JPH07196468A - Cosmetic - Google Patents

Abstract

PURPOSE:To provide a cosmetic enhanced in the aging stability of viscosity against heat, pH, salts, etc., and capable of holding a stable quality over a long period by compounding a high quality N-acylated chitosan under a specific condition. CONSTITUTION:The cosmetic contains 0.01-20wt.% of a high quality N-acylated chitosan obtained by perfectly N-acylating chitosan having a deacetylation degree of >=75%. The N-acylated chitosan is negative to a ninhydrin reaction, is excellent in solubility in water and in the stability of viscosity with time, can be compounded without relating to the preparation forms of an aqueous solution, an oil and an aerosol, has both a moisture-retaining effect and an effect as a thickening agent, exhibits an excellent moisture-absorbing and retaining property, and gives an excellent touch free from tackiness and tension. The N-acylated chitosan has an antistatic effect and a good coating film-forming ability originated from the structure of the polymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has a deacetylation degree of 75%.
The present invention relates to a cosmetic composition containing a high-quality raw material that improves the decrease in viscosity of chitosan over time by completely N-acylating chitosan, and particularly enhances the viscosity stability over time of heat, pH, salt, etc. .

[0002]

2. Description of the Related Art Among various dosage forms of cosmetics and pharmaceuticals, semisolid or liquid preparations such as lotions, creams, ointments, essences and emulsions have an appropriate viscosity adjustment / holding property. Therefore, thickeners having an appropriate viscosity have been used. Currently known thickeners represent a great variety of synthetic and natural products. However, when actually using these, in addition to being excellent in safety, there is little influence on the stability of the product over time, and there is no limitation on the usage amount or application, or the feeling of use. Etc. are selected in consideration of some important conditions such as not hindering the performance of the product.

Commonly used synthetic thickeners include, for example, carboxyvinyl polymer, PCA soda,
Polyvinyl alcohol or polyvinyl pyrrolidone,
Examples include polyacrylic acid. However, although these thickeners have an appropriate viscosity like carboxyvinyl polymers, their molecular structure is destroyed by the presence or addition of a salt to cause a decrease in viscosity, or they are affected by pH, so that they may change with time. Since it is unstable, there is a problem that it is very difficult to use in designing the formulation. Further, for the purpose of solving such a problem, it has been attempted to add other polymer compounds as appropriate, but the feeling of use is impaired (causing stickiness), or white turbidity occurs. It was often

On the other hand, natural products include hyaluronic acid, sodium alginate, xanthan gum, polysaccharides obtained from seaweed, and like sodium alginate, they are hydrolyzed and their viscosity decreases with time. There was a problem. Further, in recent years, various attempts have been made to use chitin / chitosan, which is an inexpensive natural polymer and is abundant as a resource, in cosmetics and medical materials, paying attention to its moisture absorption and retention and good feeling of use. To disclose such technology, for example,
JP-A-48-8889, JP-A-49-19040
JP-A-54-95740, JP-A-59-
106409, JP60-1110A, JP61-253065A, and JP2-1058A.
No. 01 publication is cited.

However, any chitin / chitosan or its derivative has insufficient solubility, or viscosity decreases with time, so that the original excellent feeling of use of chitin / chitosan is impaired, and it can be used with confidence. There were many limiting conditions to do. For example, JP-A-48-8889, JP-A-49-19040 and JP-A-54-95.
The N-acylated chitosan, chitosan, and water-soluble partially deacetylated chitin disclosed in Japanese Patent Laid-Open No. 740 and JP-A-60-1110 are solubilized with an organic acid or an inorganic acid to produce products such as cosmetics. However, as a disadvantage, the pH range of the product is restricted by the relationship with the acid used, and the solubility of itself is not stable in a wide pH range, so that p
It was a formulation requirement that H be soluble in a wide range of 3.5 to 10.

Further, the chitin / chitosan derivatives disclosed in JP-A-59-106409, JP-A-2-105801 and the like are stably dissolved in a wide pH range of pH 3.5 to 10. However, by derivatizing chitin / chitosan, the excellent usability of chitin / chitosan is impaired, and as a result, for example, stickiness or tightness occurs when blended into the product, so the blending amount However, it is not suitable for use as a thickener because it is naturally limited or its viscosity decreases with time. On the other hand, although the technology for improving the solubility of chitosan has achieved some results, there are no examples that have solved the problems of viscosity stability while maintaining the full taste of chitosan.

