JPH07304801A - Polysaccharide derivative, its production and cosmetic and cleaning agent composition containing the derivative - Google Patents

Abstract

PURPOSE:To produce a polysaccharide derivative useful as a cosmetic and a cleaning agent having excellent water-retainability and feeling, keeping the effect over a long period, giving excellent feeling to the skin and resistant to sweat and water by introducing a carboxybetaine group to a polysaccharide. CONSTITUTION:This polysaccharide derivative is expressed by the formula (Z is a polysaccharide residue obtained by removing n-OH groups from a polysaccharide molecule; R<1> and R<2> each is a 1-3C straight or branched chain alkyl which may have hydroxyl group; A is a 1-3C straight or branched chain alkylene; (n) is a number not larger than the total number of hydroxyl groups in the polysaccharide molecule). The polysaccharide is selected from beta-1,4-glucan, alpha-1,4-glucan, alpha-1,6-glucan, pullulan, their hydroxyethyl derivatives, hydroxypropyl derivatives and 2,3-hydroxypropyl derivatives, for example cellulose or starch. The average degree substitution of the carboxybetaine group per one sugar residue in the polysaccharide molecule is 0.1-0.3. The derivative is produced by converting a polysaccharide of formula Z-(OH)n to a deoxyhalogenated polysaccharide, reacting with an amine and reacting the resultant aminopolysaccharide with a monohalogenated carboxylic acid salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysaccharide derivative having an excellent moisturizing effect and a protective effect on hair and skin, a method for producing the same, and a cosmetic and detergent composition containing the same.

[0002]

2. Description of the Related Art Hitherto, various moisturizers have been incorporated into many shampoos, rinses, cosmetics and the like in order to impart a moist feel to hair and skin. Generally, glycols such as glycerin and propylene glycol; sugar alcohols such as sorbitol and maltitol; urea and alkylene oxide adducts of sugars are used as these moisturizing agents. However, these moisturizers are not always satisfactory in terms of moisturizing properties and feel, and they easily diffuse and flow out with sweat or water, and their effect is difficult to last. In most of the surfactants, they were washed out, and it was often impossible to exhibit sufficient moisturizing properties.

[0003]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a moisturizer having excellent moisturizing properties and having a strong moisturizing effect against sweat and water and a long-lasting protective effect. .

[0004]

Under the circumstances, the inventors of the present invention have conducted diligent research and, as a result, have found that a polysaccharide derivative in which a carboxybetaine group is introduced into a polysaccharide has excellent moisturizing properties and feel, and its effects. The present invention has been completed based on the finding that cosmetics and detergents having a good feeling of use can be obtained by maintaining these ingredients for a long time and further by blending these polysaccharide derivatives.

That is, the present invention provides the following general formula (1):

[0006]

[Chemical 3]

(In the formula, Z represents n hydroxyl groups in the polysaccharide molecule.
The polysaccharide residue excluding the group is¹And R ²Are the same or different
Is a straight chain having 1 to 3 carbon atoms which may have a hydroxy group.
A chain or branched alkyl group, A is a straight chain having 1 to 3 carbon atoms
Or represents a branched alkylene group, and n is a polysaccharide molecule in the polysaccharide molecule.
New natural number less than the total number of hydroxyl groups)
A sugar derivative is provided.

The present invention also provides a method for producing this polysaccharide derivative. Furthermore, the present invention provides a cosmetic and cleaning composition containing this polysaccharide derivative.

In the formula (1) of the present invention, Z represents a polysaccharide residue in which n hydroxyl groups substituted with a carboxybetaine group are removed from the polysaccharide molecule, and Z- (OH) _n The polysaccharides represented by β-1,4-glucan, α
Examples include -1,4-glucan, α-1,6-glucan, pullulan, and their hydroxyethyl derivatives, hydroxypropyl derivatives and 2,3-dihydroxypropyl derivatives.

