JPH1180201A - Novel polysaccharide derivative, method for producing the same, and cosmetic containing the same - Google Patents

Abstract

(57) [Summary] A part or all of H of a hydroxyl group of a polysaccharide or a derivative thereof has the following groups (1) and (2): [B is a C1-6 optionally substituted by a single bond or a hydroxyl group;
A is O or carbonyl group, R is C
4-43 alkyl groups, n represents 0 or 1, and M ¹ and M ² represent H or a monovalent cation. H of the hydroxyl group in the group (1) and M ¹ and M ^{2 in} the group (2) may be further substituted with another group (1) or (2). ] The novel polysaccharide derivative substituted by the above. [Effect] Gives a highly transparent aqueous solution, shows an excellent thickening effect with a small amount of addition, has little viscosity change due to coexistence of salts and temperature, has excellent dispersion stabilizing effect, cosmetics, toiletry products, hair care Thickeners for products, building materials, pharmaceuticals, etc.
Useful as gelling agents, excipients, emulsion stabilizers, flocculants and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative, and more particularly, to an aqueous solution which is excellent in transparency when used as an aqueous solution, exhibits excellent viscosity at low concentrations, and coexists with metal salts and changes in temperature. The present invention relates to a novel polysaccharide derivative exhibiting little change in viscosity and exhibiting extremely good emulsion stability, a method for producing the same, and a cosmetic containing the polysaccharide derivative.

[0002]

2. Description of the Related Art As one of important constituents of cosmetics, toiletry products, external medicines, water-soluble paints, etc., various cellulose ethers are used as thickeners, gelling agents, excipients, emulsion stabilizers, Widely used as a flocculant. Examples of such cellulose ethers include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, water-soluble nonionic cellulose ethers such as ethylhydroxyethylcellulose, carboxymethylcellulose, cationized cellulose, and cationized hydroxyethylcellulose. Cellulose ethers and the like are commercially available and used.

[0003] Although these cellulose ethers are relatively superior in viscosity stability of an aqueous solution in the presence of an inorganic metal salt and an organic metal salt as compared with a polyacrylic acid thickener such as Carbopol, Low viscosity at the same aqueous solution concentration, especially when used as a thickener or emulsion stabilizer for cosmetics and toiletry products, it is necessary to use a large amount of cellulose ethers in order to fully exhibit the properties. Was. However, if cellulose ethers are blended in a large amount, stickiness, a problem on the touch surface such as film feeling occurs, and the change with temperature change is large,
There is a disadvantage that it is difficult to maintain a stable product form.

On the other hand, for example, JP-A-55-110103 and JP-A-56-801 disclose long-chain alkyl groups having 8 to 24 carbon atoms in a part of nonionic water-soluble cellulose ethers. It has been disclosed that a hydrophobized non-ionic cellulose derivative into which is introduced a relatively high viscosity with a small mixing amount. In addition, JP-A-3-24001, JP-A-3-41210, JP-A-3-41214, JP-A-3-218316, as seen in JP-A-3-218316, topical pharmaceuticals for these alkyl-substituted cellulose derivatives, cosmetics Attempts have been made to apply it to such applications.

[0005]

However, although these alkyl-substituted cellulose derivatives show a higher viscosity than the above-mentioned cellulose ethers, they are poor in water solubility and are difficult to dissolve uniformly when incorporated into products. There have been problems such as the need for time and poor viscosity stability over time.

[0006] Therefore, these cellulose ethers and alkyl-substituted cellulose derivatives have the properties required as ideal thickeners used in cosmetics and toiletries, that is, they dissolve easily and have an excellent thickening effect. Coexistence of metal salts, oils and other additives, temperature, pH
The effect of the change in viscosity on the viscosity was small, the change in viscosity over time was small, the stickiness was small, the feeling of use was excellent, and the microbial resistance was not fully satisfied.

Accordingly, an object of the present invention is to provide a thickener which sufficiently satisfies the above-mentioned properties, a method for producing the same, and a cosmetic containing the thickener.

[0008]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a novel polysaccharide in which a hydrogen atom of a hydroxyl group of a polysaccharide is substituted with a specific hydrophobic group and a hydrophilic group. Derivatives have excellent water-solubility and exhibit high viscosity at very low concentrations in aqueous solutions, and have a stable viscosity that is hardly affected by additives such as inorganic metal salts, organic metal salts, oils, pH, and temperature. The present invention has been found to exhibit excellent emulsification stabilizing action and to have a good feeling of use when used in cosmetics and toiletry products, thereby completing the present invention.

That is, in the present invention, a part or all of the hydrogen atoms of the hydroxyl group of a polysaccharide or a derivative thereof are represented by the following groups:
(1) and (2)

[0010]

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In the formula (1), B represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group, A represents an oxygen atom or a carbonyl group, R represents a linear or branched alkyl group having 4 to 43 carbon atoms, and n represents 0 or 1. (2) wherein M ¹ and M ²
Are the same or different and represent a hydrogen atom or a monovalent cation. The hydrogen atom of the hydroxyl group in the group (1) and M ¹ and M ² in the group (2) may be further substituted with another group (1) or (2). And a method of producing the same and a cosmetic containing the novel polysaccharide derivative.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the novel polysaccharide derivative of the present invention, when a cellulose is used as a polysaccharide or a derivative thereof, its repeating unit is represented by the following general formula.

