JPH0448766B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a cosmetic pack material that is highly flexible and has excellent water retention and adhesion to the skin. This invention relates to a method for producing a cosmetic pack material that can promote regeneration.

[Technical background and explanation of conventional technology]

Chitin exists as an organic skeletal material in arthropods, annelids, molluscs, etc., and also in fungal hyphae or spores, and collagen exists in connective tissues, bones, teeth, ginseng bands, etc. of mammals, birds, etc. It is a natural polymer that exists in the skin, dermis, and fascia, and plays an important role in forming the skeletons of these organisms and protecting them from the outside world. Chitin is insoluble in water and difficult to handle as it is, so it is often used in the form of chitosan, which dissolves in dilute acids and is easy to form and process.

Chitosan is a deacetylated product of chitin, and there are many proposals for its use. It has been proposed to crosslink a composite material of chitosan and collagen and use it as a sausage casing or a medical material (Japanese Patent Application Laid-open No. 183344/1983), and chemically processed chitosan to make it water-soluble has been proposed as a cosmetic product. It was proposed to use it (Japanese Unexamined Patent Publication No. 106409/1983),
It has also been reported that gels made of N-methylene chitosan have excellent water retention properties and have obtained good results in germination tests of plant seeds.

[R&D Report No. 30, p. 210, published by CNC Co., Ltd.] It is difficult to stabilize the shape of chitosan when molded, so in order to stabilize the shape of chitosan molded products, we Attempts have been made to cross-link materials, but the cross-linked products of chitosan have reduced water retention.

The present inventors have continued to research the use of chitosan, and in their research, they found that when a solution of chitosan acetate was diluted with methanol, an anhydride of a saturated or unsaturated fatty acid was added, and the mixture was left to stand, chitosan They solidified to form a gel, and the gel was found to have water retention properties. However, it was discovered that when the gel was freeze-dried to make it into a sponge, its water-retention properties were reduced, so they continued their research and created a molded body with a sponge structure by freeze-drying a chitosan solution. It was discovered that when this chitosan sponge molded product is brought into contact with saturated or unsaturated fatty acids to acylate the chitosan, a sponge-like molded product that is flexible and has excellent water retention can be obtained. Based on this, the present invention has been achieved.

[Object of the invention and summary of the invention]

An object of the present invention is to provide a cosmetic material that is highly flexible and has excellent water retention and adhesion to the skin. Specifically, it is an object of the present invention to provide a cosmetic material that can promote skin protection and regeneration. In particular, in more detail, the beauty treatment,
Another object of the present invention is to provide a cosmetic material that can be used as a base material for a pack. That is, the present invention is a method for producing a sponge-like cosmetic material, characterized in that a mixture of chitosan and collagen is formed into a sponge-like shape without crosslinking, and then acylated.

The sponge-like cosmetic pack material according to the production method of the present invention can be obtained by molding a mixture of chitosan and collagen into a sponge shape and then acylating it. Chitosan with a degree of conversion of 40 to 100% can be used, and a chitosan-collagen mixture with a collagen content of 5 to 50% can be used.
(by weight), and the acylation is performed on the amino groups of the chitosan-collagen composite by saturated or unsaturated fatty acids having 1 to 32 carbon atoms and/or dicarboxylic acids having 2 to 8 carbon atoms. Chemical modification using an acid can achieve 30 to 10%, and the sponge can also be further impregnated with a water-soluble polymeric material after acylation.

The sponge produced in this way is highly flexible, has excellent water retention and good adhesion to the skin, and is suitable for use as a pack and its base material in beauty treatments. The pack and its base material can also be impregnated with cosmetics for use.

[Specific description of the invention]

To produce the cosmetic pack material of the present invention, first, an acid solution of chitosan is prepared. To prepare a spongy molded article of chitosan, chitosan is dissolved in an acid to prepare an acid solution of chitosan, which is placed in a mold of a desired shape and freeze-dried.

The raw material chitosan has a deacetylation degree of 40 to 100.
% of chitosan is preferably used, and the acid used to prepare the acid solution of chitosan can be any acid as long as it can dissolve chitosan, but acetic acid, Formic acid, lactic acid, succinic acid or hydrochloric acid can be used. By selecting the concentration of chitosan in the acid solution of chitosan, the apparent density of the sponge can be varied from 0.005 to 0.5.
g/cm ³ (preferably 0.01 to 0.03 g/cm ³ ). It is preferable that the concentration of chitosan in the acid solution of chitosan is 0.5 to 5%.