Specific examples of these polysaccharides include cellulose, starch, amylose, pullulan, dextran, hydroxyethylated cellulose, hydroxypropylated cellulose, 2,3-dihydroxypropylated cellulose, hydroxyethylated starch, hydroxypropylated. Starch, 2,3-dihydroxypropylated starch, hydroxyethylated amylose, hydroxypropylated amylose, 2,3-dihydroxypropylated amylose, hydroxyethylated pullulan, hydroxypropylated pullulan, 2,3-dihydroxypropylated pullulan, hydroxy Mention may be made of ethylated dextran, hydroxypropylated dextran and 2,3-dihydroxypropylated dextran, among which cellulose, starch, Mirosu, pullulan, dextran preferable, cellulose, starch is particularly preferred.

R ¹ and R ² in the formula (1) are hydroxyethyl group, 2-hydroxypropyl group and 2,3-
Examples thereof include a dihydroxypropyl group, a methyl group, an ethyl group, a propyl group and an isopropyl group, with a hydroxyethyl group and a methyl group being particularly preferable.

Examples of A include a methylene group, an ethylene group, a propylene group and a 2-hydroxypropylene group, and a methylene group and an ethylene group are particularly preferable.

[0013] n represents the number of those substituted with carboxybetaine groups among all the hydroxyl groups in the polysaccharide molecule. Generally, polysaccharides have three hydroxyl groups per sugar residue,
Up to a maximum degree of substitution of 3 can be substituted with a carboxybetaine group. The average substitution degree of the carboxybetaine group per sugar residue in the polysaccharide molecule of the present invention may be 0.1 to 3.0, but in consideration of water solubility and easiness of production,
It is more preferable that the average degree of substitution is 0.3 to 1.5.

The polysaccharide derivative (1) of the present invention is obtained by halogenating the polysaccharide (2) into a deoxyhalogenated polysaccharide (3) according to the following reaction formula, and then reacting this with an amine (4). At least no aminated polysaccharide (5),
Further, it is produced by reacting this with a monohalogenated carboxylic acid salt (6).

[0015]

[Chemical 4]

(In the formula, X and Y are halogen atoms, B is an alkali metal, and Z, R ¹ , R ² , A and n have the same meanings as above).

The halogenation of the polysaccharide (2) is carried out as follows. As the halogenating agent, various ones such as thionyl halide, phosphorus oxyhalide and phosphorus pentahalide are used, but thionyl chloride and thionyl bromide are particularly preferable. The polysaccharide (2) is dispersed in a solvent such as N, N-dimethylformamide (DMF) in an amount of 1 to 20 times by weight, preferably 5 to 15 times by weight, and 0.5 to 5 times by weight of the polysaccharide. , Preferably 1 to 3 times by weight of a halogenating agent, and added to 0 to 100 ° C., preferably 40 to 80 ° C.
It is preferable to react at the temperature of 1 to 10 hours. After distilling off the solvent from the reaction mixture under reduced pressure, ice water was added to the residue to precipitate a solid, which was neutralized with an alkali such as sodium hydroxide or potassium hydroxide, and then filtered and dried to remove the deoxyhalogenated poly. Sugars (3) can be obtained.

Examples of amines (4) which can be reacted with the deoxyhalogenated polysaccharide (3) include dimethylamine, N-methylethanolamine, N-methyl-3-amino-1-propanol and N-methyl-3. -Amino-
1,2-dihydroxypropane, N-methyl-3-amino-2-propanoldiethylamine, N-ethylethanolamine, N-ethyl-3-amino-1-propanol, N-ethyl-3-amino-1,2- Dihydroxypropane, N-ethyl-3-amino-2-propanoldipropylamine, N-propylethanolamine, N
-Propyl-3-amino-1-propanol, N-propyl-3-amino-1,2-dihydroxypropane, N
-Propyl-3-amino-2-propanol, diethanolamine, bis (2,3-dihydroxypropyl) amine, bis (3-hydroxypropyl) amine, bis (2-hydroxypropyl) amine and the like can be mentioned.

The reaction between the deoxyhalogenated polysaccharide (3) and the amines (4) is performed by using the deoxyhalogenated polysaccharide (3)
Is dissolved in a solvent such as dimethyl sulfoxide (DMSO), N, N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), and DMF, and the amines (4) are added thereto to obtain 50-200. ℃, preferably 80
The reaction is preferably carried out at ˜150 ° C. for 10 to 50 hours.
The amount of the solvent is 1 to 20 times the weight of (3), especially 5 to 1
It is preferably 5 times by weight, and the amount of the amines (4) is preferably 1 to 5 equivalent times, particularly preferably 1 to 3 equivalent times with respect to the halogen equivalent of (3).