[0013]

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Wherein R ¹ is the same or different and (A) is a hydrogen atom, methyl group, ethyl group, hydroxyethyl group, hydroxypropyl group and the like; (B) is a hydrophobic substituent (1);
(C): represents a group selected from hydrophilic substituents (2), Q is the same or different, represents an alkylene group having 2 to 4 carbon atoms,
a, b and c are the same or different and represent a number of 0-10.
The QO group, R ¹ group, a, b and c may be the same or different within the repeating unit or between the repeating units, and the hydrogen atom and the substituent of the hydroxyl group in the above substituent (1)
M ¹ and M ² in (2) may be further substituted with another substituent (1) or (2). ]

In the novel polysaccharide derivative of the present invention, the substituents (1) and (2) are contained as R ¹ in the constituent monosaccharide residue represented by the above general formula, Does not necessarily mean that the substituents (1) and (2) must be present, but it is sufficient that the substituents (1) and (2) are introduced when viewed as a whole molecule. The remaining R ¹ is a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group or the like as described above.

In the group represented by B in the hydrophobic substituent (1), the hydroxyl group may have 1 carbon atom which may be substituted.
Examples of the linear or branched alkylene group of methylene, ethylene, propylene, trimethylene, 1-methyltrimethylene, tetramethylene, pentamethylene, 3-methyltetramethylene, 1,1-dimethyltrimethylene, hexamethylene, 2-hydroxytrimethylene, 2-hydroxytetramethylene, 3-hydroxytrimethylene, 1-hydroxymethylethylene and the like. Preferred B ¹ is a single bond, ethylene, propylene, trimethylene,
2-hydroxytrimethylene, 1-hydroxymethylethylene and the like.

Examples of the linear or branched alkyl group having 4 to 43 carbon atoms represented by R in the hydrophobic substituent (1) include butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henycosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group , Heptacosyl group, octakosyl group, nonakosyl group, triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group,
Tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group, nonatriacontyl group, tetracontyl group, neopentyl group, 2-ethylhexyl group, 2,3,
4-trimethylpentan-3-yl group, 3,5,5-trimethylhexyl group, 3,7-dimethyloctyl group, 3,7-dimethyloctan-3-yl group, methylundecyl group, 2,3,4 , 6,6-pentamethylheptane-3-yl group, 3,7,11-trimethyldodecyl group, 2-hexyldecyl group, 2-hexylundecyl group,
Methylheptadecyl group, ethylhexadecyl group, propylpentadecyl group, 2-hexyldodecyl group, 2-heptylundecyl group, isostearyl group, methyloctadecyl group, 2-octyldodecyl group, 3,7,11,15- Tetramethylhexadecyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecyloctadecyl group, 2-tetradecylbehenyl group and the like are preferably those having 12 to 18 carbon atoms, for example, dodecyl group, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, methylundecyl, 2,3,4,6,6-
Pentamethylheptane-3-yl, 3,7,11-trimethyldodecyl, 2-hexyldecyl, 2-hexylundecyl, methylheptadecyl, ethylhexadecyl, propylpentadecyl, 2-hexyl Examples include a dodecyl group, a 2-heptylundecyl group, an isostearyl group, and more preferably a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an isostearyl group.

In the hydrophobic substituent (1), A represents an oxygen atom or a carbonyl group, preferably an oxygen atom, and n represents 0
Or 1 is shown, but 1 is preferred.

These hydrophobic substituents (1) include not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule,
Substitution with the hydrogen atom of the hydroxyl group of the hydroxyethyl group or hydroxypropyl group bonded to the polysaccharide molecule, or the hydrogen atom of the hydroxyl group of another substituent (1) or M ¹ and M ² of the substituent (2) May be. The degree of substitution by these hydrophobic substituents (1) is 0.0001 per constituent monosaccharide residue.
The range is preferably from 1.0 to 1.0, particularly preferably from 0.002 to 0.5.

The hydrogen atom or the monovalent cation represented by M ¹ and M ² in the hydrophilic substituent (2) includes a hydrogen atom, an ion of an alkali metal such as lithium, sodium, potassium, rubidium and cesium, and the like. , An ammonium ion or a substituted ammonium ion, and among them, a sodium ion and a potassium ion are preferable.

These hydrophilic substituents (2) include not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule,
Hydrogen atom or substituent of hydroxyl group of hydroxyethyl group or hydroxypropyl group bound to polysaccharide molecule
It may be substituted with a hydrogen atom of a hydroxyl group of (1) or M ¹ and M ^{2 of} another substituent (2). The degree of substitution by these hydrophilic substituents (2) is from 0.01 to
2.0, more preferably 0.02 to 1.5, especially 0.1 to 0.6.

The novel polysaccharide derivative of the present invention is produced, for example, by reacting a polysaccharide or a derivative thereof with a compound represented by the following general formula (3) and a compound represented by the following general formula (4). it can.

[0023]

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In the formula (3), A, R and n have the same meanings as described above, and D represents a halogen atom, a hydroxyl group, an epoxidized alkyl group having 3 to 6 carbon atoms, or a hydroxyl group. And a straight-chain or branched alkyl group having 1 to 6 carbon atoms substituted with a halogen atom. (4) In the formula, X represents a halogen atom. ]

The reaction between the polysaccharide or its derivative and the compound (3) (introduction of the hydrophobic substituent (1)) and the reaction with the compound (4) (introduction of the hydrophilic substituent (2)) May be performed first, or when purification is not necessary, the purification can be performed at the same time. However, the reaction is preferably performed in the order of compound (3) → compound (4).

The polysaccharides or derivatives thereof used in the present invention include cellulose, guar gum, starch, hydroxyethyl cellulose, hydroxyethyl guar gum,
Hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, Hydroxypropyl methyl guar gum, hydroxypropyl methyl starch, pullulan and the like can be mentioned, and among them, cellulose, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose and hydroxypropyl cellulose are preferable. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group and hydroxypropyl group of these polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. The degree of substitution per constituent monosaccharide residue is preferably from 0.1 to 10, particularly preferably from 0.5 to 5. The weight average molecular weight of these polysaccharides or derivatives thereof is preferably in the range of 10,000 to 10,000,000, and particularly preferably in the range of 50,000 to 5,000,000.