In preparing a chitosan-collagen sponge-like molded article, collagen is added to an acid solution of chitosan to prepare a chitosan-collagen solution,
This can be freeze-dried to prepare a chitosan-collagen sponge-like molded article, and the addition of collagen improves the strength properties of the sponge. Although any collagen or collagen derivative can be used as the collagen, it is particularly preferable to use insoluble collagen isolated from bovine Achilles tendon, which has excellent strength properties. Collagen is present at 5-50% (by weight) in the chitosan-collagen mixture.
It is preferable to mix at a ratio of .

Freeze-drying can be carried out by any known freeze-drying method, but by selecting conditions for adding collagen to an acid solution of chitosan and freezing it, it is possible to freeze chitosan-collagen. The average pore size of the sponge can be adjusted. For example, if an acid solution of chitosan and a collagen additive are rapidly frozen using dry ice (-70°C) or liquid nitrogen (-70°C) and then dried under vacuum, the average pore size of the bubbles is small and the cells are tightly packed. You can get a sponge.

A sponge-like molded product of chitosan-collagen composite is placed in a solution of an organic acid anhydride at room temperature.
Soak for 10-24 hours to acylate.

Any organic acid anhydride can be used as long as it is not harmful to living organisms, but saturated or unsaturated organic acid anhydrides having 1 to 32 carbon atoms, or 2 carbon atoms may be used as the organic acid anhydride. Preference is given to using dicarboxylic acid anhydrides of .about.8.

The solution of the organic acid anhydride is prepared by dissolving the organic acid anhydride in a water-free organic solvent, preferably methanol, ethanol or acetone is used as the organic solvent, and the organic acid anhydride is 2
Preferably, it is used as a solution in an organic solvent at a concentration of %.

In acylation with organic acid anhydrides, chitosan-
The degree of acylation of the acylated product can be adjusted by adjusting the molar ratio of the organic acid anhydride to the total amino groups of the collagen complex. The degree of acylation of the acylated product is preferably 30 to 100%.

The chitosan-collagen composite sponge which has been acylated by reacting with an organic acid anhydride is thoroughly washed with water and then freeze-dried again to obtain a sponge-like cosmetic pack material according to the production method of the present invention.

The sponge-like cosmetic pack material of the present invention is highly flexible, has excellent water retention and adhesion,
Moreover, it feels good on the skin, and since the material itself is a natural polymer extracted from living organisms, it is highly safe, so it can be used not only for cosmetics.
It can also be used as a physiological product or a quasi-drug. It is also effective in protecting the skin and promoting regeneration, so it can be used as a base material for use as a face pack by impregnating cosmetics in beauty treatments, and as a facial mask. suitable for.

In the present invention, a sponge made of chitosan-collagen composite that has been acylated by reacting with the organic acid anhydride is thoroughly washed with water, and then immersed in a solution of a material having desired properties. The sponge impregnated with this material can be freeze-dried again to give the sponge-like cosmetic pack material the desired properties.

Examples of materials that improve water retention in materials having desired properties include methylcellulose, ethylcellulose, carboxymethylcellulose, carboxymethyl chitin, carboxymethyl chitosan, glycol chitin, glycol chitosan, N
-succinyl chitosan, succinylated collagen, methylated collagen, allylated collagen,
Examples include polyvinyl alcohol, gelatin, hyaluronic acid, chondroitin sulfate, and dermatan sulfate.An example of a material that imparts bactericidal properties is a disinfectant, and an example of a material that can be used with oil-based cosmetics is a surfactant. However, from the viewpoint of safety, it is preferable that these materials be natural substances.

The cosmetic pack material of the present invention has a dry weight of
Can handle 40-50 times more water,
Since it has excellent water retention ability and can be imparted with sterilizing properties if desired, it can also be suitably used as a sanitary product.

In the following, the invention will be explained in more detail by means of examples.

Example 1 (Preparation of N-acetyl chitosan-acetylated collagen sponge) 15 g of chitosan (degree of deacetylation: 99%) at 2%
The mixture was dissolved in acetic acid aqueous solution 2, and 5 g of insoluble collagen separated from bovine Achilles tendon was added thereto, followed by thorough stirring and mixing in a homogenizer. This solution was poured into an aluminum vat to a depth of 5 mm, and the vat was held horizontally and vacuum freeze-dried at 0.2 mmHg to obtain a chitosan-collagen sponge. This sponge was immersed in 2% acetic anhydride methanol solution 3 and left at room temperature for 10 hours to effect acetylation.

