JPH09110901A - Novel polysaccharide derivative - Google Patents

Abstract

(57) Abstract: A glyceryl ether group in which at least two hydrogen atoms of a hydroxyl group of a polysaccharide or a derivative thereof have a linear or branched alkyl and / or alkenyl group having 8 to 40 carbon atoms ( 1) and a polysaccharide derivative or a salt thereof each substituted with a carboxymethyl group (2), the substitution degree of the glyceryl ether group (1) is 0.01 to 1.0 per constituent monosaccharide residue, and the carboxymethyl group (2)
A degree of substitution of 0.01 to 2.0 per constituent monosaccharide residue, and a content of glyceryl ether group (1) in the polysaccharide derivative of 3.0 to 50% by weight, or a polysaccharide salt thereof, Manufacturing method and cosmetics containing the same. [Effect] It gives a highly transparent aqueous solution, shows excellent thickening effect even when added in a small amount, has little change in viscosity due to coexistence of salts and temperature, and has excellent emulsion stability, and is suitable for cosmetics and toiletry products. It is useful as a thickener and a gelling agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative, a method for producing the same, and a cosmetic containing the same. More specifically, the present invention has excellent transparency when used as an aqueous solution, exhibits excellent thickening at low concentrations, has viscosity stability with little change in aqueous solution viscosity due to temperature changes, and has extremely good emulsion stability. TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative exhibiting sex and a method for producing the same. Utilizing this property, the novel polysaccharide derivative of the present invention can be widely used as a thickener for cosmetics, a gelling agent, an excipient, an emulsion stabilizer, and an aggregating agent.

[0002]

2. Description of the Related Art Thickeners are one of the important constituents of cosmetics, territories, external medicines and water-soluble paints. As an ideal thickener used for cosmetics and toiletry products, it has excellent thickening effect, little change in viscosity due to metal salts, surfactants, oils, and other additives, and little change in viscosity over time. It also has less stickiness and is excellent in usability and excellent in microbial resistance.

Cellulose ethers have been widely used as thickeners, gelling agents, excipients, emulsion stabilizers and flocculants. As the cellulose ethers, water-soluble nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and ethyl hydroxyethyl cellulose; ionic celluloses such as carboxymethyl cellulose, cationized cellulose, cationized hydroxyethyl cellulose, etc. Ether and the like are commercially available and used.

These cellulose ethers are relatively excellent in aqueous solution viscosity stability in a system coexisting with inorganic metal salts and organic metal salts, as compared with polyacrylic acid type thickeners such as carbopol.

However, cellulose ethers have a lower viscosity increase in an aqueous solution at the same concentration than polyacrylic acid type thickeners, and particularly when used as a thickener or emulsion stabilizer for cosmetics and toiletry products. It was necessary to increase the amount used in order to fully utilize the properties of cellulose ethers. As a result, there is a problem in that there is a problem in the touch surface such as stickiness or film feeling, and moreover, there is a large change in viscosity with a change in temperature, making it difficult to maintain a stable product form.

On the other hand, it has been reported that an alkyl-substituted cellulose obtained by introducing a long-chain alkyl group having 8 to 24 carbon atoms into a part of nonionic water-soluble cellulose ether exhibits a relatively high viscosity (Patent Publication 1). No. 28041, Japanese Patent Publication No. 1-28042), and an attempt to further apply it to external medicines and cosmetics has been made (JP-A 3-1).
2401, JP 3-141210 A, JP 3-141214 A, JP 3-218316 A).

However, although these alkyl-substituted celluloses have excellent thickening properties as compared with conventional cellulose ethers, their solubility in water is low and it takes a long time to uniformly dissolve them in a product. However, there were problems such as poor viscosity stability over time.

[0008]

Therefore, an object of the present invention is to have a high solubility in water and to exhibit a high viscosity when made into an aqueous solution, and further to provide an inorganic metal salt, an organic metal salt or a pH.
It is intended to provide a polysaccharide derivative which is not easily affected by the above and which has a good feeling when used in cosmetics and toiletry products and exhibits an excellent effect in thickening and stabilizing emulsion.

