JPS62238209A - Production of spongy material for cosmetic - Google Patents

Abstract

PURPOSE:To obtain a material for cosmetic, which has flexibility to promote protection and reproduction of skin, improved water retention properties and adhesivity to the skin, by molding chitosan into a spongy state and acylating the prepared molded article. CONSTITUTION:Chitosan or a mixture of chitosan and collagen containing 5-50wt% collagen is molded into a spongy state, the prepared molded article is acylated and preferably 30-100% amino group of chitosan having 40-100% deacetylation degree is chemically modified with preferably 1-32C saturated or unsaturated fatty acid and/or 2-8C dicarboxlic acid. Optionally further, the material is impregnated with a water-soluble high polymer material and/or surface active agent to give a spongy material for cosmetic. The spongy mate rial has the above-mentioned effects, improved touch and high safety so it is useful as cosmetics such as pack, base, etc., and usable as sanitary products or quasi-drugs as well.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cosmetic material that is highly flexible and has excellent water retention and adhesion to the skin. The present invention relates to cosmetic materials that can be used.

The cosmetic material of the present invention can be used as a material that comes into 1α contact with the skin or mucous membranes, as a bag or its base material in cosmetics, beauty treatments, sanitary products, or quasi-drugs.

[Description of technology and prior art] Chitin exists as a skeletal material in arthropods, protozoa, and molluscs, and is present in fungal hyphae or spores, and collagen is present in nu milk. It is a natural polymer that acts on the connective tissues, bones, teeth, cords, skin, dermis, muscles, etc. of animals and birds, and plays an important role in the formation of the skeletons of these organisms and the protection of the organisms from the outside world. is in charge of

Chitin is insoluble in water as it is and is difficult to handle, so it is often used in the form of chitosan, which is bath-dissolved in Wi acid and is easy to mold and process.

Chitosan is a deacetylated product of chitin, and there are many proposals for its use. It has been proposed to develop a composite material of chitosan and collagen and use it in so-safe casings and medical materials (Japanese Patent Laid-Open No. 183344/1983).
Publication), chemically treat chitosan to make it water-soluble! ζ
The use of cosmetics as cosmetics was proposed (Japanese Unexamined Patent Publication No. 5
9-106409), and the gel made of N-methylene chitosan has improved water retention! No, good set was obtained in the germination test of the plant dish! , = has also been reported.

(R&D Rebo-h No. 30, p. 2to, Published by CMC Co., Ltd.) When chitosan is molded, it is difficult to stabilize its shape. As a first step to stabilizing the shape of the product, attempts have been made to subject molded products of Gi-san to a cross-wetting process, but the cross-wet-processed products of Ki-san have reduced water retention. .

The present inventors have been continuing research on the use of chitosan, and in this research, a solution of chitosan acetate was diluted with Medanol, and the solution was saturated until it reached 1. It was found that when an anhydride of an unsaturated fatty acid was added to the formula (14), the x1-san solidified to form a gel, and the gel had a high water retention property. However, it was discovered that when the gel was freeze-dried to form a sponge, its water-retention properties decreased.Continuing research, they freeze-dried a solution of x-1-san to create a sponge structure. The molded chitosan sponge is brought into contact with a saturated or unsaturated fatty acid to acylate the chitosan, resulting in a sponge-like molded product that is flexible and has excellent water retention. Based on this knowledge, we have arrived at the present invention1.
No.

[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, and more specifically, it promotes skin protection and regeneration! Our goal is to provide moisturizing cosmetic materials.
An object of the present invention is to provide a cosmetic material E that can be used as a bag or a base material for a bag in beauty treatments.

The present invention is a method for producing a sponge-like cosmetic material, which is characterized by molding chitosan into a sponge shape and acylating the spongy chitosan molded product.

In producing the sponge-like cosmetic material of the present invention, acylation is performed to convert the amino group of chitosan or chitosan-collagen composite into a saturated or unsaturated fatty acid having 1 to 32 carbon atoms and/or a saturated or unsaturated fatty acid having 2 to 32 carbon atoms. This can be done by chemically modifying the dicarboxylic acids of 8 and 1. Therefore, it is possible to use chitosan with a degree of deacetylation of 40 to 100%.
This is the 30-amino group of KiI-san-collagen.
This can be done by acylating 100% of the material, and after the acylation, the sponge can be impregnated with a water-soluble polymer material, and then collagen is mixed with 1) and formed into a sponge. `` After 1-1, it can be acylated, and with a mixture of chitosan and collagen, collagen is 5-50% (heavy f1K)
Those contained in the acid can be used conveniently.