The solvent is distilled off from the reaction solution under reduced pressure, alcohols such as methanol and ethanol or ketones such as acetone and methyl ethyl ketone are added to the residue to precipitate a solid, and the solid is further filtered and dried. Thus, the aminated polysaccharide (5) can be obtained.

As the monohalogenated carboxylic acid salt (6) which is reacted with the aminated polysaccharide (5), monochloroacetic acid, 2-chloropropionic acid, 3-chloropropionic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, 2-chloroisobutyric acid monobromoacetic acid, 2-bromopropionic acid, 3-bromopropionic acid, 2-bromobutyric acid, 3-bromobutyric acid, 4-bromobutyric acid, 2-bromoisobutyric acid, monoiodoacetic acid, 2-iodo Propionic acid, 3-
Mention may be made of sodium salts or potassium salts of monohalogenated carboxylic acids such as iodopropionic acid, 2-iodobutyric acid, 3-iodobutyric acid, 4-iodobutyric acid and 2-iodoisobutyric acid.

The reaction between the aminated polysaccharide (5) and the monohalogenated carboxylate (6) is carried out in the presence of alkali. First, the aminated polysaccharide (5) is dissolved in 1 to 20 times by weight, preferably 2 to 10 times by weight, of water, and 1 to 2 equivalent times of the hydrogen halide in the aminated polysaccharide is dissolved therein. Add sodium hydroxide, potassium hydroxide, etc. in the state of solid or aqueous solution. Then, the monohalogenated carboxylate (6) is added to this solution in an amount of 1 to 5 equivalent times, preferably 1.5 to 3 equivalent times with respect to the amino group in a solid or aqueous solution state, 20 to 100 ° C., preferably The reaction is carried out at 50 to 90 ° C. for 5 to 50 hours. During the reaction, the pH of the reaction solution may decrease due to hydrogen halide generated by the hydrolysis of the monohalogenated carboxylate, but in this case, the pH of the reaction solution is raised to 9 or more by adding the above alkaline substance at any time. Adjust to keep.

After completion of the reaction, acetic acid was added to the obtained reaction mixture.
Neutralize by adding inorganic or organic acid such as sulfuric acid or hydrochloric acid, unreacted monohalogenated carboxylic acid salt by dialysis and electrodialysis, hydroxycarboxylic acid salt by-produced by hydrolysis, and further during reaction or neutralization By removing the inorganic or organic acid salts that are sometimes produced, an aqueous solution of the desired polysaccharide derivative (1) is obtained. In addition, this polysaccharide derivative can be used in a state where the desalting operation is not performed unless there is a problem depending on the application. The solid product of the polysaccharide derivative (1) can be obtained by freeze-drying this aqueous solution or solidifying it with a solvent such as methanol, ethanol, isopropyl alcohol, or acetone.

Since the polysaccharide derivative of the present invention has excellent moisturizing properties, it serves as a moisturizing agent for skin and hair cosmetics,
It can be used as a cleaning agent such as shampoo and kitchen detergent. When used in cosmetics, the content of the polysaccharide derivative is 0.
01 to 20% by weight (hereinafter simply referred to as%), particularly 0.1
10% is preferable, and if it is less than 0.01%, a sufficient moisturizing effect cannot be obtained, and even if it exceeds 20%, an effect commensurate with the blending amount cannot be expected, and it is not preferable from the economical aspect.