As described above, among the synthetic or natural thickeners that have been conventionally used, there are those having a good feeling in use and having an appropriate thickening effect and excellent viscosity stability. Therefore, there is a demand for the development of a thickener that is stable against heat, pH, and salt.

[0008]

Therefore, the present inventor has paid attention to chitin / chitosan, which is inexpensive and has excellent usability characteristics, and as a result of earnest studies to solve the above problems, it is a starting material for production. By carefully selecting chitosan and completely N-acylating the amino group therein, heat, pH,
The present inventors have completed the present invention based on the finding that a raw material having excellent stability of viscosity with time with respect to salt can be obtained. That is, according to the present invention, a deacetylation degree of 75
% Or more of chitosan is completely N-acylated to obtain a high-quality N-acylated chitosan, which is particularly characterized in that the stability of viscosity with time, pH, salt, etc. is improved. Provided cosmetics are provided. The fully N-acylated high-quality N-acylated chitosan referred to herein (hereinafter, may be simply referred to as acylated chitosan).
Means that it is negative in the ninhydrin reaction known in the confirmation test of amino groups.

The acylated chitosan in the present invention has an important feature that the chitosan obtained by deacetylating natural chitin or chitin by 75% or more is completely N-acylated. The N-acylation method for obtaining an acylated chitosan is N-acylation of the chitosan with a saturated or unsaturated acid anhydride without any special equipment or steps, and in the case of the unsaturated anhydride, Further, it can be easily carried out by adding a carboxyl group or a sulfonic acid group which enhances solubility to the double bond.

The N-acylation reaction of chitosan has a concentration of 0.
It is carried out by adding a compound introducing an amino group of chitosan to an aqueous solution of a salt of chitosan of 2 to 10% and stirring the mixture. The reaction is preferably carried out in a homogeneous solution state, and when adjusting the pH of the reaction solution during the reaction, it is preferable not to form an insoluble matter. Further, the reaction temperature affects the viscosity of the reaction solution and the N-acylation reaction rate, and when the viscosity of the chitosan solution is high, the reaction at a high temperature is preferable in order to improve the homogeneity of the reaction solution. Since the N-acylation reaction is advantageous for the reaction with chitosan in the production at a high temperature, the amount of the compound introduced into the amino group may be smaller than that at a low temperature. Depending on the physical properties such as the deacetylation degree and viscosity of chitosan, the reaction conditions such as the addition amount of the compound introduced into the amino group also differ. For example, chitosan having a deacetylation degree of 85% at 15 to 25 ° C. (Viscosity of 0.5% solution 200c
Regarding ps), 2 to 10 times equivalent of organic acid anhydride is added to 1 equivalent of amino group present in chitosan, and the mixture is stirred for about 2 hours. In this reaction, the acid anhydride can be used in the form of powder or dispersed and dissolved in an inert solvent such as dioxane, tetrahydrofuran or ethyl acetate. Further, since the acylated chitosan of the present invention is an anionic chitosan which is already stably dissolved in a wide pH range at the end of production, it is possible to add a solvent such as alcohol or acetone or to make the pH of the solution strongly acidic. A method of isolating a precipitate from the aqueous solution can be used.

Structure of chitosan as a raw material for achieving the present invention A. N-acetyl-D-glucosamine building block 25%
Less than B. D-glucosamine building block 75%
Super

Structure of acylated chitosan incorporated into the cosmetic of the present invention A. N-acetyl-D-glucosamine building block The same composition as N-acetyl-D-glucosamine in raw material chitosan C. D-Glucosamine Modified Structural Unit In the same composition formula C as D-glucosamine of the starting material chitosan, R is any one of formula (1) to formula (5). Formula (4) Formula (5) (However, R ₁ represents a hydrogen atom or a methyl residue, and m =
When 0 or when n = 0, they are the same or different. R ₂ , R ₃ , R ₄ , and R ₅ , R
₆ and R ₇ are a hydrogen atom, a methyl residue, a hydroxyl residue, an acetoxy residue or a carboxyl residue, a sulfone residue and an acetylthio residue, respectively, and R ₂ and R
₃ or R ₅ and R ₆ together form a methylene group, or when m = 1 or n = 1, R
₂ , R ₃ , R ₄ or R ₅ , R ₆ , R ₇ each represents a hydrogen atom. )

The acidic groups represented in the molecule of the polymers according to the invention can be ionized in aqueous solution and give a salt within building block C. These ionized forms also appear in the presence of inorganic or organic bases. Salts made with these bases are also part of this invention. These salts include, for example, sodium hydroxide, potassium hydroxide,
With a base such as ammonia, lime magnesia, alkanolamine, triethanolamine, triisopropanolamine, aminomethyl propanol, or aminomethyl propanediol, or even more specifically an amino acid having a basic character such as lysine or arginine. Obtainable.