The hydrophobization reaction (introduction of the hydrophobic substituent (1)) and the hydrophilization reaction (introduction of the hydrophilic substituent (2)) will be separately described below.

<Introduction of Hydrophobic Substituent (1)> The introduction of a hydrophobic substituent (1) into a polysaccharide or a derivative thereof can be performed, for example, by introducing a polysaccharide or a derivative thereof (introducing a hydrophilic substituent (2)). May be dissolved or dispersed in a suitable solvent, if necessary, and reacted with the compound (3) as a hydrophobizing agent, preferably in the presence of an alkali.

In the group represented by D in the general formula (3), examples of the halogen atom include a chlorine atom, bromine atom and iodine atom, and examples of the epoxidized alkyl group having 3 to 6 carbon atoms include 2,3- An epoxypropyl group, a 3,4-epoxybutyl group, a 4,5-epoxypentyl group, a 5,6-epoxyhexyl group, and the like. The hydroxyl group may be substituted and the halogen atom is substituted with 1 carbon atom. As the straight-chain or branched alkyl group of (1) to (6), 2-chloroethyl group, 3-chloropropyl group, 4-chlorobutyl group, 6-chlorohexyl group, 2-bromoethyl group, 2-hydroxy-3-chloropropyl group, 1 -Hydroxymethyl-2-chloroethyl group and the like. Preferred examples of D include a chlorine atom, an iodine atom, a 2,3-epoxypropyl group, a 2-chloroethyl group, a 3-chloropropyl group, and a 2-hydroxy-3-chloropropyl group. These compounds (3) can be used alone or in combination of two or more. The amount of the compound (3) used can be appropriately adjusted depending on the desired amount of the hydrophobic substituent (1) introduced to the polysaccharide or its derivative. , 0.01 to 10 equivalents, particularly preferably 0.02 to 1 equivalent.

This reaction is preferably carried out in the presence of an alkali, if necessary. Such an alkali is not particularly limited, but may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, etc. And tertiary amines such as triethylamine, among which sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is preferably in the range of 0.01 to 10 times, especially 0.1 to 5 times the molar amount of the compound (3) to be used, and good results are obtained, and thus it is preferable.

Examples of the solvent include polar solvents, for example, lower alcohols such as isopropyl alcohol and tert-butyl alcohol, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran and the like. For the purpose of swelling the polysaccharide or a derivative thereof to increase the reactivity with the hydrophobizing agent, 1 to 50
The reaction may be carried out using a mixed solvent to which water is added in an amount of 2% by weight, more preferably 2 to 30% by weight.

The reaction temperature is preferably in the range of 0 to 200 ° C., particularly 30 to 100 ° C., and the reaction time is 1 to 24 hours, especially 2 to 12 hours.
Time is preferred. After completion of the reaction, the alkali is neutralized using an acid. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used.

When the polysaccharide into which the hydrophobic substituent (1) has been introduced in the manner described above is subsequently used for the introduction reaction of the hydrophilic substituent (2), it may be separated by filtration or the like and used as it is. However, if necessary, it can be used after washing with hot water, aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted compound (3) or salts produced as a result of neutralization or the like. In the case where the hydrophilic substituent (2) has been introduced before the present reaction, after separation by filtration or the like, washing and neutralization are performed as necessary, followed by drying and drying of the present invention. New polysaccharide derivatives can be obtained.

<Introduction of Hydrophilic Substituent (2)> The introduction of the hydrophilic substituent (2) into the polysaccharide or its derivative may be carried out, for example, by introducing the polysaccharide or its derivative (introduction of the hydrophobic substituent (1)). May be dissolved or dispersed in an appropriate solvent, if necessary, and reacted with the compound (4) as a hydrophilizing agent, preferably in the presence of an alkali.

Examples of the halogen atom represented by X in the general formula (4) include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is particularly preferable. The amount of the compound (4) used is a hydrophilic substituent for the polysaccharide or a derivative thereof.
It can be appropriately adjusted depending on the desired introduction amount of (2), but is usually preferably 0.01 to 10 equivalents, particularly preferably 0.05 to 5 equivalents, per monosaccharide residue constituting the polysaccharide or a derivative thereof.

This reaction is preferably carried out in the presence of an alkali, if necessary. Such an alkali is not particularly limited, but may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate, etc. And tertiary amines such as triethylamine. Of these, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, pyridine, triethylamine and the like are preferable.
The amount of the alkali used is 1.0 to 3.
A molar amount of 0 mol, particularly a range of 1.05 to 2.0 molar times gives good results and is preferred.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol,
Examples include dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydrofuran and the like. In order to enhance the reactivity between the polysaccharide or a derivative thereof and the compound (4), the reaction is carried out using a mixed solvent in which 0.1 to 100% by weight, more preferably 1 to 50% by weight of water is added to the solvent. May be performed.

[0038] The reaction temperature is preferably in the range of -10 to 80 ° C, particularly 0 to 30 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, sulfuric acid, hydrochloric acid, inorganic acids such as phosphoric acid,
Organic acids such as acetic acid can be used.

