JPS6030649B2 - powder pack agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved powder pack that becomes a film-forming pack (film-type pack) by adding water and kneading (dispersing in water).

Conventionally, commercially available film-type packs (combining heat insulating agents, thickeners, alcohol, preservatives, etc. with an aqueous solution of film-forming agents such as polyvinyl alcohol) seal the skin by forming a film, and improve the pack effect (skin Makes it fresh and smooth,
Although the method has a high performance (in terms of removal of dirt and dirt), it has drawbacks such as the fact that it takes a long time to form the pack film (about 1 hour).

On the other hand, an aqueous solution containing water-soluble alginate (first agent)
is applied to the skin surface, and an aqueous solution or aqueous dispersion containing an alkali metal lactate or chloride (
A pack agent that converts the alginate into an alkali metal salt (gelation due to crosslinking of the alginate) and forms a gel-like film by applying the second agent (Japanese Patent Publication No. 46-3576) Unlike the powder pack described below, which does not require the effort of preparing a coating liquid before use, the second agent is uniformly and sufficiently combined with the first agent applied to the skin to form a homogeneous gel-like film. (It is difficult to form a pack skin, and if an inhomogeneous gel-like skin is formed, the alginate itself has a weak skin strength, so when it is peeled off, it will partially break and remain on the skin surface, making it time-consuming to peel it off.) There are other difficulties.

In addition, careful formulation design is required, such as selecting an appropriate preservative (for the first agent) and surfactant to keep both of the above agents stable for a long period of time, and changes in the viscosity of the alginate aqueous solution may cause many problems. Contains. In addition, the alginate powder-alkali metal salt powder pack agent, which is used by adding water and kneading, has poor dispersibility in river water and takes a long time (5 to 10 minutes) to uniformly disperse in water. It takes.

[2} The aqueous dispersion generally has a low viscosity and has poor applicability to the skin.

[3] The gel-like skin (pack film) formed by applying it to the skin surface is heterogeneous and has low strength, so it is difficult to peel off smoothly when peeling, and a portion often remains on the skin.

Side: The adhesiveness of the formed gel-like film to the skin is poor, so the pack effect (making the skin moist and smooth and removing dirt) is relatively low.

There are drawbacks such as.

As a result of intensive research in view of the current situation, the present inventors have found that by mixing a specific fibroin-graft polymerer described below with a water-soluble alginate and a water-soluble alkali divalent metal, the conventional technology The present invention has been completed based on the discovery that an excellent powder pack can be obtained that has improved all the drawbacks of the above.

The object of the present invention is to provide a powder pack that, when used, is easily and uniformly dispersed in water, is easy to apply to the skin, has good adhesion and peelability of the pack film formed on the skin surface, and has a high pack effect. The aim is to provide agents for

That is, the present invention provides a fibroin-graft polymer in which a polymer of sodium acrylate and polyethylene glycol diacrylate is bonded to fibroin, a water-soluble alginate, calcium sulfate, and magnesium sulfate. This is a powder pack containing at least one water-soluble alkali divalent metal salt.

The fibroin-graft polymer in the present invention includes polymer components of 1 to 40% by weight of fibroin and 0.1 to 5% of polyethylene glycol diacrylate.
Preferably, the composition is 60 to 95% by weight of sodium acrylate.

The fibroin-graft polymer of the present invention is a novel polymer, which is usually prepared by polymerizing sodium acrylate and polyethylene glycol diacrylate in an aqueous solution or dispersion of fibroin in the presence of a polymerization initiator. , by washing, drying, and pulverizing the resulting polymer (mainly fibroin-graft polymer). In the polymerization reaction, oxygen in the reaction system is removed using an inert gas such as nitrogen gas, and the reaction system is irradiated with radiation, electron beams, ultraviolet rays, etc., or a radical polymerization catalyst is added to perform the polymerization.
The radical polymerization catalyst may be appropriately selected from commonly used catalysts such as hydrogen peroxide, penzoyl peroxide, potassium persulfate, ammonium persulfate, ceric salts, and azbisbutyronitrile. At the same time, sulfite, the first
Polymerization can also be carried out in a redox system using iron salts and amines in combination. However, it is preferable to use a persulfate as a polymerization catalyst because a product with a high degree of polymerization can be obtained and production is easy. Polymerization temperature is usually 10~110oo, preferably 20~
80q0, and the polymerization time is 20 to 600 minutes, preferably 30 to 300 minutes.