[0009]

In view of such circumstances, the present inventors have conducted diligent research to obtain an ideal thickener, and as a result,
A novel polysaccharide derivative obtained by substituting at least two hydrogen atoms of hydroxyl groups of a polysaccharide or a derivative thereof with a glyceryl ether group having a long-chain alkyl and / or alkenyl group and a carboxymethyl group has good solubility in water. When used in an aqueous solution, it exhibits high thickening properties and is stable against the effects of inorganic metal salts, organic metal salts, pH, etc., and shows a stable thickening property, and when used in cosmetics and toiletry products, it has a good feeling of use. The present invention has been completed and the present invention has been completed by discovering that it has excellent effects on thickening and emulsion stabilization.

That is, according to the present invention, the hydrogen atoms of at least two hydroxyl groups of the polysaccharide or its derivative have 8 to 40 carbon atoms.
In the polysaccharide derivative or its salt substituted with the glyceryl ether group (1) having a linear or branched alkyl and / or alkenyl group and the carboxymethyl group (2), the degree of substitution of the glyceryl ether group (1) is 0.01 to 1.0 per constituent monosaccharide residue, and the degree of substitution of the carboxymethyl group (2) is 0.01 per constituent monosaccharide residue.
To 2.0 and the content of the glyceryl ether group (1) in the polysaccharide derivative is 3.0 to 50% by weight, or a polysaccharide derivative or a salt thereof. The present invention also provides a method for producing the polysaccharide derivative or a salt thereof. Furthermore, the present invention provides a cosmetic containing the polysaccharide derivative or a salt thereof.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the polysaccharide derivative of the present invention include those represented by the following formula.

[0012]

Embedded image

[Wherein R ¹ , R ² and R ³ are the same or different and (1) a glyceryl ether group having a linear or branched alkyl and / or alkenyl group having 8 to 40 carbon atoms (hereinafter, referred to as Sometimes referred to as "hydrophobic substituent"),
(2) a carboxymethyl group and (3) a group selected from a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group and the like, wherein A ¹ , A ² and A ³ are the same or different and have a carbon number 2 to 4 alkylene groups are shown,
a, b and c are the same or different and each represents an integer of 0-10. A ¹ O, A ² O, A ³ O, R ¹ , R ² , R ³ ,
a, b and c may be the same or different within the repeating unit or between the repeating units. However, R ¹ , R ² and R
^At least two of 3n of 3 are a hydrophobic substituent (1) and a carboxymethyl group (2), respectively. ]

Examples of the above hydrophobic substituent (1) include 2-
Hydroxy-3-alkoxypropyl group, 2-alkoxy-3-hydroxypropyl group, 2-hydroxy-3-
Alkenyloxypropyl group, 2-alkenyloxy-
A 3-hydroxypropyl group may be mentioned, and it may be substituted with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to a polysaccharide molecule. The degree of substitution with these hydrophobic substituents (1) is 0.01 per constituent monosaccharide residue.
It is preferable to adjust appropriately within the range of 1.0 to 1.0, and it is more preferable to adjust within the range of 0.02 to 0.5 per constituent monosaccharide residue. Further, the hydrophobic substituent in the polysaccharide derivative of the present invention is substituted so that the content thereof is in the range of 3.0% by weight to 50% by weight, and more preferably 4.0% by weight to 30% by weight. Is desirable. When the content of the hydrophobic substituent is more than 3.0% by weight, sufficient thickening effect and emulsion stabilizing effect are obtained, and when it is less than 50% by weight, water solubility is improved, which is preferable. All or part of the carboxyl group in the carboxymethyl group becomes a salt with an alkali metal such as Na or K, an organic cation group such as an alkaline earth metal represented by Ca or Mg or an amine, or an ammonium ion. May be. The degree of substitution of the carboxymethyl group is
It may be appropriately selected depending on the introduction amount of the hydrophobic substituent, but is 0.01 to 2.0, particularly 0.05 to 1.0 per constituent monosaccharide residue.
Is preferable. Further, a, b and c are more preferably 0 or 1, and A ¹ , A ² and A ³ are more preferably an ethylene group, a propylene group or a trimethylene group.

The polysaccharide derivative of the present invention is hydrophobized by reacting, for example, a polysaccharide or a derivative thereof with a glycidyl ether having an alkyl and / or alkenyl group having 8 to 40 carbon atoms in the presence of an alkali in a water-soluble alcohol solvent. Let
(Hereinafter referred to as "hydrophobization reaction"), and then produced by reacting monohalogenated acetic acid or a salt thereof in the presence of alkali.