When the polysaccharide into which the hydrophilic substituent (2) has been introduced in the manner described above is subsequently used for the introduction reaction of the hydrophobic substituent (1), it may be separated by filtration or the like and used as it is. However, if necessary, unreacted compounds are washed with aqueous isopropyl alcohol, aqueous acetone solvent, etc.
Salts by-produced by (4) or neutralization may be removed before use. Note that the hydrophobic substituent (1) has already been added before this reaction.
In the case where is introduced, the novel polysaccharide derivative of the present invention can be obtained by performing a separation by filtration or the like, washing and neutralizing if necessary, and then drying.

As described above, the substituents (1) and (2) in the polysaccharide derivative of the present invention obtained as described above include not only the hydroxyl group of the polysaccharide or its derivative used as a raw material, but also other groups. The hydroxyl group of the substituent (1) or M ¹ and M ² of the substituent (2) may be substituted, and such substitution may occur in an overlapping manner. That is, in addition to the compound in which only the hydrogen atom of the hydroxyl group of the polysaccharide or a derivative thereof is substituted with the substituents (1) and (2), when the phosphorylation is performed after the hydrophobicization, the compound is further substituted with the substituent (1). Group (1) or
(2) may be substituted, and the substituent (2) may further include a substituent (2) .When the phosphorylation is made hydrophobic after the phosphorylation, the substituent (1) is further substituted. (1) may be substituted, and the substituent (2) may further include the substituent (2) or (1) .When the hydrophobicization and the phosphorylation are performed simultaneously, the substituent (1) may be further substituted with a substituent (1) or (2), and the substituent (2) may further include a substituent (1) or (2) further substituted. It may include those in which substitution to a group occurs in an overlapping manner. Therefore, the present invention includes any of such polysaccharide derivatives.

When the novel polysaccharide derivative of the present invention is used in cosmetics, its amount is not particularly limited, but is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 3% by weight.

When the novel polysaccharide derivative of the present invention is used in skin cosmetics, surfactants, oils, humectants, film-forming agents, oil gelling agents, metal oxides commonly used as skin cosmetics components , Any combination with organic ultraviolet absorbers, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, pigments, fragrances, etc. Thus, various forms, for example, oil / water, water / oil type emulsified cosmetics, creams, emulsions, lotions, oily lotions, lipsticks, foundations, skin cleansers and the like can be obtained.

When the novel polysaccharide derivative of the present invention is used in hair cosmetics, surfactants, other thickeners, oil gelling agents, metal oxides, organic ultraviolet rays generally used as hair cosmetic ingredients are used. Absorbents, inorganic metal salts, organic metal salts,
It can be blended with a pearlizing agent, an antioxidant, a preservative, a medicinal ingredient, a pigment, a fragrance, and other components in any combination. In order to improve the feel of the hair, a cationic polymer such as cationized cellulose and a silicone derivative such as dimethylpolysiloxane, amino-modified silicone, and polyether-modified silicone can also be blended. The dosage form of the hair cosmetic is not particularly limited, and depending on the use, an emulsion, a suspension, a gel, a transparent solution,
Hair cosmetics in various dosage forms such as aerosols, such as preshampoos, shampoos, hair rinses, hair treatments, hair conditioners, conditioning blowing agents and the like can be used.

The cosmetic of the present invention exhibits excellent feeling in use and viscosity stability, but when used in combination with metal oxides, inorganic metal salts, organic metal salts, etc., particularly good feeling in use and viscosity stability. Sex can be obtained. In addition, by blending an organic ultraviolet absorber, it is possible to provide a sun care cosmetic product and the like excellent in use feeling and viscosity stability. Also, by using a metal oxide and an organic ultraviolet absorber in combination,
Further, the effect of preventing ultraviolet rays can be enhanced.

Examples of the metal oxide include titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, etc., silica treatment, alumina treatment, silica / alumina treatment, metal soap treatment, fatty acid treatment, amino acid treatment, silicone It may have been subjected to a treatment, an alkyl phosphoric acid treatment, a fluorine treatment or the like. Further, two or more of these, or a composite of these with another organic or inorganic powder may be used. The particle size, shape, and the like of these metal oxides are not particularly limited, and they may be used alone or in combination of two or more. The compounding amount of these metal oxides is 0.001 to 50
% By weight, especially 0.005 to 30% by weight.

Examples of the inorganic metal salts and organic metal salts include all monovalent metal salts, divalent metal salts and trivalent metal salts used in cosmetics.
Valent metal salts, specifically, sodium sulfate, potassium sulfate, magnesium sulfate, magnesium chloride, sodium chloride, zinc chloride, zinc sulfate, aluminum potassium sulfate, aluminum chloride, ferric chloride, zinc paraphenol sulfonate And monovalent metal salts, divalent metal salts, and trivalent metal salts of organic acids such as lactic acid, tartaric acid, succinic acid, and citric acid. These can be used alone or in combination of two or more, and the compounding amount is preferably 0.001 to 30% by weight, particularly preferably 0.005 to 20% by weight.

Further, other thickeners include xanthan gum, hyaluronic acid, and polyanthes (Polianthes).
L.) and polysaccharides such as acidic heteropolysaccharides derived from callus of plants belonging to plants and derivatives thereof.
Examples include polyvinyl alcohol, soluble collagen, polyethylene glycol having a molecular weight of 20,000 to 4,000,000, and examples of the oil gelling agent include dextrin fatty acid esters.