After pulling out the sponge and rinsing it under running water for 24 hours, the sponge was again freeze-dried in a vacuum of 0.2 mmHg, and N-acetylchitosan-
A sponge of acetylated collagen (degree of acetylation: 70%) was obtained.

The above chitosan-collagen sponge was
After neutralizing with % ammonia methanol solution and immersing this sponge in running water and washing with water for 24 hours, the sponge was again vacuum freeze-dried in a vacuum of 0.2 mmHg to obtain chitosan-collagen (degree of acetylation: 0).
%) sponge was obtained.

Comparative example: 2 g of insoluble collagen isolated from bovine Achilles tendon was immersed in 300 ml of 2% acetic anhydride methanol solution, left to stand at room temperature for 10 hours, and the insoluble precipitate was filtered, thoroughly washed with water, and air-dried to acetylate. 2g of 70% acetyl collagen
I got it.

Apart from this, chitosan (degree of deacetylation: 99
%) was dissolved in 120 ml of 10% acetic acid aqueous solution, 480 ml of 1% acetic anhydride methanol solution was added thereto, and the mixture was left at room temperature for 10 hours. The resulting gel was suspended in 1200 ml of methanol, stirred overnight at room temperature, further suspended in distilled water and freeze-dried to obtain 7 g of N-acetyl chitosan with a degree of acetylation of 70%.

The entire amount of this N-acetyl chitosan was dissolved in 3,500 g of 8% lithium chloride-dimethylacetamide solution, and the entire amount of acetylated collagen obtained above was added thereto and mixed by thorough stirring in a homogenizer. Pour this liquid into an aluminum vat to a depth of 5 mm and hold it horizontally.
Perform vacuum freeze-drying in a vacuum of 1.0 mmHg,
A sponge of N-acetyl chitosan-acetyl collagen was obtained.

Test Example (Evaporation test of absorbed water) Sponge of N-acetylchitosan-acetylated collagen (degree of acetylation: 70%) which was acetylated after molding the sponge obtained in Example 1 and chitosan-collagen (degree of acetylation: 70%) :0%) sponge, N-acetyl chitosan obtained in the comparative example which was pre-acetylated and then molded into a sponge shape.
A sponge made of acetylated collagen (degree of acetylation: 70%) was immersed in water to absorb sufficient water. N-acetylchitosan-acetylated collagen that was acetylated after sponge molding (degree of acetylation:
70%) sponge supplies 41.8 g/g (sponge) of water, and chitosan-collagen (acetylation degree: 0%) sponge supplies 47.7 g/g (sponge).
A sponge of N-acetylchitosan-acetylated collagen (degree of acetylation: 70%), which was formed into a sponge after being acetylated in advance, absorbed 40.9 g/g (sponge) of water.

These water-absorbed sponges were placed in an electronic dry auto-desiccator (CM-made by Sanko Plastics).
3Auto), and when the time shown in Figure 1 had elapsed, the weight of each sponge was measured and the moisture content of each was calculated.

The results of the evaporation test were as shown in the diagram of FIG.

In Figure 1, the horizontal axis is the elapsed time [hours (days)] from the time the absorbed sponge was placed in the electronic dry autodesiccator, and the vertical axis is the relative moisture content of the sponge. The water content before putting the water-absorbed sponge into the electronic auto-desiccator is 100 (%),
The water content after each time period is expressed as a percentage (%). In FIG. 1, (-○-) is the relative moisture content (%) of the chitosan-collagen (degree of acetylation: 0%) sponge, and (-△-) is the acetyl content after molding the sponge by the manufacturing method of the present invention. N-acetyl chitosan-acetylated collagen (degree of acetylation:
70%) is the relative moisture content (%) of the sponge,
(−×−) is the relative moisture content (%) of the N-acetylchitosan-acetylated collagen sponge (degree of acetylation: 70%) that has been acetylated in advance and then molded into a sponge shape. The outside numbers are the temperature (°C) and humidity (%) of the gas phase inside the electronic dry autodesiccator containing each absorbent sponge.

According to the diagram in FIG. 1, N-acetylchitosan-acetylated collagen (degree of acetylation:
70%) sponge is a sponge of chitosan-collagen (degree of acetylation: 0%) and a sponge of N-acetylchitosan-acetylated collagen (degree of acetylation:
The evaporation rate of absorbed water is slower than that of sponges (70%), which indicates that sponges have superior water retention.