The acylated chitosan of the present invention has the formulas (6) to (10) (However, R ₁ represents a hydrogen atom or a methyl residue, m
= 0, or n = 0, they are the same or different. R ₂ , R ₃ , R ₄ and R ₅ , R
₆ and R ₇ are each a hydrogen atom, a methyl residue, a hydroxyl residue, an acetoxy residue, a carboxyl residue, a sulfone residue, or an acetylthio residue, and R
₂ , R ₃ or R ₅ , R ₆ together form a methylene group, or when m = 1 or n = 1, R ₂ , R ₃ , R ₄ or R ₅ , R ₆ , Each R ₇ represents a hydrogen atom. By N-acylating chitosan with a saturated or unsaturated acid mineral of
Made according to the method completed by the Applicant, so that when using unsaturated anhydrides, the resulting product may have one or several nitrogen atoms intervening in the hydrocarbon residue and (Or) It can be subjected to an addition reaction with at least one primary or secondary amine which may be substituted by one or several amine, hydroxyl, carboxyl, sulfone or mercapto residues.

As the salt of chitosan used in this N-acylation reaction, for example, chlorohydrate or acetate, hydrochloride, lactate and the like are preferably used.

The saturated acid anhydride used may be, for example, succinic anhydride, acetoxysuccinic anhydride, methylsuccinic anhydride, tartaric anhydride, diacetyltartaric anhydride, phthalic anhydride or diglycolic anhydride. The unsaturated acid anhydride used may be, for example, maleic anhydride or itaconic anhydride. If the starting acid anhydride is unsaturated, this N-acylation reaction can be followed by an addition reaction, which allows the product to be very extensive.

The acylated chitosan in the present invention can be used as a thickener, which is the object of the present invention, by selecting those which do not impair the solubility in water, the viscosity stability over time, and the feeling of use of chitosan. It was done. The acylated chitosan of the present invention has not only the effect as a thickening agent but also a moisturizing effect, and shows excellent moisture absorption and retention properties, and solubility in water and viscosity stability over time which cannot be achieved by conventional chitosan and chitosan derivatives. , And sticky,
At the same time, it has an excellent feeling of use without a feeling of tightness. Further, the acylated chitosan of the present invention is a highly safe substance like chitosan, and also has a film-forming ability derived from a polymer structure, an antistatic effect and the like.

Therefore, the acylated chitosan of the present invention is thickened to paints, bath salts, toothpaste, paper products, etc. as well as daily sundries such as foods, cosmetics, pharmaceuticals and shoe creams for the purpose of suppressing water loss. Not only can it be used for the purpose of imparting effects, but it can also be used for the antistatic effect of these products, the feeling of use of the products, or the improvement of the texture after use. Further, the acylated chitosan of the present invention has excellent solubility in water and viscosity stability over time, and therefore can be blended regardless of the form of cream, lotion, gel, aqueous solution, or oil or aerosol product. It is possible to provide a product that can achieve the above effects. When the acylated chitosan of the present invention is added to various products as a thickener, it does not affect the substance of the intended product due to its excellent solubility in water, viscosity stability over time, and usability. Therefore, it can be optionally blended according to the characteristics, viscosity, and purpose of use of the product, but usually 0.01 to 2
If 0% by weight is blended, the initial purpose can be achieved.