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 and the like, among them, 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 and hydroxypropyl starch are preferable, and hydroxyethyl cellulose, methyl cellulose and hydroxypropyl starch are particularly preferable. Also, the methyl group of the polysaccharide used here,
Substituents such as an ethyl group, a hydroxyethyl group, and a hydroxypropyl group may be used alone or may be substituted with a plurality of substituents. Furthermore, these polysaccharides may be used alone or in combination. Furthermore, the weight average molecular weight of the polysaccharide or its derivative used in the present invention is 350,000 to 10,000,000, and further 40
It is preferably in the range of 10,000 to 5,000,000. Increasing the molecular weight above 350,000 produces a considerable thickening effect, and those above 10 million are not common.

The method for producing the polysaccharide derivative of the present invention will be described below.
The hydrophobization reaction and the carboxymethylation reaction will be described separately. (Hydrophobization reaction) The hydrophobization reaction of the polysaccharide or its derivative is
It is carried out by dissolving or dispersing a polysaccharide or a derivative thereof in a water-soluble alcohol solvent and reacting it with an alkyl glycidyl ether and / or an alkenyl glycidyl ether in the presence of an alkali.

The alkyl glycidyl ether and / or alkenyl glycidyl ether used in the hydrophobizing reaction is the glyceryl ether group (1) of the polysaccharide derivative of the present invention.
Therefore, the number of carbon atoms of the alkyl or alkenyl group is 8 to 40. The alkyl group and alkenyl group may be linear or branched, and the branching position in the case of branching, the number and position of unsaturated bonds in the alkenyl group are not particularly limited. Specific examples of the alkyl group here include n-octyl group as linear alkyl, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, and n-tetradecyl group as n-nonyl group. , N
-Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-
Icosyl group, n-henicosyl group, n-docosyl group, n
-Tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-
Octacosyl group, n-nonacosyl group, n-triacontyl group, n-hentriacontyl group, n-dotriacontyl group, n-tritriacontyl group, n-tetratriacontyl group, n-pentatriacontyl group, n- The hexatriacontyl group, the n-heptatriacontyl group, the n-octatriacontyl group, the n-nonatriacontyl group and the n-tetracontyl group are the branched alkyl groups of 2-
Ethylhexyl group, methylundecyl group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group,
2-octyldodecyl group, 2-heptylundecyl group,
Examples thereof include a 2-decyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecyloctadecyl group, and a 2-tetradecylbehenyl group. Specific examples of the alkenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group, henicocenyl group, Examples thereof include a tococenyl group, a tricocenyl group, a tetracocenyl group, a pentacocenyl group, a hexacocenyl group, a heptacocenyl group, an octacocenyl group, a nonacocenyl group, a triacontenyl group, an oleyl group, a linoleyl group and a linolenyl group. Of these, an alkyl group and an alkenyl group having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms are preferable, and an alkyl group, particularly a linear alkyl group, is preferable from the viewpoint of stability. These alkyl glycidyl ethers and alkenyl glycidyl ethers can be used alone or in combination of two or more. The amount of the alkyl glycidyl ether and / or the alkenyl glycidyl ether used can be appropriately adjusted depending on the desired introduction amount of the hydrophobic substituent to the polysaccharide or its derivative, but it is usually a constituent monosaccharide of the polysaccharide or its derivative. 0.1 to 10 equivalents per residue, especially 0.
A range of 2-5 equivalents is preferred.

The alkali used for the hydrophobizing reaction is not particularly limited, but examples thereof include alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, among which sodium hydroxide, potassium hydroxide, Calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is preferably 0.01 to 10 mol times, particularly 0.1 to 5 mol times the amount of the alkyl glycidyl ether or alkenyl glycidyl ether to be used, since good results are obtained.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of swelling the polysaccharide or its derivative to enhance the reactivity with the hydrophobizing agent, a mixed solvent obtained by adding 1 to 50% by weight, and more preferably 2 to 30% by weight of water to these lower alcohols is used. It is preferable to carry out the reaction.

The reaction temperature is 0 to 200 ° C., especially 30 to 10
The range of 0 ° C 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 and lactic acid can be used.

The hydrophobized polysaccharide thus obtained is
It can be separated by filtration and used for carboxymethylation as it is, but if necessary, washed with hot water, hydrated isopropyl alcohol, hydrated acetone solvent, etc., and by-produced by unreacted hydrophobizing agent or neutralization. It can also be used after removing the salts.