The sponge manufactured in this way is highly flexible,
1) Good adhesion to worn water retention and skin
The bag is suitable for use as a bag in the central care method, and can also be used by impregnating it with cosmetics.

[Detailed description of the invention]

To produce the cosmetic material of the present invention, first, a sponge-like molded article of chitosan is prepared. In preparing a spongy molded article of chitosan, chitosan is dissolved in an acid, and an acid solution of chitosan is added to A1. It is then put into a mold of a desired shape and freeze-dried.

The raw material chitosan has a degree of deacetylation of 40 to +oo9.
It is preferable to use chitosan; any acid can be used as long as it can completely dissolve chitosan in the preparation of the acid solution of chito4F. Acetic acid, 4: acid, lactic acid, succinic acid or hydrochloric acid can be used.

Depending on the moisture content of chitosan in the acid solution, the apparent density of the sponge can vary from 0.005 to 0-5 g/
It is preferable that the aIf of chitosan in the acid solution of chitosan is adjusted to 0.05 to 5%.

The average pore size of the chitosan sponge can be adjusted by selecting the conditions for freezing the acid solution of chitosan, although freeze-drying can be done by any method of freeze-drying known so far. can do. For example, a chitosan acid solution was placed on dry ice (-7
o°C) JI is rapidly frozen than leaf body nitrogen (-170'c), and when 1':tl is dried under 11 T2], the Xv-uniform pore diameter of the bubbles is small; You can get a dense sponge.

To prepare a spongy molded article of chitosan, add chitosan acid a liquid and prepare a solution of chitosan-collagen for 1 day, freeze it, Experimentally, sponge-like moldings of x1-san-collagen can be prepared, 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 a non-adhesive material that has long-awaited strength properties and is distinguished from cow skin. Preference is given to using collagen. Collagen is chitosan-
It is a good idea to add 5 to 50% (weight of 1 liter) of collagen to the collagen mixture.

A sponge-like molded product of chitosan or chitosan-collagen composite is acylated by immersing it in a solution of an organic acid anhydride at room temperature for 10 to 24 hours.

Any organic anhydride can be used as long as it is not harmful to living organisms, but any saturated or unsaturated organic acid anhydride having 1 to 12 carbon atoms can be used. Alternatively, it is preferable to use a dicarboxylic acid anhydride having 2 to 8 carbon atoms.

The organic acid anhydride solution is prepared by dissolving the organic acid anhydride in a water-free 11 organic solvent, and methanol, ethanol or acetone is preferably used as the organic solvent. In the acylation with cylindrical acid anhydride, which is preferably used as a 0.1 to 2% solution in an organic solvent, the amino groups of chitosan and the chitosan-collagen complex are By adjusting the molar ratio of O-organic acid anhydride to the total amino groups, the degree of acylation of the acylated product can be adjusted to 4%.It is preferable that the degree of acylation of the acylated product is 30 to 100%. The chitosan-collagen composite sponge that has been acylated by reacting with an acid anhydride is thoroughly washed with water and freeze-dried again, thereby forming the sponge-like cosmetic product 4 of the present invention. get a fee.

The sponge-like cosmetic material of the present invention is highly flexible, has excellent water retention and adhesion, and has a good texture, and the material itself is a natural polymer extracted from living organisms. Since it is highly safe, it can be used not only as cosmetics but also as sanitary products or quasi-drugs.

It is also effective in protecting the skin and promoting regeneration, so it can be used as a backing material in beauty treatments and as a base material for impregnating cosmetics to be backed up and used as a balm. Suitable for use as a mask. .

In the present invention, a sponge made of chitosan or chitosan-collagen composite which has been acylated by q-acid anhydride/reactive reaction is thoroughly washed with water, and then immersed in a solution of a material having desired properties. A sponge is sufficiently impregnated with this material, and the sponge impregnated with this material is freeze-dried again.
Desired properties can be imparted to the spongy eaves material.

Among materials that have desired properties, examples of materials that improve water retention include methyl cellulose, ethyl cellulose, carboxymethyl cellulose, carboxymethyl chitin, carboxymethyl chitosan, glycol chitin, glycol chitosan, N-succinylated 1) , succinylated collagen, methylated collagen, acylated collagen, polyvinyl alcohol, gelatin, hyaluronic acid, chondroitin sulfate and dermatan sulfate.
Also, an example of a material that imparts bactericidal properties is a bactericide, and an example of a material that can be used with oil-based cosmetics is w.
There are surface-active substances, but these materials are preferably natural substances from the viewpoint of safety.

