JPH07304626A - Cosmetic having improved moisture retention - Google Patents

Abstract

PURPOSE:To obtain a cosmetic having excellent water retention by synergistic effect. CONSTITUTION:This cosmetic is obtained by blending (A) an N-(3- carboxypropanoyl)-6-O-(carboxymethyl) chitosan of the formula (M is H or an alkali metal; (n) is 10-5,000) with (B) a water-soluble chitin derivative or a water-soluble chitosan derivative (except the compound of the formula) which is made water soluble by introducing a hydrophilic group into a chitin or a chitosan in the weight ratio of the component A:B:(9.5:0.5) to (0.5:9.5), preferably (9.0:1.0) to (1.0:9.0) and has 0.001-5.0wt.%, preferably 0.005-3.0wt.% of the total of both the components. (1) Polyoxyethylene-polyoxypropylene chitin or polyoxyethylene-polyoxypropylene chitosan, (2) carboxymethyl chitin or carboxymethyl chitosan, (3) phosphorylated chitin or phosphorylated chitosan, (4) sulfated chitin or sulfated chitosan, (5) hydroxypropyl chitin or hydroxypropyl chitosan and (6) chitosan 2-hydroxypropylsulfonate may be cited the component B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a derivative of chitosan, N- (3-carboxypropanoyl) -6-O- (carboxymethyl) chitosan (hereinafter abbreviated as CPCM chitosan) and other specific water-soluble chitin. The present invention relates to a cosmetic having excellent moisturizing power, which contains a derivative or a water-soluble chitosan derivative as an essential component.

[0002]

2. Description of the Related Art In recent years, cosmetics having an excellent moisturizing effect have been desired. As substances having such an effect, acidic mucopolysaccharides such as hyaluronic acid, chondroitin sulfate and carboxymethyl chitin are used. Has been done. On the other hand, CPCM chitosan has been proposed as an inexpensive substance having a moisturizing power equivalent to that of hyaluronic acid (Japanese Patent Laid-Open No. 2-105801).

However, although these substances have moderate moisturizing power, they do not have sufficient moisturizing power as a moisturizing agent used for lotions and emulsions used under dry conditions, and development of a moisturizer having high moisturizing power. Was desired by those skilled in the art.

[0004]

An object of the present invention is to improve the moisturizing power of the above-mentioned conventional cosmetics and to provide a cosmetic having excellent moisturizing power.

[0005]

Means and Actions for Solving the Problems The present inventors have
As a result of diligent studies to solve the above problems, it was found that the combined use of CPCM chitosan and other specific water-soluble chitin derivative or water-soluble chitosan derivative at a certain ratio enhances the moisturizing power synergistically. The present invention has been completed based on the above.

That is, in the present invention, the weight ratio of the following components (A) and (B) is 9.5: 0.5 to 0.5:
The present invention relates to a cosmetic having improved moisturizing properties, which is characterized in that it is contained at a blending ratio of 9.5.

(A) General formula (1)

[0008]

[Chemical 1]

(Wherein, M represents hydrogen or an alkali metal, and n represents an integer of 10 to 5000), and N- (3-carboxypropanoyl) -6-O- (carboxymethyl) chitosan ( B) A water-soluble chitin derivative or a water-soluble chitosan derivative which is made water-soluble by introducing a hydrophilic group into chitin or chitosan (however, excluding the chitosan derivative of the general formula (1)) is one of the essential components of the cosmetic composition of the present invention. A component (A), CPCM chitosan, is a product in which the hydroxy group at the 6-position of the glucosamine skeleton constituting chitosan is carboxymethylated and the amino group at the 3-position is carboxypropanoylated to impart water solubility.

As a method for producing this CPCM chitosan, it can be easily obtained by reacting 6-O- (carboxymethyl) chitosan with succinic anhydride, as described in JP-A-2-105801. it can.