(Carboxymethylation) Carboxymethylation is carried out by dissolving or dispersing a (hydrophobized) polysaccharide in a suitable solvent and reacting it with a monohalogenated acetic acid and / or a salt thereof in the presence of an alkali. Done. Specific examples of the monohalogenated acetic acid and monohalogenated acetate include monochloroacetic acid, sodium monochloroacetate,
Potassium monochloroacetate, sodium monobromoacetate,
Examples include potassium monobromoacetate, with monochloroacetic acid and its sodium salt being preferred. The amount of the monohalogenated acetic acid to be used may be appropriately selected according to the degree of substitution of the carboxymethyl group, but is usually 0.1 to 10 times the mole number per the constituent monosaccharide residue of the hydrophobized polysaccharide, Especially,
The range of 0.2 to 5 mol times is preferable. The alkali used in this reaction is preferably alkali hydroxide, and specific examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide. The amount of alkali hydroxide used is 1.0 to 3.0 times the molar amount of the monohalogenated acetic acid and / or its salt, particularly 1.05.
A preferable amount is up to 1.5 molar times. These monohalogenated acetic acid and salts thereof can be used alone or in combination of two or more kinds.

Examples of the solvent used include isopropyl alcohol and tert-butyl alcohol. Further, for the purpose of enhancing the reactivity between the hydrophobized polysaccharide and the monohalogenated acetic acid, isopropyl alcohol or tert-butyl alcohol is mixed with 0.1 to 100% by weight, more preferably 1 to 50% by weight of water. A solvent may be used.
The reaction temperature for carboxymethylation is 0 ° C to 150 ° C, particularly preferably 30 ° C to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. The acid used here is
Inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid and lactic acid can be used. The obtained polysaccharide derivative of the present invention is used after being separated by filtration or the like and dried. If necessary, the unreacted alkylating agent and salts by-produced by neutralization and the like can be removed by washing with a hydrated isopropyl alcohol or hydrated acetone solvent and then dried before use.

In the polysaccharide derivative of the present invention, the hydrogen atom of the hydroxyl group of the polysaccharide or its derivative is partially substituted with a hydrophobic substituent as described above, and then all or a part of the hydrogen atoms of the remaining hydroxyl group is replaced. Although it can be obtained by substituting an atom with a carboxymethyl group, it may be substituted with a hydrophobic substituent after the substitution with the carboxymethyl group, or both may be performed simultaneously.

When the polysaccharide derivative of the present invention is used in cosmetics, the compounding amount is not particularly limited, but is 0.01-10.
%, Especially 0.05 to 3% by weight is preferred.

When the polysaccharide derivative of the present invention is used in skin cosmetics, surfactants, oils, moisturizers, film-forming agents, oil gelling agents, which are generally used as skin cosmetic ingredients,
Metal oxides, organic UV absorbers, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, dyes, fragrances, etc. By blending, various forms such as oil / water, water / oil type emulsified cosmetics, creams, lotions, lotions, oily lotions, lipsticks, foundations, skin cleansing agents and the like can be obtained.

When the polysaccharide derivative of the present invention is used in hair cosmetics, surfactants, other thickeners, oil gelling agents, metal oxides, organic UV absorption which are generally used as hair cosmetic ingredients. It can be blended in any combination with components such as an agent, an inorganic metal salt, an organic metal salt, a pearling agent, an antioxidant, an antiseptic, a medicinal component, a dye and a fragrance. In addition, 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 hair cosmetics is not particularly limited, and depending on the application, general hair cosmetics of various dosage forms such as emulsions, suspensions, gels, transparent solutions, aerosols, that is, pre-shampoo agents, shampoos, hair rinses, hair treatments,
It can be used as a hair conditioner, a conditioning blow agent, or the like.

The cosmetics of the present invention exhibit 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. You can get sex. 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 metal oxides used in cosmetics 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, It may be subjected to amino acid treatment, silicone treatment, alkyl phosphoric acid treatment, fluorine treatment and the like. In addition, these 2
It may be one or more or a composite of these and other organic powder or inorganic powder. The 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, particularly 0.005 to 30%.
% By weight is preferred.