The medicinal components include plant extracts such as hamamelis, button, chamomile and chamomile; amino acids such as glycine and serine and derivatives thereof; oligopeptides; guanidine derivatives described in JP-A-6-223023; glycyrrhizin; A salt thereof, glycyrrhetin and a salt thereof,
Anti-inflammatory agents such as allantoin, epsilon aminocaproic acid and salts thereof; vitamins such as α-carotene, β-carotene, ascorbic acid and tocopherol; antioxidants such as tannins and flavonoids; 6-hydroxyhexanoic acid;
Hydroxy acids such as 8-hydroxyundecanoic acid, 9-hydroxyundecanoic acid, 10-hydroxyundecanoic acid, ethyl 11-hydroxyundecanoate and salts thereof; 1- (2-hydroxyethylamino) -3-isostearyloxy-2- Amine derivatives such as propanol, 1- (2-hydroxyethylamino) -3- (12-hydroxystearyloxy) -2-propanol, 1- (2-hydroxyethylamino) -3-methyloxy-2-propanol, etc. No.

[0049]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

In the following examples, the degree of substitution of the substituent (1) of the novel polysaccharide derivative of the present invention is determined by the Zeisel method (DG Anderson) when the substituent (1) is introduced into the polysaccharide through an ether bond. , Anal. Chem., 43, 894 (1971)). When the substituent (1) is introduced into the polysaccharide by an ester bond, the sample is hydrolyzed with an acid, neutralized, and then treated with diazomethane. Esterification was performed and quantified by gas chromatography. The substitution degree of the substituent (2) was determined by potentiometric titration. That is, a thickener solution having a known concentration is prepared, and a 1N hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) of known weight is added thereto with stirring, and the solution is titrated with a 0.1N aqueous potassium hydroxide solution (manufactured by Wako Pure Chemical Industries). And the degree of substitution was calculated from the titration constant. In the following examples, "degree of substitution" indicates the average number of substituents per constituent monosaccharide residue.

Example 1 Weight average molecular weight 800,000, molar substitution degree of hydroxyethyl group
A mixture of 80.0 g of 1.8 hydroxyethyl cellulose (HEC-QP4400, manufactured by Union Carbide), 640 g of 80% isopropyl alcohol [water: isopropyl alcohol = 20: 80 (weight ratio)] and 5.5 g of a 48% aqueous sodium hydroxide solution was obtained. The obtained slurry solution was stirred at room temperature under a nitrogen atmosphere for 30 minutes. Stearyl glycidyl ether 3.
5 g was added, and the mixture was stirred at 80 ° C. for 8 hours to perform a hydrophobic reaction. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product is 80% isopropyl alcohol [water: isopropyl alcohol = 20: 80 (weight ratio)] 80
After washing once with 0 g and then twice with 800 g of isopropyl alcohol, it was dried under reduced pressure at 70 ° C. for 24 hours to obtain 73.7 g of a hydrophobized hydroxyethyl cellulose derivative. 15.0 g of the obtained hydrophobized hydroxyethylcellulose derivative, aqueous TH
F [water: THF = 20: 80 (weight ratio)] 150 g and pyridine 14.
8 g were mixed and cooled to 5 ° C. Add 10 ° C to this reaction solution.
While maintaining the pH below 7 and 8, 11.3 g of phosphorus oxychloride
And a 48% aqueous sodium hydroxide solution were added dropwise. After completion of the dropwise addition, the mixture was aged at 10 ° C. or lower for 2 hours to perform phosphorylation. After the completion of the reaction, the reaction product was separated by filtration. The reaction product was treated with 70% isopropyl alcohol [water: isopropyl alcohol = 3
0:70 (weight ratio)], washed three times with 400 g and then twice with 300 g of isopropyl alcohol, dried under reduced pressure at 70 ° C. all day and night, and substituted with a 3-stearyloxy-2-hydroxypropyl group and a phosphate group. 23.4 g of the hydroxyethyl cellulose derivative (Compound 1 of the present invention) was obtained. The obtained hydroxyethylcellulose derivative 3-stearyloxy-2-
The substitution degree of the hydroxypropyl group was 0.0039, and the substitution degree of the phosphate group was 0.31.

Example 2 In Example 1, hydroxyethyl cellulose was used as hydroxyethyl cellulose with a weight average molecular weight of 1.5 million and the degree of molar substitution of hydroxyethyl groups.
Hydrophobization reaction was carried out by the same operation and charge amount except that 1.8 was used, and further 15.0 g of hydrophobized hydroxyethyl cellulose obtained, 18.5 g of phosphorus oxychloride, pyridine 2
4.7 g and water-containing THF [water: THF = 20: 80 (weight ratio)] 150 g
The phosphorylation reaction, washing, and drying were performed in the same manner as in Example 1 to obtain a hydroxyethyl cellulose derivative (Compound 2 of the present invention). The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative was 0.0040, and the degree of substitution of the phosphate group was 0.48.
Met.

Example 3 In Example 1, the weight average molecular weight was 1.5 million as hydroxyethyl cellulose, and the molar substitution degree of hydroxyethyl groups was
A hydrophobic reaction was carried out in the same manner as in Example 1 except that the amount of stearyl glycidyl ether was changed to 14.0 g, and a phosphorylation reaction, washing and drying were carried out in the same manner as in Example 1 to obtain hydroxyethyl cellulose. A derivative (Compound 3 of the present invention) was obtained. The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative was 0.0123, and the degree of substitution of the phosphate group was 0.35.
Met.

Example 4 In Example 1, the weight average molecular weight was 1.5 million as hydroxyethyl cellulose, and the degree of molar substitution of hydroxyethyl group was 1.
A hydrophobic reaction was carried out in the same manner as in Example 1 except that the amount of stearyl glycidyl ether used was changed to 3.6 g, and a phosphorylation reaction, washing and drying were carried out in the same manner as in Example 1 to obtain hydroxyethyl cellulose. A derivative (the present compound 4) was obtained. The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative was 0.0041, and the degree of substitution of the phosphate group was 0.29.
Met.