The water-soluble chitin derivative and the water-soluble chitosan derivative of the component (B), which is another essential component of the cosmetic composition of the present invention, are water-soluble derivatives obtained by introducing a hydrophilic group into chitin or chitosan. There are things.

Polyoxyethylene / polyoxypropylene chitin or polyoxyethylene / polyoxypropylene chitosan

[0013]

[Chemical 9]

(Where n is an integer of 10 to 5000,
R ¹ , R ² and R ³ are R ¹ : —H, —COCH ₃ or — (EO) _i — (PO) _m.
H where i = 0 to 5, m = 0 to 5, i + m ≠ 0 R ² : -H, or-(EO) _j- (PO) _p H where j = 0 to 5, p = 0 to 5, j + p ≠ 0 R ³ : —H, or − (EO) _k − (PO) _q H, where k = 0 to 5, q = 0 to 5, k + q ≠ 0. Here, EO represents an oxyethylene group, PO represents an oxypropylene group, and the binding order of EO and PO does not matter. For example, first, PO is added to the D-glucosamine skeleton, and then EO is added. EO
And PO may be added at random. In addition, R ¹ , R ² , and R in each of the bonded D-glucosamine skeletons are
³ , i, j, k, m, p, and q may be the same or different, but R ¹ , R ² , and R ³ are not -H at the same time).

Carboxymethyl chitin or carboxymethyl tochitosan

[0016]

[Chemical 10]

(In the formula, n is an integer of 10 to 5000, R ⁴
Is —H or —COCH ₃ , R ⁵ and R ⁶ are —H, —
_{CH 2 COOH, -CH 2 COONa,} -CH 2 COOK
Alternatively, it represents a substituent selected from —CH ₂ COONH ₄ . Further, R ⁵ and R ⁶ in each of the bonded D-glucosamine skeletons may be the same or different, but they do not simultaneously become —H).

Phosphorylated chitin or phosphorylated chitosan

[0019]

[Chemical 11]

Sulfated chitin or sulfated chitosan

[0021]

[Chemical 12]

Hydroxypropyl chitin or hydroxypropyl chitosan

[0023]

[Chemical 13]

Chitosan N-2-hydroxypropyl sulfonate

[0025]

[Chemical 14]

The compounding ratio of the component (A) CPCM chitosan to the component (B) water-soluble chitin derivative or water-soluble chitosan derivative is 9.5: 0.5 to 0.5: 9.5 by weight.
And preferably 9.0: 1.0 to 1.0: 9.0. When the compounding ratio of the component (A) exceeds 9.5,
When it is less than 0.5, or when the blending ratio of the component (B) is less than 0.5 or exceeds 9.5, no synergistic effect is exhibited and the moisturizing effect is not sufficient.

CPC of component (A) in the cosmetic of the present invention
The content of M chitosan and the water-soluble chitin derivative or the water-soluble chitosan derivative of the component (B) is such that the total amount of both components is 0.001 to 5% by weight, preferably 0.005 to 0.005% by weight.
It is 3% by weight. If it is less than 0.001% by weight, the moisturizing effect is insufficient, and if it exceeds 5% by weight, a sticky feeling is produced, which is not preferable.

In the cosmetic of the present invention, various surfactants and auxiliaries commonly used in the following cosmetics can be used, if necessary.