In the case of preparing the cosmetic of the present invention, various known active ingredients which are usually used, for example, carpronium chloride, cepharanthin, vitamin E and vitamin E.
Peripheral vasodilators such as nicotinate, nicotinic acid, nicotinic acid amide, benzyl nicotinate, ginger tincture, capsicum tincture, refreshing agents such as camphor, menthol, peppermint oil, antibacterial agents such as hinokitiol, benzalkonium chloride, undecylenic acid , Corticosteroids,
Anti-inflammatory agents such as ε-aminocaproic acid, lysozyme chloride, glycyrrhizin and allantoin, skin-whitening agents such as kojic acid, ascorbic acid and arbutin, placenta extract, liver extract, purple root extract, lactic acid bacterium culture extract, etc.
Various extracts derived from microorganisms and the like can be appropriately added and used according to the purpose at each time. Further, in addition to known active ingredients in the above-mentioned cosmetics, in addition to base components such as oils and fats, known ultraviolet absorbers / scattering agents, humectants, preservatives, antioxidants, chelates, if necessary. Agent, pH adjuster,
Various additives such as fragrances and colorants can be used in combination.

[0020]

EXAMPLES Next, the present invention will be explained based on examples, but these do not limit the present invention in any way.

<Production Example 1> Chitosan with succinic anhydride
Of chitosan (deacetylation degree of 85
%) 2.5 g, and 1.8 g of concentrated hydrochloric acid for neutralizing the free D-glucosamine constitutional unit is added and completely dissolved. After filtering to separate undissolved particles of chitosan,
5 g of succinic anhydride was added and stirred for 1 hour. Subsequently, after adjusting the pH of the reaction solution to 7, 5 g of succinic anhydride was further added and the mixture was stirred for 1 hour. After completion of the reaction, the pH of the reaction solution was adjusted to 10, and the mixture was allowed to stand overnight and then precipitated with ethanol. The precipitate was washed with 50% ethanol and then with acetone to obtain a dried sodium salt of chitosan derivative.

The amount of the functional group to be introduced can be determined by using a total nitrogen analyzer which is a known method. That is, the degree of N-succinylation of the product chitosan derivative is obtained from the change in the total nitrogen ratio contained in the raw material chitosan and the product chitosan derivative. According to it, the degree of N-succinylation is obtained by dissolving approximately 100 mg of a dry sample in 100 ml of purified water and injecting 30 μl of this sample solution into a total nitrogen analyzer to determine the total nitrogen ratio. As a result, the degree of N-succinylation was 85%.

The amino group of the obtained acylated chitosan was further confirmed by a ninhydrin reaction.
About 100 mg of a dried sample of acylated chitosan was exactly dissolved in 100 ml of purified water, and 0.1 ml was added to 10 ml of this sample solution.
% A few drops of ninhydrin aqueous solution were added, and after boiling and cooling for about 15 minutes, the color tone of the blank test sample containing no acylated chitosan treated in the same manner was compared with that of the solution. Was negative and the presence of amino group could not be confirmed. When this ninhydrin reaction is performed on the raw material chitosan or a chitosan derivative that has not been completely N-acylated, the sample solution exhibits a bluish purple color and the ninhydrin reaction is positive.

<Equation 1> Formula for Deacetylation Degree of Raw Material Chitosan Deacetylation Degree: a ₁ Total Nitrogen Ratio Obtained by Total Nitrogen Analyzer: N ₁ (a) N-acetyl-D-glucosamine constitutional unit Molecular weight: 203 (b) D-glucosamine constituent unit molecular weight: 161 Nitrogen atom molecular weight: 14

<Formula 2> Formula for calculating N-acylation degree of N-acylated chitosan N-acylation degree: a ₂ total nitrogen analysis Total nitrogen ratio determined by nitrogen: N ₂ (c) N-acylation -Molecular weight of D-glucosamine derivative sodium salt: 283

<Production Example 2> Chitosan with maleic anhydride
The chitosan (deacetylation degree 94) was dispersed in 500 g of water.
%) 2.5 g, and 1.8 g of concentrated hydrochloric acid for neutralizing the free D-glucosamine constitutional unit is added and completely dissolved. After filtering to separate undissolved particles of chitosan,
5 g of maleic anhydride was added and stirred for 1 hour. Subsequently, the pH of the reaction solution was adjusted to 7, then 5 g of maleic anhydride was further added, and the mixture was stirred for 1 hour. After completion of the reaction, the pH of the reaction solution was adjusted to 10 and left overnight, and then the pH of the reaction solution was adjusted to 3.5 to deposit a precipitate. The precipitate was washed with 50% ethanol and then with acetone, and dried to obtain a chitosan derivative. The amount of the introduced functional group is determined by using a total nitrogen analyzer, which is a known method similar to Production Example 1. As a result of the measurement, the N-succinylation degree was 94%. A ninhydrin reaction was also performed on this chitosan derivative, but the result was negative. Other compounds summarized in Table 1 below were prepared by the same procedure as in Preparation Example 1 or Preparation Example 2.