The water-impervious fibroin-grafted polymer of the invention thus obtained has a high hydrophilicity (hydration), i.e. at least 60 times its own weight (60 times), preferably 100 to 500 times its own weight. Double (100 fences/evening to 500 fences/evening)
It exhibits a water absorption rate of , does not lose water retention even under pressure, and stably maintains a water-containing (hydrated) gel state for a long time.

Furthermore, although this water-insoluble fibroin-graft polymer is insoluble in water, it retains a large amount of water, becomes an extremely swollen homogeneous microgel, and forms the water-soluble alginate and alkali dihydric polymers. A homogeneous skin pack (in the form of a hydrated gel) that disperses metal salts uniformly in the system in a short period of time, and also makes it easy to remove when using the pack liquid, has good spreadability and texture when applied, and is strong on the skin surface and easy to peel off. The uniqueness of these actions and effects is remarkable, such as allowing skin to adhere and form in a short period of time, making the skin moist and smooth, and easily adsorbing and removing dirt. Regarding the skin irritation of the water-insoluble fiproin-graft polymer that can be used in the present invention, please refer to Dr.
As a result of conducting the test according to the method of Aize, both the animal skin irritation score and the human skin irritation score of 1 were substantially 0, and both were confirmed to be substantially non-irritating.

[DraiZe. J. Day. , ship association o
f FMd and Dmgofficjals of
ratio United States. Appraisal
lo of the Sa frame ty of Chemical
s in Foods, Drugs and Cosmet
ics, 46 (1959).

Te×as, Snete Department
of Heartn. Austin. ] The amount of the water-insoluble fibroin-graft polymer blended in the present invention is 1 to 3% by weight, preferably 5 to 15% by weight, based on the total amount of the formulation.

If the blending amount is less than 1% by weight, it will be difficult to achieve a uniform consistency when mixed with water during use, and its low viscosity will result in poor applicability to the skin, and the formed film will be soggy that it will not come off cleanly when peeled off. Some remains on the skin. - On the other hand, if the blending amount exceeds 30%, the water holding power (moisture retention power) is too large, and when mixing with water,
It is difficult to disperse uniformly, resulting in a rough-textured film, and the viscosity during application is too high, resulting in poor application properties.
The water-insoluble fibroin-graft polymer is preferably in the form of a powder, and particularly preferably has a particle size of 100 microns or less.

Examples of the water-dropable alginates in the present invention include, but are not limited to, potassium salts, sodium salts, and ammonium salts of alginic acid.

The amount of alginate added is 5 to 5% of the total amount of the prescription.
0% by weight, preferably 10-4% by weight.

If it is less than 5% by weight, the strength of the film formed will not be sufficient,
Difficult to remove from skin.

If it exceeds 5% by weight, it will be difficult to disperse uniformly and the viscosity during coating will be too high, resulting in poor coating properties. The amount of the lagoonal alkali divalent metal salt is 20 to 7% by weight, preferably 40 to 6% by weight, based on the total amount of the formulation. If the amount is less than 2% by weight, the strength of the pack film formed will be low, and therefore a part of the pack film will tend to remain on the skin when peeled off.

On the other hand, if it exceeds 7% by weight, it will be difficult to uniformly disperse or dissolve in water during use, and the texture of the pack film to be formed will tend to be rough.