Example 5 In Example 1, the hydroxyethyl cellulose had a weight average molecular weight of 1.5 million and the degree of molar substitution of hydroxyethyl groups.
A hydrophobic reaction was performed in the same manner except that 80.0 g of 1.8 was used, and 4.0 g of dodecyl glycidyl ether was used instead of stearyl glycidyl ether. Further, a phosphorylation reaction, washing and drying were performed in the same manner as in Example 1. A hydroxyethyl cellulose derivative (Compound 5 of the present invention) was obtained.
The substitution degree of the 3-dodecyloxy-2-hydroxypropyl group of the obtained hydroxyethyl cellulose derivative is 0.0132,
The substitution degree of the phosphate group was 0.33.

Example 6 Weight average molecular weight 800,000, molar substitution degree of hydroxyethyl group
80.0 g of 1.8 hydroxyethyl cellulose (HEC-QP4400, manufactured by Union Carbide), 400 g of 80% isopropyl alcohol [water: isopropyl alcohol = 20: 80 (weight ratio)] and 3.4 g of a 48% aqueous sodium hydroxide solution were mixed to obtain a mixture. The obtained slurry solution was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 31.9 g of octyl bromide was added to this solution, and the mixture was stirred at 80 ° C. for 8 hours to perform a hydrophobic reaction. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of 80% isopropyl alcohol [water: isopropyl alcohol = 20: 80 (weight ratio)] and then twice with 500 g of isopropyl alcohol.
It was dried at 70 ° C. under reduced pressure for a whole day and night to obtain 75.9 g of a hydrophobized hydroxyethyl cellulose derivative. 25.0 g of the obtained hydrophobized hydroxyethyl cellulose derivative, 80% aqueous THF [water: T
HF = 20: 80 (weight ratio)] Using 250 g, 41.2 g of pyridine and 30.8 g of phosphorus oxychloride, perform a phosphorylation reaction, washing and drying in the same manner as in Example 1, and replace with octyl and phosphate groups. 39.1 g of the obtained hydroxyethyl cellulose derivative (Compound 6 of the present invention) was obtained. The degree of substitution of the octyl group of the obtained hydroxyethyl cellulose derivative was 0.25.
3. The substitution degree of the phosphate group was 0.42.

Example 7 Methyl cellulose having a weight average molecular weight of 400,000 and a degree of molar substitution of methyl group of 1.8 (Metroose SM-800, manufactured by Shin-Etsu Chemical Co., Ltd.)
60.0 g, 90% tert-butyl alcohol [water: tert-butyl alcohol = 10: 90 (weight ratio)] 600 g and 48% aqueous sodium hydroxide solution 5.7 g were mixed, and the resulting slurry solution was stirred at room temperature under a nitrogen atmosphere. Stir for 30 minutes. To this solution, 3.82 g of stearyl glycidyl ether was added, and the mixture was stirred at 80 ° C. for 8 hours to perform a hydrophobic reaction. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. 80% reaction product
After washing twice with 500 g of isopropyl alcohol [water: isopropyl alcohol = 20:80 (weight ratio)],
It was dried at 0 ° C. overnight to obtain 53.6 g of a hydrophobized methylcellulose derivative. 15.0 g of the obtained hydrophobized methylcellulose derivative, 80% THF [water: THF = 20: 80 (weight ratio)] 15
0 g, pyridine 4.9 g and phosphorus oxychloride 3.7 g,
The phosphorylation reaction, washing and drying were carried out in the same manner as in Example 1 to obtain 15.0 g of a methylcellulose derivative (compound 7 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a phosphate group. The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained methylcellulose derivative was 0.0028, and the degree of substitution of the phosphate group was 0.11.

Example 8 A slurry solution was prepared by adding 20.0 g of cellulose powder (manufactured by Merck), 250 g of tert-butyl alcohol, 30 g of ion-exchanged water and 3.7 g of tetradecylglycidyl ether, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. did. Further, 4.0 g of powdered sodium hydroxide was added, and the mixture was stirred at room temperature for 60 minutes. The temperature was raised to 80 ° C., and the mixture was further stirred for 8 hours to perform a glyceryl etherification reaction. After completion of the reaction, the reaction product was neutralized with acetic acid. The reaction product was further filtered, washed twice with 200 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. to obtain 18.2 g of hydrophobized cellulose.
I got 15.0 g of the obtained hydrophobized cellulose, 80% isopropyl alcohol [water: isopropyl alcohol = 20:
80 (weight ratio)] Using 150 g, 24.7 g of pyridine and 18.5 g of phosphorus oxychloride, a phosphorylation reaction, washing and drying were carried out in the same manner as in Example 1 to give 3-tetradecyloxy-2.
Thus, 11.2 g of a cellulose derivative (compound 8 of the present invention) substituted with a hydroxypropyl group and a phosphate group was obtained. The degree of substitution of the 3-tetradecyloxy-2-hydroxypropyl group of the obtained cellulose derivative was 0.0057, and the degree of substitution of the phosphate group was 0.
It was 40.

Example 9 30.0 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of 1.5 million and a molar substitution degree of hydroxyethyl group of 1.8, 70 g of pyridine and 5 parts of water
g were mixed. After cooling the solution to 10 ° C. or lower, 13.6 g of dodecanoic acid chloride was added dropwise to the solution while maintaining the temperature at 10 ° C. or lower. After completion of the dropwise addition, the temperature was raised to 60 ° C., and the mixture was aged for 2 hours. After completion of the reaction, the obtained reaction product was dispersed in 500 g of 80% isopropyl alcohol [water: isopropyl alcohol = 20: 80 (weight ratio)]. The resulting solid was collected by filtration, washed three times with 500 g of isopropyl alcohol, and then dried under reduced pressure.
It was dried at 0 ° C. for 24 hours to obtain 27.0 g of a hydrophobized hydroxyethyl cellulose derivative. 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained, 25 g of pyridine, 80% THF
[Water: THF = 20: 80 (weight ratio)] A phosphorylation reaction, washing and drying were carried out in the same manner as in Example 1 by using 200 g and 17 g of phosphorus oxychloride, whereby dodecanoyl and phosphate groups were substituted. 22.5 g of a hydroxyethyl cellulose derivative (Compound 9 of the present invention) was obtained. The degree of substitution of the dodecanoyl group in the obtained hydroxyethyl cellulose derivative was 0.051, and the degree of substitution of the phosphate group was 0.33.

