ingredients) (Blend! l1wt%) O small spherules Listed in Table 2 (2) Preparation method Components (A) and (9) are each heated and dissolved to a temperature of 80
Bring to °C. Add component (9) to component (A) while stirring.
t to obtain a homogeneous emulsion, and then heat at 40° while stirring.
After cooling to 30°C, the small spherules or polyethylene particles of the experimental example were uniformly stirred and mixed, and the mixture was further cooled to 30°C.

Also, TJ? Liethylene particles are a commercially available ingredient for cosmetics))! A uniform outer diameter of 0.45 m was used.

(3) Characteristics Comparative Example 4 has a skin of 71% during pine surge. ], causing pain to the skin 1d in order to actively perform pine surgery. Implementation side 7 obtained better results regarding each evaluation item.

The implementation side 7 has a beautiful appearance with blue small spheres dispersed therein, and the pine surge effect is further enhanced by breaking up some of the small spheres with the pine surge. , -2') Table (Effects of the Invention) As described above, the present invention has excellent pine surge effect and cleaning effect, actively removes aged stratum corneum, and improves skin 1
It is clear that the present invention provides a useful skin cleansing cosmetic that has a skin-conditioning effect that smooths the skin, improves the firmness and luster of the skin, and also exhibits a beautiful appearance.

Claims (2)

[Claims] (1) A skin cleansing cosmetic characterized by containing porous small spherules made of regenerated silk fibroin or regenerated silk fibroin containing a base pigment. (2) The porous small spheres have an outer diameter of 0.14 to 0.
9 mm, an apparent specific gravity of 0.3 to 0.9 g/ml, and a hardness of 0.3 to 1.0 kg/cm^2.