As the anionic surfactant, alkylbenzene sulfonate, α-olefin sulfonate, sodium lauryl sulfate, triethanolamine lauryl sulfate, lauryl sulfate such as ammonium lauryl sulfate,
POE (3) Sodium lauryl ether sulfate, POE
(3) POE lauryl ether sulfates such as triethanolamine lauryl ether sulfate, higher alcohol phosphates, acylmethyl taurine salts such as sodium cocoyl methyl taurine and sodium lauroyl methyl taurine, disodium lauryl sulfosuccinate, POE
(1-4) Disodium lauryl sulfosuccinate, POE sulfosuccinate (5) Disodium lauroylethanolamide, oleic acid amide Disodium sulfosuccinate such as disodium sulfosuccinate, alkyl ether carboxylate, acylated isethionate, fatty acid Amide ether sulfate, monoalkyl phosphate ester salt, polyoxyethylene fatty acid ethanolamide phosphate salt, sodium coconut oil fatty acid, sodium laurate, sodium myristate, sodium tallow fatty acid, coconut oil fatty acid triethanolamine, triethanol laurate Amines, triethanolamine myristate, tallow fatty acid triethanolamine, coconut oil fatty acid potassium, potassium laurate, potassium myristate,
Higher fatty acid salts such as beef tallow fatty acid potassium, cocoyl sarcosine sodium, lauroyl sarcosine sodium, myristoyl sarcosine sodium, lauroyl sarcosine potassium, lauroyl sarcosine triethanolamine and other acyl sarcosine salts, cocoylmethyl-β-alanine sodium, lauroylmethyl-β-alanine Sodium, myristoylmethyl-β-alanine sodium, palmitoylmethyl-β-alanine sodium, stearoylmethyl-β-alanine sodium, lauroylmethyl-β-alanine potassium, lauroylmethyl-
β-alanine triethanolamine and other acylmethyl-
β-alanine salt, acyl-β-alanine salt such as lauroyl-β-alanine triethanolamine, N-2-hydroxyethyl-N-2-lauric acid amidoethylglycine, N-2-hydroxyethyl-N-2- Coconut oil fatty acid amide ethylglycine, N-2-hydroxyethyl-N
-2-lauric acid amide ethyl-β-alanine, N-2
-Hydroxyethyl-N-2-coconut oil fatty acid amide ethyl-β-alanine, N- (carboxymethyl) -N-
{2- [N- (2-hydroxyethyl) lauric acid amide] ethyl} glycine, N- (carboxymethyl) -N
-{2- [N- (2-hydroxyethyl) coconut oil fatty acid amide] ethyl} amide and other amide amino acid salts, coconut oil fatty acid acyl-hydrolyzed silk peptide, lauroyl hydrolyzed silk peptide, palm kernel oil fatty acid-acyl hydrolyzed silk Peptide, coconut oil fatty acid acyl hydrolyzed collagen peptide, lauroyl hydrolyzed collagen peptide, palm kernel oil fatty acid acyl hydrolyzed collagen peptide, coconut oil fatty acid acyl hydrolyzed casein peptide, lauroyl hydrolyzed casein peptide, palm kernel oil fatty acid hydrolyzed casein Peptide, coconut oil fatty acid acyl hydrolyzed keratin peptide, lauroyl hydrolyzed keratin peptide, palm kernel oil fatty acid acyl hydrolyzed keratin peptide acylated product, N-cocoy Sodium L-L-glutamate,
There are, but are not limited to, acylglutamates such as sodium N-lauroyl-L-glutamate and triethanolamine N-cocoyl-L-glutamate.

Further, as the amphoteric surfactant, 2-coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2-palm kernel oil alkyl-N-carboxyethyl-N-hydroxyethylimidazole Alkyl-N-carboxyethyl-N-hydroxyethyl imidazolinium betaine, such as nium betaine, 2-coconut oil alkyl-N-carboxymethyl-N-
Alkyl-N such as hydroxyethyl imidazolinium betaine, 2-palm kernel oil alkyl-N-carboxymeethyl-N-hydroxyethyl imidazolinium betaine
-Carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amide propyl betaine, lauric acid amide propyl betaine, palm kernel oil fatty acid amide propyl betaine and other amidopropyl betaines, lauryl betaine and other alkyl betaines, lauric acid amide hydroxy There are sulfobetaines, sulfobetaines such as lauric acid amide sulfobetaines, and alkyldiaminoethylglycine hydrochloride.

Examples of the cationic surfactant include lauryl trimethyl ammonium chloride and distearyl dimethyl ammonium chloride.