Test Example 1 Viscosity Test Each 1.0 g of the compound of the present invention or the comparative compound was dissolved in 200 ml of ion-exchanged water, 1.0% calcium chloride aqueous solution or 1.0% sodium chloride aqueous solution, respectively, and allowed to stand at room temperature for 24 hours. The viscosity of each aqueous solution was measured. The viscosity was measured using a Brookfield viscometer (12 rpm, 25 ° C.). The following compounds were used as comparative compounds. Table 1 shows the results.

Comparative compound 1: hydroxyethyl cellulose used in Example 2 (weight average molecular weight 1.5 million, molar substitution degree of hydroxyethyl group 1.8) Comparative compound 2: carboxymethyl cellulose (weight average molecular weight 1,000,000, molar substitution of carboxymethyl group) Degree 0.78) Comparative compound 3: sodium polyacrylate (Carbopol 941, manufactured by Goodrich) Comparative compound 4: phosphorylated hydroxyethylcellulose (same as Example 2 without hydrophobizing hydroxyethylcellulose used in Example 2) Compound subjected to the phosphorylation reaction by the method described in 1 above; the degree of molar substitution of the phosphate group is 0.51)

[0062]

[Table 1]

The novel polysaccharide derivative of the present invention not only gives a highly transparent aqueous solution, but also exhibits an excellent thickening property as shown in Table 1, and also has an excellent salt resistance.

Test Example 2 Emulsion Stability Test An emulsion having the following composition was prepared, and the emulsion stability immediately after emulsification and when stored at 50 ° C. for one or two weeks was visually evaluated. In addition, when the emulsion is uniformly emulsified,
The case where they were separated was designated as x. Table 2 shows the results.

<Emulsion composition> Vaseline 50.0% by weight Lanolin 8.0% by weight Polyoxyethylene (5) lauryl ether 0.5% by weight Compound of the present invention or comparative compound 0.2% by weight Water balance

[0066]

[Table 2]

As is clear from Table 2, the novel polysaccharide derivatives of the present invention had excellent emulsion stability.

Example 10 Emulsion Emulsion 1 of the present invention and Comparative Emulsion 1 having the following compositions were prepared, and their viscosities, emulsion stability, and usability were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 3 shows the results.

<Emulsion 1 of the Present Invention (Comparative Emulsion 1)> Compound 4 of the Present Invention (or Comparative Compound 4) 0.5% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 15.0% by weight Methylpolysiloxane 1.0% by weight Glycerin 3.0% by weight Water balance

[0070]

[Table 3]

Example 11 Emulsion Emulsion 2 of the present invention and Comparative Emulsion 2 having the following compositions were prepared, and their viscosity, emulsion stability and usability were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 4 shows the results.

<Emulsion 2 of the Present Invention (Comparative Emulsion 2)> Compound 5 of the Present Invention (or Comparative Compound 4) 0.6% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 12.0% by weight Methylpolysiloxane 1.0% by weight 2-Ethylhexyl paramethoxycinnamate 5.0% by weight Zinc oxide treated with silicone 3.0% by weight Glycerin 2.0% by weight Water balance

[0073]

[Table 4]

Example 12 Lotion A lotion 3 of the present invention and a comparative lotion 3 having the following compositions were prepared, and their viscosities, emulsification stability and feeling in use were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 5 shows the results.

<Emulsion 3 of the Present Invention (Comparative Emulsion 3)> Compound 2 of the Present Invention (or Comparative Compound 4) 0.25 wt% Water (or 53.3 wt% of water + 0.25 wt% of L-Algin) 53.55 wt% Ethanol (55 v / v%) 10.0% by weight Glycerin 2.0% by weight 2-ethylhexyl paramethoxycinnamate 3.0% by weight Methylpolysiloxane 5.0% by weight Methylcyclopolysiloxane 25.0% by weight Zinc sulfocarbonate 0.2% by weight Self-emulsifying glycerol monostearate 0.7% by weight Sorbitan monostearate 0.3% by weight

[0076]

[Table 5]

Example 13 A lotion was prepared according to the following formulation. This lotion was excellent in stability and had good feeling without stickiness. Ethanol 30.0% by weight Glycerin 5.0% by weight Polyethylene glycol 1500 4.0% by weight Polyoxyethylene oleyl ether (20EO) 0.5% by weight Polyoxyethylene hydrogenated castor oil (30EO) 0.5% by weight Compound of the present invention 1 0.2% by weight Water balance

Example 14 Emulsion An emulsion was prepared according to the following formulation. This emulsion was excellent in stability and good in feeling without stickiness. Squalane 5.0 wt% Olive oil 8.0 wt% Jojoba oil 1.0 wt% Polyoxyethylene hydrogenated castor oil (10EO) 1.0 wt% Sorbitan monostearate 1.0 wt% Compound of the present invention 2 0.5 wt% Butylparaben 0.1 wt% Methylparaben 0.1 wt% Ethanol 5.0 Glycerin 3.0% by weight Fragrance 0.05% by weight Water balance