As mentioned above, a composition containing a water-insoluble water-absorbing polymer, a hydrolyzed alginate, and the above-mentioned alkali divalent metal has good performance as a powder pack agent. When this composition is further blended with an appropriate amount of an alkali metal inorganic acid salt, a pigment, or an enzyme as described below, a more excellent powder pack of the present invention can be obtained.
These additive components may be used alone or in combination of two or more. When an inorganic acid salt of an alkali metal is further added to the composition of the present invention in an amount of at most 1% by weight based on the total amount of the formulation, the uniform dispersibility in water during use can be further improved, and A powder pack agent that can form a uniform and clean pack film can be obtained. This is because competition occurs between the alkali divalent metal ions and the alkali metal ions, resulting in rapid crosslinking (gelation) of the alginate by the alkali divalent metal ions.
This is thought to be due to the fact that it is moderately suppressed. It should be noted that if the amount of the inorganic acid salt of an alkali metal exceeds 1% by weight, the time required for film formation will be too long, and the simplicity will be impaired, which is not preferable. Examples of the inorganic acid salts of alkali metals include sodium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, and phosphoric acid. Chlorides of alkali metals such as potassium monohydrogen, potassium dihydrogen phosphate, potassium hydrogen carbonate, sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate,
Mention may be made of bromides, chlorides, phosphates and carbonates.

In addition, by further blending a pigment in the composition of the present invention in an amount of at most 60% by weight based on the total amount of the formulation, the powder pack of the present invention can be easily dispersed in water during use and has a more favorable feel when applied. agent can be obtained. If the amount exceeds 6% by weight, the characteristics of the pack film formed will deteriorate, and good peelability will not be obtained, with some of the film remaining during peeling.

Preferable examples of the pigment include talc, kaolin, titanium, iron oxide, and the like.

Furthermore, by further incorporating an enzyme into the composition of the present invention, the pack effect can be further improved. Examples of the enzyme include protease, amylase, etc., with protease and lipase being particularly preferred. By incorporating protease, the effect of removing old keratin on the skin is increased, thus making the skin smoother after the pack. Also, by incorporating lipase, old sebum is easily removed, so the skin feels refreshed after the pack. In particular, when an immobilized enzyme is blended, the stability of the product during storage is good, so it is easy to obtain a product that is excellent in the above-mentioned effects. The amount of enzyme blended varies slightly depending on the type of enzyme, but it is 0.001 to 0.001 to the total amount of the prescription.
5% by weight is preferred. If it is less than 0.001% by weight, the above effect is relatively low, and if it exceeds 5% by weight, the pack film forming properties tend to deteriorate.

The method for using the powdered pack agent of the present invention includes the method of using the powder pack agent (10
30 minutes), add 4 to 6 times its weight of water and mix to form a uniform paste, then apply to the skin of the face and the like, and peel off the formed film after about 10 to 15 minutes.

As mentioned above, the powder pack agent of the present invention is simple and highly effective in that it can be easily and uniformly dispersed in water during use and can form a high-quality backing film in a short time.

Examples will be described below.

In addition, % shown in Examples means % by weight, and parts means parts by weight. Further, the dispersibility, applicability, and film properties of the powder pack agent during use were evaluated as follows. In addition, the properties of the pack were evaluated.In particular, 20 parts of the powdered pack agent was mixed with 100 parts of water, mixed until it was homogeneous, and then applied to the face. After 10 minutes, the formed film was evaluated. was peeled off and evaluated.

{1} Dispersibility o Dispersion time 20 parts of powder pack agent and 100 parts of water were added and mixed with a spoon until uniform.

The time required for the mixture to become uniform was measured and used as the dispersion time. The shorter the better. '2} Application characteristics o How it comes off and how well it spreads on the skin A sensory test was conducted by 25 female panelists and the results are shown below.

◎・・・20 to 28 people said it was good.

○... 19 people from IB graded it as good. △...1
0 to 14 people rated it as good.

×... 5 to 9 people evaluated it as good.

'3' Film Characteristics The degree to which the pack film remained on the skin when it was peeled off was examined and evaluated.

◎・・・・・・The pack film does not remain on the skin and can be removed easily.

○: A very small amount may remain, but it can be easily removed.

△...1'5 to 1'1M standing remains.

×... About half remains.

{4' Pack Effects Ten female panelists who specialize in skin smoothness, freshness, and dirt removal evaluated the skin after using it as a pack as described below.

Take 50 minutes of the powder pack into a container, add about 25 hours of water to it, mix it up, and apply it evenly to the left face with your hands and massage.

After 1 minute, the formed film is peeled off.