Example 2 (N-myristyl chitosan-myristylated collagen sponge) 10 g of chitosan (degree of deacetylation: 99%) at 2%
The mixture was dissolved in acetic acid aqueous solution 2, and 2 g of atelocollagen extracted from bovine dermis with pepsin was added thereto and thoroughly stirred to dissolve and mix. This solution was poured into a copper vat to a depth of 5 mm, and while held horizontally, vacuum freeze-drying was carried out in a vacuum of 0.2 mmHg to obtain a flexible chitosan-collagen sponge.

Separately, dissolve 1 g of myristic acid anhydride in 50 ml of tetrahydrofuran, and add 3 ml of acetone.
An acetone solution of myristic acid anhydride was obtained. The chitosan-collagen soft sponge obtained above was immersed in this acetone solution of myristic acid anhydride and left at room temperature for 24 hours to perform myristylation. The sponge was taken up, immersed in running water, and washed for 24 hours. The sponge was again subjected to vacuum freeze-drying in a vacuum of 0.2 mmHg to obtain a cosmetic makeup sponge material of N-myristyl chitosan-myristylated collagen.

Example 3 (N-acetyl chitosan-acetylated collagen sponge containing carboxymethyl cellulose) The acetylated chitosan-collagen sponge in Example 1 was soaked in running water and washed for 24 hours, and then the sponge was soaked in carboxymethyl cellulose. A sponge was thoroughly impregnated with a 1% aqueous solution of carboxymethylcellulose. Next, this sponge was again subjected to vacuum freeze-drying in a vacuum of 0.2 mmHg to obtain a sponge cosmetic pack material of N-acetyl chitosan-acetylated collagen containing carboxymethyl cellulose.

Example 4 (N-acetyl chitosan-acetylated collagen sponge containing N-succinyl chitosan) The acetylated chitosan-collagen sponge in Example 1 was soaked in running water and washed for 24 hours, and then the sponge was The sponge was immersed in a 2% aqueous solution of N-succinylchitosan to thoroughly impregnate the sponge with the 2% aqueous solution of N-succinylchitosan.
Next, leave this sponge as it is and add 0.2mm again.
Vacuum freeze-drying was carried out in a vacuum of Hg and N-
A sponge cosmetic pack material of N-acetylchitosan-acetylated collagen containing succinylchitosan was obtained.

Example 5 (N-myristyl chitosan-myristylated collagen sponge containing N-succinylated collagen) The N-myristyl chitosan-myristylated collagen sponge obtained in Example 2 was immersed in a 0.5% aqueous solution of N-succinylated collagen. After thoroughly impregnating the sponge with a 0.5% aqueous solution of N-succinylated collagen, the sponge was pulled up and 0.2 mm
Vacuum freeze-drying was carried out in a vacuum of Hg and N-
A cosmetic pack material of N-myristyl chitosan-myristylated collagen sponge containing succinylated collagen was obtained.

〔Effect of the invention〕

Since the cosmetic pack material of the present invention has excellent water retention and flexibility, it can be used as a base material for makeup packs impregnated with cosmetic materials and applied to the skin surface to apply makeup.

Furthermore, since the cosmetic pack material obtained by the production method of the present invention has biocompatibility, antibacterial properties, and the effect of promoting wound healing, it also has the effect of promoting the protection and regeneration of cells on the skin surface to which it is applied. be.

[Brief explanation of the drawing]

FIG. 1 is a chart showing the results of the evaporation test for the products of Example 1 and Comparative Example.

Claims (1)

[Scope of Claims] 1. A method for producing a sponge-like cosmetic pack material, which comprises forming a mixture of chitosan and collagen into a sponge-like material without crosslinking, and then acylating the mixture. 2. Claim 1, wherein the acylation is chemically modifying the amino groups of chitosan and collagen with a saturated or unsaturated fatty acid having 1 to 32 carbon atoms and/or a dicarboxylic acid having 2 to 8 carbon atoms. A method for producing a sponge-like cosmetic pack material as described in . 3. According to claim 1 or 2, the chitosan is chitosan with a degree of deacetylation of 40 to 100%, and the acylation is acylation of 30 to 100% of the amino groups of chitosan and collagen. A method for producing a sponge-like cosmetic pack material. 4 Mixture of chitosan and collagen 5-50%
(by weight) of collagen
A method for producing a sponge-like cosmetic pack material according to any one of items 1 to 3. 5. A sponge characterized in that a mixture of chitosan and collagen is formed into a sponge without crosslinking treatment, then acylated, and then the acylated product is impregnated with a water-soluble polymeric material and/or a surfactant. A method for producing a cosmetic pack material.