In addition to the polysaccharide derivative of the present invention, the above-mentioned cosmetics include other components used in conventional cosmetics, such as ethylene glycol, diethylene glycol, triethylene glycol, and higher polyethylene glycols; propylene glycol, dipropylene. Glycols and other polypropylene glycols; Butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol; glycerin, diglycerin and higher polyglycerins; sorbitol, mannitol, xylitol, maltitol, etc. Sugar alcohols; ethylene oxide (hereinafter abbreviated as EO) and propylene oxide (hereinafter abbreviated as PO) adducts of glycerins; EO and PO adducts of sugar alcohols; galactose, glucose, fructose, shoe Sugars such as syrup, maltose, lactose and their EO and PO adducts; glycosides such as methyl glycoside and ethyl glycoside and their polyhydric alcohols such as EO and PO adducts: carbonization of liquid paraffin, squalane, vaseline and solid paraffin Hydrogen; natural oils such as olive oil, jojoba oil, evening primrose oil, coconut oil, beef tallow; isopropyl myristate, cetyl isooctanoate,
Ester oil such as neopentyl glycol dicaprate;
Silicone oils such as methyl silicone and methyl phenyl silicone; oily components such as higher fatty acids such as isostearic acid and oleic acid: polyoxyethylene (hereinafter abbreviated as POE) alkyl ether, POE branched alkyl ether, POE sorbitan ester, POE glycerin fatty acid Nonionic surfactants such as esters, POE hydrogenated castor oil, sorbitan esters, glycerin fatty acid esters, polyglycerin fatty acid esters; anionic surfactants such as phosphoric acid-based, sulfonic acid-based, sulfuric acid-based, carboxylic acid-based; Other amphoteric surfactants; cationic surfactants, etc .: vitamins; bactericides such as triclosan and trichlorocarban; anti-inflammatory agents such as dipotassium glycyrrhizinate and tocopherol acetate; antidandruff agents such as zinc pyrithione and octopirox; activation Cooling agents such as menthol; UV absorbers and other agents: Preservatives such as methylparaben and butylparaben: Inorganic salts: Viscosity modifiers such as polyethylene glycol stearate and ethanol: Pearling agents: Fragrances: Dyes: Antioxidants : Water-swelling clay minerals such as montmorillonite, saponite, hectorite, bee gum, cunivia, smecton: Carrageenan, xanthan gum, sodium alginate, pullulan, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and other polysaccharides: carboxyvinyl polymer, polyvinyl Other polymers such as synthetic polymers such as pyrrolidone: titanium oxide, kaolin, mica,
Inorganic pigments such as sericite, zinc white, and talc; pigments such as polymer powders such as polymethylmethacrylic acid and nylon powder, and the like can be appropriately added within a range that does not impair the effects of the present invention.

The cosmetic of the present invention can be produced by a conventional method, and its dosage form can be any dosage form such as liquid, cream, solid, powder, etc., but especially liquid or It is preferably creamy.

When the polysaccharide derivative of the present invention is added to the detergent composition, the amount of the polysaccharide derivative is 0.1 to 30.
%, Particularly 0.2 to 10% is preferable, and if it is less than 0.1%, a sufficient moisturizing effect cannot be obtained, and if it exceeds 30%, there is no great difference in the moisturizing effect, which is not preferable.

In the detergent composition of the present invention, various surfactants usually used in detergents can be optionally used within the range not impairing the effects of the present invention. Specifically, examples of the anionic surfactant include sulfate, and examples of the sulfonate system include alkyl sulfate, polyoxyethylene alkyl sulfate, sulfosuccinic acid system, taurate system, isethionate system, and α-olefin sulfonic acid system. Examples of surfactants include carboxylate-based surfactants such as fatty acid soaps, ether carboxylic acid-based surfactants, and acylated amino acid-based surfactants. Phosphate-based surfactants include alkyl phosphate ester-based surfactants. Is mentioned. Examples of the amphoteric surfactant include carbobetaine-based, phosphobetaine-based, sulfobetaine-based and imidazolinium betaine-based amphoteric surfactants. As the nonionic surfactant, polyoxyalkylene addition type, polyoxypropylene / polyoxyethylene addition type, amine oxide type, mono- or diethanolamide type,
Other sorbitan fatty acid ester and its POE adduct, glycerin fatty acid ester and its POE adduct,
Examples thereof include sucrose ester and POE adducts, alkyl saccharides and POE adducts, and N-polyhydroxyalkyl fatty acid amides. Examples of the cationic surfactant include a mono- or dialkyl-added quaternary ammonium salt having a linear or branched alkyl group and an alkylene oxide added to the alkyl group.

These surfactants may be used singly or in a combination of two or more kinds, and the compounding amount is 0.1 to 60% in the detergent composition of the present invention, though it varies depending on the dosage form.
It is particularly preferably 1 to 50%.