Among the organic UV absorbers, the oil-soluble UV absorbers include benzoic acid-based ones such as para-aminobenzoic acid (hereinafter abbreviated as "PABA"), glyceryl PABA, ethyldihydroxypropyl PABA, N-ethoxylate. PA
BA ethyl ester, N-dimethyl PABA ethyl ester,
N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, etc .; as anthranilic acid type, homomenthyl-N-acetylanthranilate, etc .; as salicylic acid type, amyl salicylate , Menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate and the like;
Octyl cinnamate, ethyl-4-isopropyl cinnamate, ethyl-2,4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxy cinnamate, isopropyl-p
-Methoxycinnamate, isoamyl-p-methoxycinnamate, 2-ethylhexyl-p-methoxycinnamate, 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β- Phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate,
Glyceryl mono-2-ethylhexanoyldiparamethoxycinnamate and the like; as a benzophenone type,
2,4-dihydroxybenzophenone, -2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-
Dihydroxy-4,4'-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxy-4'-methylbenzophenone, 4-phenylbenzophenone, 2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3 -Carboxybenzophenone and the like; as others, 3- (4'-methylbenzylidene) -dl-camphor, 3-benzylidene-dl
-Camphor, urocanic acid ethyl ester, 2-phenyl-3-methylbenzoxazole, 2,2'-hydroxy-5-methylphenylbenzotriazole, 2-
(2'-Hydroxy-5-t-octylphenyl) benzotriazole, dibenzalazine, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbornylidene)-
3-pentan-2-one, a benzenebis-1,3-diketone derivative described in JP-A-2-212579, a benzoylpinacolone derivative described in JP-A-3-220153, and the like can be mentioned.

As the water-soluble ultraviolet absorber, diethanolamine p-methoxycinnamate, 2-hydroxy-
Sodium 4-methoxybenzophenone-5-sulfonate, tetrahydroxybenzophenone, methylherperidine, sodium 3-hydroxy-4-methoxycinnamate, sodium ferulate, urocanic acid, etc., yarrow, aloe, biloba, salvia, burdock, salvia Examples include animal and plant extracts such as those having an ultraviolet absorbing action.

These organic ultraviolet absorbers may be blended alone or in combination of two or more, and the blending amount thereof is preferably 0.001 to 50% by weight, particularly preferably 0.005 to 30% by weight.

As inorganic metal salts and organic metal salts, all monovalent metal salts, divalent metal salts and trivalent metal salts used in cosmetics can be used.
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 blending amount thereof is 0.001 to
30% by weight, particularly 0.005 to 20% by weight is preferred.

Other thickeners include xanthan gum, hyaluronic acid, and Polyanthes.
L.) plant callus-derived acidic heteropolysaccharide and other polysaccharides and derivatives thereof, the film-forming agent,
Examples thereof 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 ester.

The medicinal components include plant extracts such as hamamelis, button, chamomile and chamomile; amino acids such as glycine and serine and their derivatives; oligopeptides; guanidine derivatives described in JP-A-6-223023; glycyrrhizin and Anti-inflammatory agents such as salts thereof, glycyrrhetin and salts thereof, allantoin, epsilon aminocaproic acid and salts thereof; α-carotene, β-carotene,
Vitamins such as ascorbic acid and tocopherol; Antioxidants such as tannins and flavonoids; 6-hydroxyhexanoic acid, 8-hydroxyundecanoic acid, 9-hydroxyundecanoic acid, 10-hydroxyundecanoic acid, 1
Hydroxy acids such as ethyl 1-hydroxyundecanoate and salts thereof; 1- (2-hydroxyethylamino) -3-
Isostearyloxy-2-propanol, 1- (2-
Examples thereof include amine derivatives such as hydroxyethylamino) -3- (12-hydroxystearyloxy) -2-propanol and 1- (2-hydroxyethylamino) -3-methyloxy-2-propanol.

[0037]

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.
Further, the degree of substitution of the hydrophobic substituent of the polysaccharide derivative of the present invention is NM.
The degree of carboxymethyl group substitution was measured using R, and an aqueous solution of a carboxymethylated hydrophobized polysaccharide derivative was prepared, and after adding a certain amount of hydrochloric acid, a 0.1N aqueous potassium hydroxide solution was added to titrate the carboxy group. It was determined by quantifying the content. In addition, in the following examples, "degree of substitution" indicates the number of substituents per constituent monosaccharide residue. The viscosity was measured using a B-type viscometer (rotor No. 4, 12 rpm). Viscosity is measured at 25 ° C unless otherwise specified.
Was carried out.