Nonionic surfactants include fatty acid diethanolamide, fatty acid monoethanolamide and POE.
Fatty acid monoethanolamide, amine oxide, PO
There are E higher alcohol ether, POE alkyl phenyl ether, and the like.

As auxiliary agents, polyhydric alcohols such as glycerin, propylene glycol, 1,3-butylene glycol and sorbitol, higher alcohols such as cetyl alcohol and myristic acid, higher fatty acids, hyaluronic acid and carboxymethyl chitin. , Elastin, chondroitin sulphate, dermatanic acid, fibronectin, ceramides, water-soluble polymer substances such as collagen, cell sizing agents such as aloe extract, mucin, placenta extract, eugon extract, tea extract, whey extract etc. Oxidized lipid production inhibitor, allantoin, anti-inflammatory agent such as glycyrrhizinate, chelating agent such as edetate, citric acid, malic acid, gluconic acid, benzoate, salicylate, sorbate, dehydroacetate, paraoxybenzoate Acid salt, 2,4,4'-trichloro-2'-hi Russia carboxymethyl ether, 3,
4,4'-trichlorocarbanito, benzalkonium chloride, hinokitiol, resorcin and other preservatives, fungicides,
Anti-dandruff agents such as zinc pyrithione and piroctone olamine,
Antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, propyl gallate, and ascorbic acid, UV absorbers such as oxybenzone, 4-tert-butyl-4′-methoxybenzoylmethane, 2-ethylhexylparadimethylaminobenzoate, amino-modified Silicone, silicon compounds such as polyether-modified silicone, whitening agents such as kojic acid, arbutin, and vitamin C, perfumes, and pigments can be used.

The cosmetic of the present invention may be in any state, such as a solvent system, a solubilization system, an emulsification system, a powder dispersion system, or a water-oil two-layer system. In addition, the use of cosmetics is optional as long as it can be expected to retain moisture on the skin, but typical examples are lotions, emulsions, creams, packs,
Hair tonic, cleansing cream, beauty essence, foundation, soap, facial cleanser, cleansing foam,
Examples include shampoo, conditioner, body shampoo and the like.

[0035]

EXAMPLES Next, the effect of the combination of the component (A) CPCM chitosan and the component (B) water-soluble chitin derivative or water-soluble chitosan derivative will be described in detail with reference to examples and comparative examples.

The study prescription and the effect were measured by the following methods.

<Formulation of lotion> -Ethanol 10.0 wt% -Glycerin 3.0-CPCM chitosan (component (A)) Amount shown in Table 1-Water-soluble chitin derivative, water-soluble chitosan derivative (component (B)) Amount shown in Table 1-POE (50) oleyl ether 0.5-methyl paraben 0.2-Purified water residue.

<Evaluation of Moisture Retention> The prepared sample was actually used by 10 professional panelists and a sensory test was conducted.
The evaluation results are represented by the following display. ◎ ・ ・ ・ ・ 8 or more out of 10 responded that they were good. ○ ・ ・ ・ ・ 6 out of 10 respondents answered good. △ ・ ・ ・ ・ 4 or more out of 10 respondents answered good. × ・ ・ ・ ・ Less than 4 out of 10 respondents answered good.

The CPCM chitosan, water-soluble chitin derivative and water-soluble chitosan derivative used were as follows. Component (A) -CPCM chitosan: n = 2,500 Component (B) -Ethylene glycol chitin: n = 3,000 Ethylene oxide average addition mole number = 0.8-Hydroxypropyl chitosan n = 3,000 Substitution rate = 0 .8 ・ Sulfated chitin n = 2,500 Replacement ratio = 1.0

[0040]

[Table 1]

From the results shown in Table 1, the lotion containing no CPCM chitosan and water-soluble chitin derivative or water-soluble chitosan derivative of Comparative Example 1 or CPCM chitosan or water-soluble chitin derivative or water-soluble chitosan derivative of Comparative Examples 2 to 5 was used. Of the cosmetics of Examples 1 to 8 in comparison with the cosmetics of which the compounding ratios of the CPCM chitin and the water-soluble chitin derivative of Comparative Examples 6 to 11 are out of the range of the present invention. It can be seen that water has excellent moisturizing properties.