In the detergent composition of the present invention, in addition to the above-mentioned components, components used in ordinary detergents, such as ethylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycols higher than them; propylene glycol, diethylene glycol Propylene glycol and higher polypropylene glycols; Butylene glycols such as 1,3-butylene glycol and 1,4-butylene glycol; glycerin, diglycerin and higher polyglycerins; sorbitol, mannitol, xylitol, maltitol, etc. Sugar alcohols of glycerin; ethylene oxide and propylene oxide adducts of glycerin; EO and PO adducts of sugar alcohols; sugars such as galactose, glucose, fructose, sucrose, maltose and lactose As EO, PO adducts; methyl glycoside, glycosides such as ethyl glycoside and its E
Polyhydric alcohols such as O and PO adducts: Hydrocarbons such as liquid paraffin, squalane, vaseline and solid paraffin: Natural oils such as olive oil, jojoba oil, evening primrose oil, coconut oil and beef tallow; isopropyl myristate, cetyl isooctano Ester oils such as pentate and neopentyl glycol dicaprate; Silicone oils such as methylsilicone and methylphenylsilicone; Oily components such as higher fatty acids such as isostearic acid and oleic acid: vitamins; fungicides such as triclosan and trichlorocarbane; glycyrrhizin Anti-inflammatory agents such as dipotassium acid and tocopherol acetate; antidandruff agents such as zinc pyrithione and octopirox; activators;
Cooling agents such as menthol; UV absorbers and other agents: Preservatives such as methylparaben and butylparaben: Inorganic salts: Polyethylene glycol stearate, viscosity modifiers such as ethanol: Pearling agents: Fragrances: Dyes: Antioxidants: Water-swelling clay minerals such as montmorillonite, saponite, hectorite, veegum, cunivia, smecton: carrageenan, xanthan gum, sodium alginate, pullulan, methylcellulose, carboxymethylcellulose,
Polysaccharides such as hydroxyethyl cellulose and hydroxypropyl cellulose: Other polymers such as synthetic polymers such as carboxyvinyl polymer and polyvinylpyrrolidone: Inorganic pigments such as titanium oxide, kaolin, mica, sericite, zinc white, and talc; polymethyl Pigments such as methacrylic acid and polymer powder such as nylon powder can be appropriately blended within a range that does not impair the effects of the present invention.

The detergent composition of the present invention can be produced by a usual method, and its dosage form can be any dosage form such as liquid, paste, solid and powder.
In particular, it is preferably liquid or paste.

[0032]

INDUSTRIAL APPLICABILITY The polysaccharide derivative of the present invention has an excellent moisturizing ability, does not easily lose its effect even when washed off, and has a moist feel without stickiness. It is extremely useful as a moisturizer to be added to a composition or the like.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples and test examples, but the present invention is not limited thereto.

Example 1 Synthesis of (N-methyl-N-hydroxyethyl-N-carboxymethyl) aminodeoxycellulose: Cellulose powder (made by MERCK) in a 2 liter reaction vessel.
81 g was dispersed in 1500 g of N, N-dimethylformamide, and 120 g of thionyl chloride was added dropwise at room temperature over 30 minutes, and further reacted at 80 ° C. for 4 hours. After completion of the reaction, 750 g of the solvent was distilled off at 80 ° C. under reduced pressure, the residue was poured into 5 l of ice water to precipitate, and a 20% aqueous sodium hydroxide solution was added for neutralization. The precipitate was collected by filtration, washed with water and ethanol, dried under reduced pressure at 100 ° C. for 24 hours, and 87 g of chlorodeoxycellulose as a pale yellow powder having a chlorine substitution degree of 0.75 (C1%: 15.2%) (yield). 99%).
77 g of the obtained chlorodeoxycellulose was dissolved in 1200 g of N-methylpyrrolidone, 63 g of N-methylethanolamine was added, and the mixture was reacted at 140 ° C. for 24 hours. The solvent was distilled off from the reaction solution under reduced pressure at 100 ° C., acetone was added to the residue to precipitate the reaction product, and the precipitate was collected by filtration. The obtained precipitate was washed with acetone and ethanol and dried under reduced pressure at 100 ° C. for 24 hours to obtain N-methyl-N.
58 g (yield 57%) of the hydrochloride of hydroxyethylaminodeoxycellulose was obtained. Furthermore, N-methyl-N-
46 g of hydroxyethylaminodeoxycellulose was dissolved in 500 g of ion-exchanged water, and 32 g of 30% aqueous sodium hydroxide solution was added. Next, 47 g of sodium monochloroacetate was added to the reaction solution and reacted at 65 ° C. for 12 hours. After the reaction was completed, the reaction solution was neutralized with acetic acid, 300 g of water was distilled off under reduced pressure at 65 ° C., the reaction mixture was desalted using a dialysis membrane, and then the desalted solution was freeze-dried to give a yellow powder. Of (N
22 g (yield 45%) of -methyl-N-hydroxyethyl-N-carboxymethyl) aminodeoxycellulose was obtained. The N content of the obtained compound was 4.15%, and the substitution degree of the carboxybetaine group was 0.73.