The cosmetic material of the present invention can absorb 40 to 50 times more water than its dry weight, has excellent water retention ability, and can be imparted with bactericidal properties as desired. Since it can also be used as a sanitary product, it can 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 W) 15 g of chitosan (deacetylated J9: 99%) was dissolved in a 2% acetic acid aqueous solution 21, and an insoluble material isolated from bovine quince was added to the solution. 5 g of collagen was added and mixed thoroughly with a homogenizer.

This solution was poured into an aluminum vat to a depth of 5 mm, and vacuum freeze-drying was carried out under a vacuum of 0.2 x 11 g while the vat was kept in water to obtain a chitosan-collagen sponge. This sponge was immersed in a 2% acetic anhydride methanol solution 31 and left at room temperature for 10 hours to effect acetylation.

After pulling up the sponge and immersing it in running water for 24 hours, the sponge was again subjected to air freeze-drying in a vacuum of 0.12% Hg to obtain a sponge of N-acetylchitosan-acetylated collagen (degree of acetylation near 0%). Ta.

(Absorbed moisture evaporation test) The above chitosan-collagen sponge was neutralized with a 1% ammonia methanol solution, soaked in running water, rinsed for 24 hours, and then reapplied. (
A sponge of chitosan-collagen (degree of acetylation: 20%) was obtained by vacuum freeze-drying in a vacuum of 100 g.

The N-acetylchitosan-acetylated collagen (degree of acetylation: 0%) sponge obtained in Section 2 and the sponge of chitosan-collagen (degree of acetylation: 0%) were immersed in water to absorb enough water. I let it happen. A sponge made of N-acetyl chitosan-acetylated collagen (degree of acetylation = 70%) absorbs 4 [, 81/I (sponge) of water, and a sponge made of chitosan-collagen (degree of acetylation = 20%) absorbs water of u, xj/g<sponge) of water was absorbed.

These water-absorbed sponges were placed in an electronic triode dessicator (CM-3Auto manufactured by Sanko Plastics).
), and the time shown in Figure 1 has passed! At this time, measure the double yang of each sponge and find out the moisture content of each sponge.
The amount was calculated.

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

The horizontal axis in Figure 1 is the electronic triode desiccator.
The elapsed time C hours from the time the absorbent sponge was put in (
)], and the vertical axis is the relative moisture content of the sponge.
00 (%), and the water content after each time period is expressed as a percentage (%) of this. 1st
In the figure, (-0-) is the relative water charge (%) of the chitosan-collagen (acetylation degree: 0%) sponge, and (- to one) is the N-acetyl chitosan-acetylated collagen (acetylation degree: 0%). The numbers outside each line represent the temperature (°C) and humidity of the gas phase in the electronic triode desiccator containing each absorbent sponge. (%).

According to the diagram in Figure 1, the acetylated chitosan-collagen sponge is different from the non-acetylated chitosan-collagen sponge.
Compared to the Sun-Collagen sponge, the evaporation rate of absorbed water is slower, indicating that the sponge has better water retention.

Example 2 (N-myristyl chil-san-myristylated flagen sponge) Chitosan (degree of deacetylation = 99%) tog was dissolved in 2% acetic acid aqueous solution 2e, and 2 g of atelocollagen extracted from bovine dermis with pepsin was added to this. The mixture was added and stirred well to dissolve and mix. Pour this solution into a copper vat to a depth of 5IIJl, hold it horizontally and hold it as it is, 0.2111
Vacuum freeze-drying was carried out in a vacuum of 111 g, and the key 1-
A flexible sponge of Sun-collagen was obtained.

Separately, myristic acid anhydride Ig was dissolved in 50+++A of tetrahydrofuran and mixed with 37% 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 hours9 to perform myristylation. Raise the sponge, soak it in running water, and wash it for 24 hours.
After Xm, the sponge was vacuum-lyophilized again in the middle of a 2ml/1g container, and N-myristylchitosan-
A cosmetic material of the present invention of a myristylated collagen sponge was obtained.

Example 3 (Sponge of N-acetylx-1-acetylated collagen containing carboxymethylcell [1-su]) The acetylated Kyl-san-flagen sponge in Example 1 was immersed in running water. After washing with water for 24 hours, the sponge was immersed in a 196 aqueous solution of carboxymethylcellulose to thoroughly impregnate the sponge with a 1% aqueous solution of carboxymethylcellulose. Next, this sponge was again subjected to vacuum freeze-drying in a vacuum of 0.2 m Jig to obtain the cosmetic material of the present invention, which is a sponge 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 treated with N-succinyl chitosan.
- The sponge was soaked in a 2% aqueous solution of N-succinylchitosan to thoroughly impregnate it with the 2% aqueous solution of N-succinylchitosan.