Example 1 (1) In a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, a weight average molecular weight of about 80 was obtained.
50 g of hydroxyethyl cellulose (HEC-QP4400, manufactured by Union Carbide Co.) having a molar substitution degree of hydroxyethyl of 1.8, and isopropyl alcohol 400.
g, 3.5 g of 48% aqueous sodium hydroxide solution was added,
The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, add 3.5 g of stearyl glycidyl ether, and add 8 g at 80 ° C.
The reaction was allowed to proceed for a period of time to complete the hydrophobization reaction.

(2) After the completion of the hydrophobizing reaction, the reaction solution is added to 40
Cooled to ℃, 48% sodium hydroxide aqueous solution 15.8
g, and 24.5 g of sodium monochloroacetate were added to give 4
After stirring at 0 ° C for 1 hour, the mixture was further reacted at 80 ° C for 2 hours to carry out carboxymethylation. After the reaction was completed, the reaction solution was cooled to 60 ° C., acetic acid was added to neutralize excess alkali, and then a cake was obtained by filtration. The cake obtained was washed 5 times with 1000 ml of 80% acetone (20% water) and 2 times with 1000 ml of acetone, and dried under reduced pressure to give 53.4 g of hydroxyethyl cellulose derivative substituted with stearyl glyceryl ether group and carboxymethyl group. Obtained. The degree of substitution of stearyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.04 (hydrophobic substituent content 4.7 weight%), and the degree of substitution of carboxymethyl group was 0.3. The hydroxyethyl cellulose derivative was transparently dissolved in a 0.5% aqueous solution and had a viscosity of 4,500 cp. The infrared absorption spectrum of this compound is shown in FIG.

Example 2 In the same manner as in Example 1, the amount of stearyl glycidyl ether was changed from 3.5 g to 6.2 g and the reaction was carried out to obtain a hydroxyethyl cellulose derivative hydrophobized with a stearyl glyceryl ether group. Table 1 shows the results.

Example 3 In the same manner as in Example 1, the amount of stearyl glycidyl ether was changed from 3.5 g to 8.8 g and the reaction was carried out to obtain a hydroxyethyl cellulose derivative hydrophobized with stearyl glyceryl ether groups. Table 1 shows the results.

Example 4 A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a hydroxyethyl molar substitution of 1.8 (HEC-QP4400, Union). Carbide) 50 g, tert-butanol 400 g, 48%
3.5 g of an aqueous sodium hydroxide solution was added, and the mixture was stirred under a nitrogen atmosphere for 30 minutes at room temperature. To this, 6.2 g of stearyl glycidyl ether was added and reacted at 80 ° C. for 8 hours to make it hydrophobic. After the hydrophobization reaction is completed, the reaction solution is kept at 40 °
Cooled to 7.0 g of 48% sodium hydroxide aqueous solution,
Add 12.3 g of sodium monochloroacetate, 40 ℃
After stirring for 1 hour, the mixture was further reacted at 80 ° C. for 2 hours to carry out carboxymethylation. After the reaction is completed,
After cooling to ℃ and adding acetic acid to neutralize excess alkali, a cake was obtained by filtration.

The cake obtained was treated with 80% acetone (20% water).
%), Washed 5 times with 1000 ml of acetone and twice with 1000 ml of acetone, and dried under reduced pressure to obtain 50.4 g of a hydroxyethyl cellulose derivative substituted with a stearyl glyceryl ether group and a carboxymethyl group. The degree of substitution of stearyl glyceryl ether groups of the obtained hydroxyethyl cellulose derivative was 0.07 (content of hydrophobic substituents was 8.2% by weight), and the degree of substitution of carboxymethyl groups was 0.15. This hydroxyethyl cellulose derivative is 0.5
% Transparently dissolved in water, and its viscosity was 16500 cp.

Example 5 In the same manner as in Example 4, the reaction was performed by changing the stearyl glycidyl ether to palmityl glycidyl ether to obtain a hydroxyethyl cellulose derivative hydrophobized with a palmityl glyceryl ether group. Table 1 shows the results.