IR (KBr tablet) cm ^-1 : (FIG. 1) 3450 (OH), 2930 (CH), 1630
^{(-COO -), 1405 (-COO} -), 1060 (C
-OC).

Example 2 Synthesis of (N, N-bishydroxyethyl-N-carboxymethyl) aminodeoxystarch: 81 g of cornstarch (manufactured by Nacalai Tesque) N, N-dimethylformamide 1500 in a 2 liter reaction vessel.
g, thionyl chloride (100 g) was added dropwise at room temperature over 30 minutes, and the mixture was further reacted at 80 ° C. for 3 hours. After the reaction was completed, the chloro substitution degree was 0.56 by the same operation as in Example 1.
84 g (yield 97%) of chlorodeoxystarch as a pale yellow powder of (C1%: 11.6%) was obtained. 52 g of the obtained chlorodeoxystarch was added to dimethylacetamide 800
After being dissolved in g, 64 g of diethanolamine was added, and the mixture was reacted at 140 ° C. for 24 hours. After completion of the reaction, 45 g of (N, N-bishydroxyethyl) aminodeoxy starch hydrochloride (yield 65
%) Was obtained. Furthermore, (N, N-bishydroxyethyl)
Aminodeoxy starch 30g ion-exchanged water 400g
20 g of a 30% aqueous sodium hydroxide solution was added. Next, 29 g of sodium monochloroacetate was added to the reaction solution and reacted at 70 ° C. for 10 hours. After the reaction was completed, the reaction solution was neutralized with acetic acid, 300 g of water was distilled off under reduced pressure at 65 ° C., the reaction mixture was desalted by electrodialysis, and the desalted solution was freeze-dried to give a yellow powder ( 11 g (yield 37%) of N, N-bishydroxyethyl-N-carboxymethyl) aminodeoxystarch was obtained. The N content of the obtained compound was 3.18%, and the substitution degree of the carboxybetaine group was 0.55.

IR (KBr tablet) cm ^-1 : 3445 (O-
H), 2930 (C-H ), 1625 (-COO -),
1400 (-COO -), 1060 ( C-O-C).

Example 3 Synthesis of (N-methyl-N-hydroxyethyl-N-carboxyethyl) aminodeoxycellulose: Cellulose powder (made by MERCK) in a 2 liter reaction vessel.
90 g of N, N-dimethylformamide was dispersed in 1500 g, 150 g of thionyl chloride was added dropwise at room temperature over 30 minutes, and the mixture was further reacted at 80 ° C. for 5 hours. After completion of the reaction, the chloro substitution degree of 0.92 (C1
%: 18.2%) of pale yellow powder chlorodeoxycellulose 93g (yield 94%) was obtained. 50 g of the obtained chlorodeoxycellulose was added to N-methylpyrrolidone 1200
After being dissolved in g, 43 g of N-methylethanolamine was added, and the mixture was reacted at 120 ° C. for 30 hours. After the completion of the reaction, the same procedure as in Example 1 was repeated to obtain 44 g of N-methyl-N-hydroxyethylaminodeoxycellulose hydrochloride.
(Yield 64%) was obtained. Further, 37 g of N-methyl-N-hydroxyethylaminodeoxycellulose was dissolved in 500 g of ion-exchanged water, 24 g of 30% aqueous sodium hydroxide solution was added, and 57 g of sodium 3-bromopropionate was added to this reaction solution at 80 ° C. The reaction was carried out for 12 hours. After the completion of the reaction, the same operation as in Example 1 was performed to obtain 22 g of (N-methyl-N-hydroxyethyl-N-carboxyethyl) aminodeoxycellulose as a yellow powder (yield 4
5%) was obtained. The obtained compound had an N content of 4.50% and a carboxybetaine group substitution degree of 0.89.