Next, leave this sponge as it is and use Q again, 2mm1.
Vacuum freeze-drying was carried out under a vacuum of 1 g to obtain the cosmetic material of the present invention, which is an N-acetylchitosan-acetylated collagen sponge containing N-succinylchitosan.

Example 5 (N-myristyl chitosan-myristylated collagen sponge containing N-succinylated collagen) The N-myristyl chitosan-myristylated collagen sponge obtained in Example 2 was mixed with 0.5% N-succinylated collagen Mizuno. After thoroughly impregnating the sponge with a 0+5% aqueous solution of N-succinylated collagen, remove the sponge and perform vacuum freeze-drying in a vacuum of 0.2111 g to obtain N-succinylated collagen. A cosmetic material of the present invention of a sponge containing N-myristylchitosan-myristylated collagen was obtained.

Example 6 (N-acetyl chitosan sponge) 15 g of chitosan (degree of deacetylation: 99%) was dissolved in 2% acetic acid water rB solution 21, poured into a copper rosette 1- to a depth of 1 inch, and horizontally held at = 0°2111111g
A chitosan sponge was obtained by vacuum freeze-drying in a vacuum. This sponge was immersed in a 2% acetic anhydride methanol solution 3e and left at room temperature for 10 hours to effect acetylation. The sponge was taken out, soaked in running water, and washed with water for 24 hours. The sponge was then freeze-dried again in a vacuum of 0.2 to 1 liter to obtain a do-acetyl chitosan (degree of acetylation: 85%) sponge. Ta.

Example 7 (N-acetyl chitosan sponge containing polyvinyl alcohol) After washing the sponge in Example 3 (soaking the sponge immediately after acetylation in running water in step 1) for 24 hours, the sponge was treated with polyvinyl alcohol (PVA) Q, 95. % aqueous solution
Soak a sponge in polyvinyl alcohol 1
Freeze-drying was carried out in 4 vacuums to obtain a sponge of N-acetyl chitosan containing polyvinyl alcohol.

Example 8 (N-acetyl chitosan sponge containing glycol chitin and Span-20) 30 g of glycol chitin was dissolved in 3 j of water, 10 g of Span-20 (trade name, Wako Pure Chemical Industries, Ltd.) was added to this solution, and the mixture was well mixed. By mixing, a glycol chitin-Span-20 mixed solution was prepared.

The x1-san sponge after acetylation [α in Example 6] was immersed in running water and washed for 24 hours, and then the sponge was immersed in a glycol chitin-Span-20 mixed solution and thoroughly impregnated. Lift the sponge out of the mixed solution and freeze-dry it in a vacuum at a pressure of 0.21131 + 1 g in the moistened state to remove the glycol chitin and span-20.・Obtain a sponge 1. 20 [Effects of the Invention] The cosmetic composition of the present invention is (Concern 1.': Water retention and I5
Because of its flexibility and flexibility, it can be used as a base for a makeup bag, which is made by soaking the material in βi and pasting it on the skin's A side to apply makeup.

Furthermore, since the cosmetic product of the present invention has biocompatibility, antifungal properties, and the effect of promoting wound healing, it also has the effect of promoting protection and regeneration of cells on the skin surface to which it is applied.゜

[Brief explanation of drawings]

FIG. 1 is a chart showing the results of an evaporation test for the product of Example 1.

Claims (6)

[Claims] (1) A method for producing a sponge-like cosmetic material, which comprises molding chitosan into a sponge shape and acylating the spongy chitosan molded product. (2) Acylation reduces the amino group of chitosan to a carbon number of 1 to 3.
2 saturated or unsaturated fatty acids and/or 2 to 2 carbon atoms
8. The method for producing a sponge-like cosmetic material according to claim 1, which comprises chemically modifying the material with a dicarboxylic acid of No. 8. (3) The first claim characterized in that 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. A method for producing a sponge-like cosmetic material according to item 1 or 2. (4) The method for producing a sponge-like cosmetic material according to claims 1 to 3, which comprises impregnating a water-soluble polymeric material and/or a surfactant after acylation. (5) The method for producing a sponge-like cosmetic material according to any one of claims 1 to 4, wherein the chitosan is a mixture of chitosan and collagen. (6) The mixture of chitosan and collagen is 5-50% (
6. The method for producing a sponge-like cosmetic material according to claim 5, characterized in that the sponge-like cosmetic material contains collagen of 50% by weight.