Example 9 A hair brushing agent composition shown below was prepared and its performance was evaluated. The hair brushing agent composition showed an excellent moist feeling. (Composition) -Cocoyl arginine ethyl ester-PCA salt 0.5 wt% -CPCM chitosan (component (A)) 0.3-phosphorylated chitin (component (B)) 0.2-ethanol 5.0-methylparaben 0.1・ Perfume 0.1 ・ Purified water balance.

Example 10 The hair treatment composition shown below was prepared and its performance was evaluated. The hair treatment composition showed an excellent moist feeling. (Composition) -Cetostearyltrimethylammonium chloride 3.0 wt% -CPCM chitosan (component (A)) 0.1-dihydroxypropylchitin (component (B)) 0.05-cetostearyl alcohol 2.5-liquid paraffin 1. 5 POE (5) stearyl ether 1.0 glycerin 5.0 preservative 0.1 purified water balance.

Example 11 The following emulsion was prepared and its performance was evaluated.
This emulsion showed an excellent moist feeling. (Composition) ・ Liquid paraffin 10.0 wt% ・ Squalane 2.0 ・ Vaseline 2.0 ・ Sorbitan sesquioleate 0.9 ・ Polyoxyethylene oleyl ether 1.2 ・ Glycerin 3.0 ・ Ethanol 3.0 ・ Carboxy Vinyl polymer 0.2 ・ Potassium hydroxide 0.1 ・ CPCM chitosan (component (A)) 0.05 ・ Carboxymethyl chitosan (component (B)) 0.03 ・ PCA soda 1.0 ・ Luffa extract 1.0 Preservative 0.5 Purified water balance.

Example 12 When the hair rinse composition shown below was prepared and its performance was evaluated, this hair rinse composition showed an excellent moist feeling. (Composition) -Stearyltrimethylammonium chloride 1.5 wt% -Distearyldimethylammonium chloride 1.5-Cetanol 3.5-Jojoba oil 2.0-Lipophilic glyceryl monostearate 1.0-Polyethylene glycol (8EO) 0 .3 ・ 1.3-butylene glycol 5.0 ・ CPCM chitosan (component (A)) 1.0 ・ N-2-hydroxypropylsulfonic acid chitosan 1.0 (component (B)) ・ hyaluronic acid 0.2 ・Amino-modified silicone polymer 0.5 Preservative 0.3 Purified water balance.

Example 13 A hair shampoo composition shown below was prepared and its performance was evaluated. The hair shampoo composition showed an excellent moisturizing sensation. (Composition) -Polyoxyethylene (3) lauryl ether sulfate sodium (25%) 10.0 wt% -lauroylmethyl-β-alanine sodium (30%) 15.0-lauric acid amidopropyl betaine (30%) 15.0 -N-cocoyl-L-glutamic acid monotriethanol amine salt (30%) 10.0-lauric acid diethanolamide 3.0-CPCM chitosan (component (A)) 1.5-hydroxypropyl chitosan (component (B)) 0.2-Carboxymethyl chitin (component (B)) 0.3-Sodium edetate 0.2-Preservative 0.3-Purified water The balance.

Example 14 When the lotion composition shown below was prepared and its performance was evaluated, this lotion showed an excellent moist feeling. -Ethanol 10.0 wt% -Glycerin 5.0-CPCM chitosan (component (A)) 0.0005-Ethylene glycol chitin (component (B)) 0.0005-Methylparaben 0.1-Sodium edetate 0.1-Purification The rest of the water.