IR (KBr tablet) cm ^-1 : 3450 (O-
H), 2925 (C-H ), 1625 (-COO -),
1405 (-COO -), 1055 ( C-O-C).

Test Example 1 The moisturizing ability and feeling of use of the polysaccharide derivative of the present invention were evaluated by the following methods. The results are shown in Table 1.

Moisture retention evaluation method: A 2% aqueous solution of each sample was prepared, and 10 μl of the sample solution per cm ² was applied to the flexion side of the human forearm conditioned at 20 ° C./40% RH and left for 10 minutes. Before and after this process
The skin conductance was measured using -200 (manufactured by IBS), and the moisturizing ability was calculated from the ratio of the conductance before and after the treatment according to the following formula. (N = 10)

[0042]

[Equation 1] Moisturizing capacity = conductance after treatment / conductance before treatment

After that, the treated area was rinsed with running water, towel-dried and allowed to stand for 10 minutes, the skin conductance was measured in the same manner, and the moisturizing ability after rinsing was determined according to the following formula.

[0044]

[Formula 2] Moisturizing ability after rinsing = Conductance after rinsing / Conductance before treatment

Feeling evaluation method: A 10% aqueous solution of each sample was prepared, and 200 μl of the solution was uniformly applied to the flexor side of the forearm of the evaluator and left for 3 minutes. Then, the application site was touched with the palm, and the "moisturizing feeling" and "stickiness feeling" were evaluated according to the following criteria.

"Moisture" Moisture: ○. Somewhat moist: △. Not moist: ×.

“Stickiness” No stickiness is felt: ○. Feel a little sticky: △. Feel sticky: ×.

[0048]

[Table 1]

Results From Table 1, the polysaccharide derivative of the present invention has a higher conductance after 10 minutes of application as compared with the comparative product, has an excellent moisturizing ability, and retains the moisturizing ability after rinsing. ,
It can be seen that it has a moist but non-greasy feel.

Example 4 Paste-type Face Wash: A paste-type face wash having the following composition was prepared by a conventional method.

[0051]

Table 2 (Composition) (%) Sodium sesquilauryl phosphate 25 Dipotassium myristyl sulfosuccinate 5 Cocoyl diethanolamide 2 Polyethylene glycol monostearate 4 Compound of Example 1 5 Carboxyvinyl polymer 0.5 Paraben 0.3 Perfume 0.1. 3 Purified water balance

The paste-like face cleansing agent obtained in Example 4 had a fresh feeling after washing, but also had a moist feel, and did not have a feeling of tightness.

Example 5 Body Shampoo: A body shampoo having the following composition was prepared by a conventional method.

[0054]

[Table 3] (Composition) (%) Lauryl phosphate triethanolamine 20 Alkyl saccharide (C ₁₂ -O- (G) _2.5 ) ^{* 1} 5 Lauroyl sarcosine sodium 5 Compound of Example 2 8 Xanthan gum 0.5 Propylene glycol 3 Fragrance 0.7 Purified water balance * 1: C ₁₂ is a lauryl group and G is glucose.

The body shampoo obtained in Example 5 was not moist even after washing and was moist.

Example 6 Anti-dandruff shampoo: An anti-dandruff shampoo having the following composition was prepared according to a conventional method.

[0057]

[Table 4] (Composition) (%) Lauryl dimethylamine acetic acid betaine 10 N-lauroyl glutamate sodium 10 piroctone auramine (octopirox, Hoechst) 0.5 ethylene glycol distearate 2 compound of Example 3 5 fragrance 0.5 Purified water balance

The anti-dandruff shampoo obtained in Example 6 was
There was no squeaky feeling when washing or rinsing, and the product was moisturized after washing without stickiness.