<Production Example 3> A sulfonic acid group is added to the compound prepared in Production Example 2.
To the dissolved compound 2.5g of manufacturing water 500g Production Example 2 compound. 5 g of sodium hydrogen sulfite (NaHSO ₃ ) was added to this homogeneous solution, and the mixture was stirred at room temperature for 2 hours. Next, the pH of the reaction solution was adjusted to 3.5 with hydrochloric acid to cause precipitation to obtain the target compound. The compound thus obtained is washed with 50% ethanol and acetone and dried. The same procedure was followed to make other compounds summarized in Table 2 below.

[0028]

[0029]

Test Example 1 Viscosity Stability Test with Time (1) Test Method Samples used in the viscosity stability test (Examples 1 to 8 and Comparative Examples 1 to 6 shown in Table 3) had a final viscosity of about 1
000 cps (concentration of chitosan derivative of about 0.5 to 4.
It was dissolved in purified water so that the concentration became 0%, B type viscometer (20 ° C.). Samples that cannot be dissolved in purified water were dissolved using known amounts of sodium hydroxide or lactic acid. The pH of the aqueous solution of the sample to be subjected to the viscosity stability test was adjusted to 6.0 to 6.5. Since the pH of Comparative Example 6 cannot be dissolved in the neutral range, the pH of the evaluation sample aqueous solution of Comparative Example 6 was adjusted to 3.8 to 4.3. Test conditions Test period: 12 weeks Viscosity is measured every 2 weeks until 4 weeks, and thereafter every 4 weeks. Storage conditions: 5 ° C, 20 ° C, 50 ° C Measuring method: B type viscometer, 20 ° C

(2) Test results Test results are shown in Tables 3 and 4.

[0032]

[0033] From the results of the viscosity stability over time of the products of the present invention in Table 3 and the comparative examples in Table 4, it can be seen that the products of the present invention have excellent viscosity stability over time. Particularly, the viscosity stability over time under high temperature conditions is excellent.

<Test Example 2> Viscosity stability test with time against pH and salt concentration (1) Test method Samples used in the viscosity stability test (Examples 1 to 4 shown in Table 5) had a final viscosity of about 1000 cps (toxane). It was dissolved in purified water so that the derivative concentration was about 2.5%, and the B-type viscometer was 20 ° C). Furthermore, sodium chloride is added to the sample aqueous solution for which the viscosity stability test is carried out so that the final concentration is 1.0%,
The pH of the solution was adjusted to 6.0 to 6.5 by adding 0%. Separately, the pH of the test sample aqueous solution
Was adjusted to 5.0 and 9.0, but a stability test was also conducted. Test conditions Test period: 12 weeks Viscosity is measured every 2 weeks until 4 weeks, and thereafter every 4 weeks. Storage conditions: 20 ° C, 50 ° C Measuring method: B type viscometer, 20 ° C

(2) Test Results Table 5 shows the test results.

[0036] It was confirmed that the present invention has excellent viscosity stability with time even in the presence of salt or in a wide pH range.

<Test Example 3> Viscosity stability test in prescription example (1) Test method Viscosity using an emulsion (prescription example 2 below) and essence (prescription example 7 below) using the chitosan derivative of the present invention Stability tests were performed. Emulsion prepared by replacing only the chitosan derivative of the present invention having the emulsion of Formulation Example 2 described below and the essence of Formulation Example 7 described below with the chitosan derivative of Comparative Examples 1 to 3 shown in Table 4, and viscosity stability using essence as a comparison example. A sex test was conducted. The viscosities of the emulsion and essence of the comparative example were adjusted to be almost the same as those of the product of the present invention. Test conditions Test period: 12 weeks Viscosity is measured every 2 weeks until 4 weeks, and thereafter every 4 weeks. Storage conditions: 20 ° C, 50 ° C Measuring method: B type viscometer, 20 ° C

(2) Test results The test results are shown in Table 6.