Example 15 When the hair essence composition shown below was prepared and its performance was evaluated, this hair essence showed an excellent moist feeling. -Ethanol 20.0 wt% -CPCM chitosan (component (A)) 0.009-hydroxypropyl chitosan (component (B)) 0.001-methylparaben 0.1-edetate sodium 0.1-purified water balance

[0049]

EFFECT OF THE INVENTION By using CPCM chitosan in combination with a specific water-soluble chitin derivative or water-soluble chitosan derivative as a moisturizing agent, a cosmetic having excellent moisturizing properties can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08B 37/08 A 7433-4C

Claims (9)

[Claims] 1. The following component (A) and component (B)
A cosmetic with improved moisturizing properties, characterized in that it is contained in a blending ratio of 9.5: 0.5 to 0.5: 9.5 by weight. (A) General formula (1) (However, in the formula, M represents hydrogen or an alkali metal, and n
Represents an integer of 10 to 5000) and is represented by N- (3-
Carboxypropanoyl) -6-O- (carboxymethyl) chitosan (B) Water-soluble chitin derivative or water-soluble chitosan derivative (however, chitosan of the general formula (1) is made water-soluble by introducing a hydrophilic group into chitin or chitosan. (Excluding derivatives) 2. The water-soluble chitin derivative or water-soluble chitosan derivative of the component (B) is polyoxyethylene / polyoxypropylene chitin or polyoxyethylene / polyoxypropylene chitosan, carboxymethyl chitin or carboxymethyl chitosan, phosphorylated chitin. The cosmetic according to claim 1, which is at least one selected from the group consisting of phosphorylated chitosan, sulfated chitin or sulfated chitosan, hydroxypropyl chitin or hydroxypropyl chitosan, and chitosan N-2-hydroxypropylsulfonate. . 3. Polyoxyethylene / polyoxypropylene chitin or polyoxyethylene / polyoxypropylene chitosan has the general formula (2): (In the formula, n is an integer of 10 to 5000, R ¹ , R ² and R
³ is R ¹ : —H, —COCH ₃ or — (EO) _i — (PO) _m
H where i = 0 to 5, m = 0 to 5, i + m ≠ 0 R ² : -H, or-(EO) _j- (PO) _p H where j = 0 to 5, p = 0 to 5, j + p ≠ 0 R ³ : —H, or − (EO) _k − (PO) _q H, where k = 0 to 5, q = 0 to 5, k + q ≠ 0. Here, EO represents an oxyethylene group and PO represents an oxypropylene group, and the binding order of EO and PO does not matter. In addition, R ¹ , R ² , R ³ , i, j, k, m, p and q in each of the bonded D-glucosamine skeletons may be the same or different, but R ¹ , R ² , R
³ is never -H at the same time. The cosmetic according to claim 2, which is a compound represented by the formula (4). 4. Carboxymethyl chitin or carboxymethyl chitosan is represented by the general formula (3): (In the formula, n is an integer of 10 to 5000, R ⁴ is —H or —COCH ₃ , and R ⁵ and R ⁶ are —H, —CH ₂ COO.
_{H, -CH 2 COONa, -CH 2} COOK or -CH
₂ represents a substituent selected from COONH ₄ . In addition, R ⁵ and R ⁶ in the individual D-glucosamine skeletons that are bonded may be the same or different, but they do not simultaneously become —H. The cosmetic according to claim 2, which is a compound represented by the formula (4). 5. Phosphorylated chitin or phosphorylated chitosan is represented by the general formula (4): The cosmetic according to claim 2, which is a compound represented by: 6. The sulfated chitin or sulfated chitosan is
General formula (5) The cosmetic according to claim 2, which is a compound represented by: 7. Hydroxypropyl chitin or hydroxypropyl chitosan has the general formula (6): The cosmetic according to claim 2, which is a compound represented by: 8. Chitosan N-2-hydroxypropylsulfonate has the general formula (7): The cosmetic according to claim 2, which is a compound represented by: 9. The cosmetic according to claim 1, wherein the total amount of the component (A) and the component (B) is 0.001 to 5.0% by weight based on the cosmetic.