Example 7-Dishwashing agent: A dishwashing agent having the following composition was prepared by a conventional method.

[0060]

[Table 5] (Composition) (%) Polyoxyethylene (4) sodium lauryl ether sulfate 8 Polyoxyethylene (20) myristyl ether 5 Lauryl dimethylamine oxide 3 Ethanol 3 Compound of Example 1 3 Perfume 0.1 Purified water balance

The dishwashing detergent obtained in Example 7 was moist with less bulky hands after use.

Example 8 Hair Treatment: A hair treatment having the following composition was prepared according to a conventional method.

[0063]

Table 6 (Composition) (%) 2-dodecylhexadecyltrimethylammonium chloride 2 Stearyltrimethylammonium chloride 5 Compound of Example 5 5 Cetanol 3 Liquid paraffin 3 Polypeptide (collagen hydrolyzate) 5 Hydroxyethylcellulose (1% aqueous solution) Viscosity 8,000cp) 0.5 Polyethylene (5) oleyl ether 0.5 Methylparaben 0.2 Perfume 0.4 Purified water balance

The hair treatment obtained in Example 8 had an excellent effect of imparting flexibility to the hair, was not sticky, and had a moist feel.

Example 9 Lotion: A lotion having the following composition was prepared by a conventional method.

[0066]

Table 7 (Composition) (%) Lactic acid 0.03 Sodium lactate 0.84 Compound of Example 3 5 Glycerin 2 Polyoxyethylene (20) oleyl ether 1 Ethanol 10 Perfume 0.3 Purified water balance

The lotion obtained in Example 8 did not lose its moisturizing ability even with sweat, was not sticky, and had a moist feeling.

[Brief description of drawings]

FIG. 1 is a diagram showing an IR spectrum of the compound obtained in Example 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location A61K 7/50 C08B 31/00 7433-4C 37/00 Z 7433-4C D 7433-4C C11D 3/26

Claims (7)

[Claims] 1. The following general formula (1):(In the formula, Z is a polysaccharide molecule in which n hydroxyl groups are removed.
Replace the sugar residue with R¹And R ²Are the same or different
A straight or branched chain having 1 to 3 carbon atoms which may have a silane group
A is a linear or branched chain having 1 to 3 carbon atoms.
Indicates an alkylene group, and n is equal to or less than the total number of hydroxyl groups in the polysaccharide molecule.
A polysaccharide derivative represented by the following natural number). 2. The polysaccharide is β-1,4-glucan, α-
The polysaccharide derivative according to claim 1, which is selected from the group consisting of 1,4-glucan, α-1,6-glucan, pullulan and their hydroxyethyl derivatives, hydroxypropyl derivatives and 2,3-dihydroxypropyl derivatives. 3. The polysaccharide derivative according to claim 2, wherein the polysaccharide is cellulose or starch. 4. The polysaccharide according to any one of claims 1 to 3, wherein the average degree of substitution of the carboxybetaine group per sugar residue in the polysaccharide molecule is 0.1 to 3.0. Derivative. 5. A compound represented by the general formula Z- (OH) _n (wherein Z represents a polysaccharide residue in which n hydroxyl groups are removed from the polysaccharide molecule, and n is equal to or less than the total number of hydroxyl groups in the polysaccharide molecule). And a deoxyhalogenated polysaccharide represented by Z- (X) _n (wherein Z and n are as defined above, and X represents a halogen atom) by halogenating the polysaccharide represented by Then, a compound represented by the general formula R ¹ -NH-R ² (wherein R ¹ and R ² are the same or different and may have a hydroxy group, and have a linear or branched alkyl group having 1 to 3 carbon atoms) Of the general formula: (Wherein Z, R ¹ , R ² and n have the same meanings as defined above), and an aminated polysaccharide represented by the general formula Y-
A monohalogenated carboxylic acid salt represented by A-COOB (in the formula, A is a linear or branched alkylene group having 1 to 3 carbon atoms, B is an alkali metal, and Y is a halogen atom) is reacted. The method for producing a polysaccharide derivative according to claim 1, wherein 6. A cosmetic comprising the polysaccharide derivative according to any one of claims 1 to 4. 7. A detergent composition comprising the polysaccharide derivative according to any one of claims 1 to 4.