[0039] The product of the present invention is incorporated into a milky lotion and an essence as a thickener,
It was confirmed that the composition exhibits excellent viscosity stability over time.

<Test Example 4> Evaluation test of feeling of use (1) Test method A conventional polysaccharide (chitosan, carboxymethyl chitin, hyaluron) was prepared by using a lotion containing the chitosan derivative of the present invention (prescription example 3 of the subsequent operation). The feeling of use with (sodium acid salt) was compared by a sensory test. The feeling of use was evaluated by panelists who randomly divided 50 dry skin women into 5 groups of 10 women in each group. To the first group, the lotion of Formulation Example 3 (product of the present invention), to the second group, the lotion containing only the chitosan derivative of Formulation Example 3 changed to chitosan (Comparative Example 1), and to the third group, the formulation A lotion in which only the chitosan derivative of Example 3 was changed to sodium hyaluronate (Comparative Example 2), and a lotion in which only the chitosan derivative of Formulation Example 3 was replaced with carboxymethyl chitin (Comparative Example 3) was used in the fourth group. For the fifth group, a lotion excluding the chitosan derivative of Formulation Example 3 (base: Comparative Example 4) was used. Comparative Examples 1 to 3 were adjusted so that the viscosity of the lotion of Formulation Example 3 used for evaluating the feeling of use was almost the same,
In Comparative Example 4, the viscosity was not adjusted because only the base material was used.

These 5 groups of panelists were asked to apply lotion twice daily in the morning and at night, after washing the face and applying an appropriate amount on the face for 2 months. After 2 months, the "moisturizing feeling of the skin" was obtained. The effectiveness was evaluated with regard to "smoothness during use", which relates to the viscosity of the lotion during use, and "familiarity with the skin (tightness, stickiness)" during use. The evaluation of "moisturizing feeling of the skin" was made according to the following four grades: "Excellent effect", "Effective", "Slightly effective", and "No change" depending on how they were improved before use. Regarding "smoothness during use", regarding the feeling of use for 2 months including the viscosity change of the lotion during use, "good", "somewhat good", "not very good", "not good" We had you judge in four steps of "ta",
As for "familiarity with the skin (tightness, stickiness)", "Feel well" was asked whether it was felt during use.
I was asked to judge in four stages: "I felt a little", "I did not feel much", "I did not feel at all". The results are shown in Tables 7 to 9. The effective rate in the table means that calculated above the effective rate.

[0042]

[0043]

[0044] As is clear from the results of Tables 7 to 9, it was confirmed that the present invention is effective as a lotion, and the viscosity stability with time is improved. It was also confirmed that the efficacy was enhanced more than the reduction of chitosan.

[0045]

[Prescription example] The prescription example of the present invention is given below. In the prescription examples, the “appropriate amount” means an amount that makes the entire prescription 100% by weight. <Prescription example 1> Cream (% by weight) 1. Polyethylene glycol monostearate (40E.0.) 2.00 2. Self-emulsifying glyceryl monostearate 5.00 3. Stearic acid 5.00 4. Behenyl alcohol 1.00 5. Liquid paraffin 10.00 6. Glyceryl trioctanoate 10.00 7. Ethyl paraoxybenzoate 0.20 8.1,3-butylene glycol 5.00 9. Disodium edetate 0.01 10. Chitosan derivative (Compound No. 2 in Table 1) 0.50 11. Purified water Proper amount Manufacturing method A. Heat 1 to 6 to dissolve. B. 7 to 11 are heated and dissolved. C. Add B to A, emulsify, stir, and cool. D. After C is cooled, it is filled in a container to be a product after inspection. To inunction usage and dose an appropriate amount on the face.

<Formulation Example 2> Emulsion (wt%) 1. Monostearic acid Polyoxyethylene sorbitan (20E.0.) 2.00 2. Tetraoleic acid polyoxyethylene sorbit (60E.0.) 0.50 3. 3. Lipophilic glyceryl monostearate 1.00 4. Stearic acid 0.50 5. Behenyl alcohol 0.50 6. Avocado oil 4.00 7. Glyceryl trioctanoate 4.00 8. Methyl paraoxybenzoate 0.20 9.1,3-butylene glycol 5.00 10. Disodium edetate 0.01 11. Chitosan derivative (Compound No. 1 in Table 1) 0.20 12. Purified water Proper amount Manufacturing method A. Heat 1 to 7 to dissolve. B. Dissolve 8 to 12 by heating. C. Add B to A, emulsify, stir, and cool. D. After C is cooled, it is filled in a container to be a product after inspection. To inunction usage and dose an appropriate amount on the face.