The pack effect was evaluated based on the difference in appearance and feel between the left and right halves of the face. o Expression of evaluation results {1} When expressed by the number of people who answered that the pack effect was good (evaluation symbol, etc.) ◎... 8 to 10 people said that their skin became clearly smooth or dewy. I felt that the dirt had been cleaned and I had become clean.

○... 6 to 7 people felt the same way as above.

△...4 to 5 people felt as above. ×・・・・・・
...Two to three people felt the same way as above. '2' When expressed on a five-point scale, the evaluation is good...5 points, somewhat good/
...4 points, average...3 points, slightly poor...
...2 points, defective ...1 point.

Example 1 ○} Production of fibroin-sodium acrylate polyethylene glycol diacrylate graft polymer 900 parts of fibroin after removing sericin and oil by scouring raw silk waste with an aqueous soap solution was added to 2000 parts of a 65% aqueous calcium nitrate solution. The mixture was soaked and heated at 70-75 pm to obtain a fibroin solution.

Next, this fibroin solution was diluted in 200 parts of water, and then dialyzed using a holofiber type dialyzer to obtain an aqueous fibroin solution (5% fibroin concentration). 5 times the amount, 2 times the amount, 1 times the amount, 1 times the amount of fibroin and the weight of fibroin in the fibroin aqueous solution
．． 6 times the amount and the same amount of each acrylic acid and polyethylene glycol diacrylate (PEGDA) [CH2=CH
CO0 (C ratio CH20), 4COCH=C black] was added to fibroin in an equal amount of 1/40th and 1/20th, respectively.
Quantity equivalent, 1/20th amount equivalent, 1/20th amount equivalent, 10% including 1/20th amount equivalent, and add water to make the total amount 10%.
The mixture was charged into a polymerization machine separately, and 0.2 parts of ammonium persulfate (polymerization initiator) was added under a nitrogen stream, and a graft polymerization reaction was carried out at a polymerization temperature of 80 qo for 2 hours.

After neutralizing each of the obtained reaction solutions (dispersion of fibroin-acrylic acid graft polymer) with an aqueous sodium hydroxide solution, 10 g of ethyl alcohol was added to form fibroin-sodium acrylate-polyethylene glycol. The diacrylate graft polymer was precipitated, separated, and then
% alcohol for purification. After that 60qo
Dry under reduced pressure for 8 hours and crush to fine powder (particle size 10-50
(Buddha).

The obtained graft polymer is insoluble in water, but has the property of absorbing a large amount of water.

Table 1 Next, a powder pack was prepared by mixing one part each of these graft polymers (water-absorbing polymers) with 35 parts of sodium alginate and 55 parts of calcium sulfate.

Each of the obtained powder packs was evaluated as a cosmetic pack, and the results are shown in Table 2.

Table 2 As is clear from Table 2, fiproin-sodium acrylate consists of 1 to 4% by weight of fibroin, 60 to 95% by weight of sodium acrylate, and 0.1 to 5% by weight of polyethylene glycol diacrylate. - Polyethylene glycol diacrylate graft polymers are preferred.

Example 2 No. 1 of Example 1 produced and used in Example 1. Example 3 except that the blending amount of fibroin-sodium acrylate-polyethylene glycol diacrylate graft polymer (F-GP) was changed as shown in Table 3 below, and calcium sulfate was increased or decreased according to the amount of change. Each powder pack was prepared in the same manner as in 1, and the products were evaluated and shown in Table 3.

As is clear from Table 3, the blending amount of the fibroin-sodium acrylate-polyethylene glycol diacrylate graft polymer is 1 to 30%, particularly 5 to 15%.
is preferred. Table 3 Example 3 Fibroin-sodium acrylate polyethylene glycol diacrylate graft polymer (No. 1 of Example 1)
3) (F-GP), carboxymethyl cellulose (CM
C) A powder pack was prepared by blending 1 part each of carboxyvinyl polymer (Carboball) and polyvinyl alcohol (PVA), 40 parts of sodium alginate, and 5 parts of calcium sulfate. Product characteristics were evaluated and shown in Table 4.

As is clear from Table 4, the fibroin-graft polymer of the present invention was particularly excellent in coating properties and film properties.