Example 15 Toner A lotion was prepared according to the following formulation. This lotion is 1 at 50 ℃
It was stable for months and had a good usability. Ethanol 5.0% by weight Glycerin 3.0% by weight Polyethylene glycol 1500 4.0% by weight Polyoxyethylene oleyl ether (20EO) 0.3% by weight Polyoxyethylene hydrogenated castor oil (30EO) 0.2% by weight Compound 3 of the present invention 0.15% by weight zinc p-phenolsulfonate 0.2% by weight water balance

Example 16 Sun care cream A sun care cream was prepared according to the following formulation. This sun care cream was stable at 50 ° C. for one month or more, and had a good feeling upon use. Dimethylsiloxane / methyl (polyoxyethylene) siloxane polymer 2.0% by weight Polyoxyethylene (20EO) sorbitan monooleate 0.5% by weight Methylpolysiloxane (5cs) 7.0% by weight Methylphenylpolysiloxane 2.0% by weight Jojoba oil 2.0% by weight Palmitin Acid dextrin 0.5% by weight Octyldimethyl PABA 4.0% by weight Silicone-coated fine particle titanium oxide 5.0% by weight Acidic heteropolysaccharide 0.03% by weight Magnesium sulfate 0.5% by weight Glycerin 5.0% by weight Dibutylhydroxytoluene 0.05% by weight Compound of the present invention 4 0.5% by weight Water balance

Example 17 Foundation A foundation was prepared according to the following formulation. This foundation was stable at 50 ° C. for one month or more, and had a good usability. Compound 7 of the present invention 0.2% by weight α-monoisostearyl glyceryl ether 2.0% by weight Aluminum diisostearate 0.2% by weight Liquid paraffin 10.0% by weight Neopentyl glycol dioctanoate 5.0% by weight Methylphenyl polysiloxane (14cs) 5.0% by weight p- 2-ethylhexyl methoxycinnamate 3.0% by weight 2-hydroxy-4-methoxybenzophenone 1.0% by weight Silicone-coated fine particles of titanium oxide 5.0% by weight Silicone-coated fine particles of zinc oxide 1.0% by weight Sericite 2.0% by weight Talc 2.0% by weight Bengala 0.4% by weight % Iron yellow oxide 0.7% by weight Black iron oxide 0.1% by weight Magnesium sulfate 1.0% by weight Methyl paraben 0.2% by weight Fragrance Trace water Balance

Example 18 Lipstick A lipstick was prepared according to the following formulation. This lipstick was stable at 50 ° C. for one month or more and had a good feeling upon use. Castor oil 52.0% by weight Lanolin 5.0% by weight Liquid lanolin 5.0% by weight Beeswax 4.0% by weight Ozokerite 7.0% by weight Candelilla wax 2.0% by weight Carnauba wax 1.0% by weight Dodecyl-modified silicone 10.0% by weight The present compound 1 0.2% by weight homomenthyl salicylate 7.8% by weight Titanium oxide 1.0% by weight Red No. 201 1.0% by weight Red No. 202 2.0% by weight Yellow 4 aluminum lake 1.0% by weight Red No. 223 0.1% by weight Fragrance trace amount Butylated hydroxytoluene 0.1% by weight Propyl paraben 0.3% by weight

[0083]

Industrial Applicability The novel polysaccharide derivative of the present invention gives a highly transparent aqueous solution and shows an excellent thickening effect with a small amount of addition.
Emulsions that exhibit little change in viscosity due to coexistence of salts and temperature and have extremely excellent stability. Therefore, the novel polysaccharide derivative of the present invention can be widely used as a thickener, a gelling agent, an excipient, an emulsion stabilizer, a flocculant and the like for cosmetics, toiletry products, hair care products, building materials, medicines and the like.

Claims (5)

[Claims] 1. A method according to claim 1, wherein a part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof has the following groups (1) and (2). [In the formula (1), B represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group; A represents an oxygen atom or a carbonyl group;
Represents a linear or branched alkyl group having 4 to 43 carbon atoms;
Represents 0 or 1. (2) In the formula, M ¹ and M ² are the same or different and each represent a hydrogen atom or a monovalent cation. In addition,
Hydrogen atom of hydroxyl group in (1) and M ^{1 in} group (2)
And M ² may be further substituted with another group (1) or (2). ] The novel polysaccharide derivative characterized by being substituted by: 2. The average degree of substitution per constituent monosaccharide residue by substituent (1) is 0.0001 to 1.0, and the average degree of substitution per constituent monosaccharide residue by substituent (2) is 0.01 to 2.0. The novel polysaccharide derivative according to claim 1. 3. The polysaccharide or a derivative thereof is cellulose,
Guar gum, starch, hydroxyethyl cellulose,
Hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, 3. The novel polysaccharide derivative according to claim 1, which is selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylmethylguar gum, hydroxypropylmethylstarch and pullulan. 4. A polysaccharide or a derivative thereof represented by the following general formula:
A method for producing a polysaccharide derivative, which comprises reacting a compound represented by (3) and a compound represented by the following general formula (4). Embedded image [In the formula (3), D is a halogen atom, a hydroxyl group, an epoxidized alkyl group having 3 to 6 carbon atoms, or a straight chain having 1 to 6 carbon atoms which may be substituted by a hydroxyl group and substituted by a halogen atom. Alternatively, A represents a branched alkyl group, A represents an oxygen atom or a carbonyl group, R represents a linear or branched alkyl group having 4 to 43 carbon atoms, and n represents 0 or 1. (4) In the formula, X represents a halogen atom. ] 5. A cosmetic comprising the novel polysaccharide derivative according to claim 1.