<Formulation Example 3> Lotion (% by weight) 1. Polyoxyethylene hydrogenated castor oil (60E.0.) 8.00 2. Chitosan derivative (Compound No. 4 in Table 1) 0.20 3. Ethanol 15.00 4. Ethyl paraoxybenzoate 0.10 5. Citric acid 0.10 6. Sodium citrate 0.30 7.1,3-butylene glycol 4.00 8. Disodium edetate 0.01 9. Purified water Proper amount Manufacturing method A. Stir 1 to 9 uniformly and dissolve. B. A is filled in a container and the product is obtained after the inspection. To inunction usage and dose an appropriate amount on the face.

(Wt%) <Formulation Example 4> Ointment 1. Polyethylene glycol monostearate (40E.0.) 2.00 2. Self-emulsifying glyceryl monostearate 5.00 3. Stearic acid 5.00 4. Behenyl alcohol 1.00 5. Liquid paraffin 10.00 6. Glyceryl trioctanoate 10.00 7. Ethyl paraoxybenzoate 0.20 8.1,3-butylene glycol 5.00 9. Disodium edetate 0.01 10. Chitosan derivative (Compound No. 2-1 in Table 2) 3.00 11. Purified water Proper amount Manufacturing method A. Heat 1 to 6 to dissolve. B. 7 to 11 are heated and dissolved. C. Add B to A, emulsify, stir, and cool. D. After C is cooled, it is filled in a container to be a product after inspection. To inunction usage and dose an appropriate amount on the face.

<Formulation Example 5> Pap agent (% by weight) 1. Chitosan derivative (Compound No. 3-1 in Table 2) 3.00 2. Sodium polyacrylate 20.00 3. Aluminum chloride 0.30 4. Concentrated glycerin 20.00 5. Sorbitan monooleate 1.00 6. Titanium oxide 4.00 7. Purified water Proper amount Manufacturing method A. 1 to 2, 5 and 7 are heated and dissolved. B. Dissolve 3 to 4 and 6 by heating. C. Add B to A, stir evenly, and mix. D. After cooling C, it is applied to a coating agent, and a product is obtained after inspection. Usage and dose: Remove the liner and apply to the affected area.

<Formulation Example 6> Bath agent (% by weight) 1. Liquid paraffin 50.00 2. Glycerin di-2-heptyl undecanoate monostearate 5.00 3. Polyoxyethylene (2E.0.) Glycerin monostearate 2.00 4. Polyoxyethylene (9E.0.) Monooleate 2.00 5. Polyoxyethylene (3E.0.) Lauryl ether 5.00 6. Vitamin E 0.20 7. Chitosan derivative (from Production Example 1) 5.00 8. Fragrance 1.00 9. Small amount of dye 10. Ethanol Proper amount production method A. Mix and dissolve 1 to 8. B. Add 9 to 10 and dissolve. C. Add B to A and stir uniformly. D. C is filled in a soft capsule and the product is obtained after the inspection. Dosage and dosage Put an appropriate amount in the bath and take a bath.

<Formulation Example 7> Essence (% by weight) 1. Elastin hydrolysis solution 1.00 2. Glycerin 20.00 3. Sodium hyaluronate 0.50 4. Ethanol 7.00 5. Chitosan derivative (from Production Example 2) 2.00 6. Purified water Appropriate amount Manufacturing method Mix the above components, stir evenly and dissolve them to manufacture essence, and make the product after inspection. To inunction usage and dose an appropriate amount on the face. It was confirmed that all of the skin cosmetics of Formulation Examples 1 to 7 are preparations having an effect satisfying the object of the present invention.

[0052]

According to the present invention, the degree of deacetylation is 75%.
The above chitosan is a fully N-acylated high quality N
-Provided is a cosmetic composition containing an acylated chitosan, which is characterized in that the stability of the viscosity over time, especially with respect to heat, pH, salt, etc., is enhanced, and stable quality can be maintained for a long period of time.

Claims (1)

[Claims] 1. A cosmetic comprising a complete N-acylated chitosan having a deacetylation degree of 75% or more.