Particularly in the case of other polymers, the film formation time is long and the removability deteriorates when peeled off after 1 minute. Table 4 Example 4 No. of Example 1. Using the fibroin-graft polymer of No. 3, the amount of sodium alginate blended was changed as shown in Table 5, and the amount of magnesium sulfate was increased or decreased accordingly, so that the total amount in the formulation was 100 parts. A pack agent was prepared.

Note that the amount of fibroin graft polymer was 15 parts. The obtained pack agent was evaluated and the results are shown in Table 5. As is clear from Table 5, the blending amount of sodium alginate was preferably 5 to 5% by weight, particularly 10 to 4% by weight.

If it is too low, the strength of the film formed will not be sufficient, and therefore,
The releasability becomes poor, and the viscosity is also too high, resulting in poor applicability. Table 5 Example 5 No. of Example 1 Fibroin-graft polymer 5 of 3
1 part, 2 parts of sodium alginate, and 2 parts of alkali divalent metal salt, calcium sulfate was varied as shown in Table 6, and the remaining part was prepared in Yuruk to make a total of 100 parts.
Each powder pack was prepared and the evaluation results are shown in Table 6.

At the same time, various powder packs were prepared using various alkali divalent metal salts, and the evaluation results are also shown in Table 6.
As is clear from Table 6, the blending amount of the alkali divalent metal salt is preferably 20 to 7% by weight, particularly preferably 40 to 6% by weight.

If the amount is less than 2% by weight, the strength of the film formed will not be sufficient and the film properties will deteriorate.

On the other hand, when it exceeds 7% by weight, the drying with water during use is not uniform and the texture of the formed film becomes rough. Table 6 Example 6 No. of Example 1 Fibroin-graft polymer 7 of 3
2 parts sodium alginate, 4 parts calcium sulfate, sodium chloride as the alkali metal was varied as shown in Table 7, and the remaining part was talc to prepare a powder pack for each part so that the total amount was 100 parts. The evaluation results are shown in Table 7.

At the same time, various powder packs were prepared using various alkali metal salts, and the evaluation results are also shown in Table 7. As is clear from Table 7, the content of the alkali metal salt was preferably at most 1% by weight.

When the amount exceeds 1% by weight, the time required to form a film increases, and the film remains on the face when peeled off 10 minutes after application.

Table 7 Example 7 No. of Example 1. Fibroin-graft polymer 1 of 3
Foundation part, sodium alginate 3 sparse part, calcium sulfate 4
Base part: Each enzyme was mixed as shown in Table 8, and the remaining part was titanium oxide to prepare each powder pack so that the total amount was in the range of 10. Table 8 shows the evaluation results.

The immobilized protease used here was prepared as follows.

◎Preparation of immobilized protease (silk fibroin immobilized protease) *Silk fibroin is dissolved by heating in an aqueous calcium chloride solution, and after dialysis, protease (protease manufactured by Nagase Sangyo) is added, and ammonium sulfate is added while stirring for salting out. The precipitate is dried and pulverized to obtain silk fibroin-immobilized protease.

The enzyme content of the immobilized enzyme (weight of protease/weight of immobilized enzyme x 100%) is 10%. As is clear from Table 8, a good packing effect can be obtained by incorporating enzymes. The blending strength is preferably 5% by weight at most. Table 8 Example 8 A powder pack containing an enzyme was prepared, and the formulation and results are shown in Table 9.

The immobilized protease used here is the same as the immobilized enzyme used in Example 7. Table 9 Contactance (〃9) (moisture retention) is measured in a constant humidity room at 20°C. ``The higher the conductance, the better the rope retention.

As is clear from the results in Table 9, by further blending an enzyme, a moist feel (moist feeling) can be given to the skin after the pack film is peeled off.

Although not listed in Table 9, all of the pack agent samples containing enzymes had a good pack effect (smooth skin) similar to the results of Example 7 (Table 8).

Claims (1)

[Claims] 1. A fibroin-graft polymer in which a polymer consisting of sodium acrylate and polyethylene glycol diacrylate is bonded to fibroin, a water-soluble alginate, and a water-soluble alkaline earth selected from the group consisting of calcium sulfate and magnesium sulfate. A powder pack containing at least one divalent metal salt.