Example 6 In a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a cooling tube, methylcellulose (Metroze SM-800, Shin-Etsu, methylose having a weight average molecular weight of about 400,000 and a methyl group substitution of 1.8) was used. (Chemical Industry Co., Ltd.) 50 g, isopropyl alcohol 400 g, and 48% sodium hydroxide aqueous solution 4.5 g were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, 8.0 g of stearyl glycidyl ether was added and reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobic reaction, the reaction solution was cooled to 40 ° C., 20.3 g of 48% sodium hydroxide aqueous solution and 31.5 g of sodium monochloroacetate were added, and the mixture was stirred at 40 ° C. for 1 hour,
Further, the mixture was reacted at 80 ° C. for 2 hours to carry out carboxymethylation. After the reaction was completed, the reaction solution was cooled to 60 ° C., acetic acid was added to neutralize excess alkali, and then a cake was obtained by filtration.

The cake obtained is treated with 80% acetone (20% water).
%) 5 times with 1000 ml and twice with 1000 ml of acetone, and then dried under reduced pressure to obtain 49.5 g of a methylcellulose derivative substituted with a stearyl glyceryl ether group and a carboxymethyl group. The degree of substitution of stearyl glyceryl ether group of the obtained methyl cellulose derivative is 0.0
7 (hydrophobic substituent content 10.3% by weight) The degree of carboxymethyl group substitution was 0.12. This methylcellulose derivative was transparently dissolved in a 0.5% aqueous solution and had a viscosity of 14,000 cp.

Example 7 In the same manner as in Example 6, stearyl glycidyl ether was replaced with isostearyl glycidyl ether and reacted to obtain a methylcellulose derivative hydrophobized with an isostearyl glyceryl ether group. Table 1 shows the results.

Example 8 In the same manner as in Example 6, stearyl glycidyl ether was replaced with palmityl glycidyl ether and reacted to obtain a methylcellulose derivative hydrophobized with a palmityl glyceryl ether group. Table 1 shows the results.

Example 9 In the same manner as in Example 6, the amount of stearyl glycidyl ether was changed from 8.0 g to 2.4 g and the reaction was carried out to obtain a methylcellulose derivative hydrophobized with a stearyl glyceryl ether group. Table 1 shows the results.

Example 10 In the same manner as in Example 6, 8.0 g of stearyl glycidyl ether was added to 3.0 g of isostearyl glycidyl ether.
The reaction was carried out instead, and a methylcellulose derivative substituted with an isostearyl glyceryl ether group was obtained. Table 1 shows the results.

Example 11 In the same manner as in Example 6, 8.0 g of stearyl glycidyl ether was replaced with 6.0 g of isostearyl glycidyl ether.
The reaction was carried out instead, and a methylcellulose derivative substituted with an isostearyl glyceryl ether group was obtained. Table 1 shows the results.

Example 12 In the same manner as in Example 6, 8.0 g of stearyl glycidyl ether was replaced with 10.0 g of behenyl glycidyl ether and reacted to obtain a methylcellulose derivative substituted with a behenyl glycidyl ether group. Table 1 shows the results.

Example 13 In a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, hydroxypropyl starch (Matsutani Chemical Co., Ltd.) having a weight average molecular weight of about 5,000,000 and a hydroxypropyl group molar substitution of 0.6 was used. 50 g, isopropyl alcohol 400 g, and 48% sodium hydroxide aqueous solution 4.3 g were added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, 7.5 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was cooled to 40 ° C., 8.6 g of 48% sodium hydroxide aqueous solution and 14.6 g of sodium monochloroacetate were added, and the mixture was stirred at 40 ° C. for 1 hour.
Further, the mixture was reacted at 80 ° C. for 2 hours to carry out carboxymethylation. After the reaction was completed, the reaction solution was cooled to 60 ° C., acetic acid was added to neutralize excess alkali, and then a cake was obtained by filtration.

The cake obtained was treated with 80% acetone (20% water).
%) 5 times with 1000 ml and twice with 1000 ml of acetone, and then dried under reduced pressure to obtain 50.3 g of hydroxypropyl starch derivative substituted with stearyl glyceryl ether group and carboxymethyl group. The degree of substitution of stearyl glyceryl ether groups of the obtained hydroxypropyl starch derivative was 0.07 (content of hydrophobic substituents was 9.3% by weight), and the degree of substitution of carboxymethyl groups was 0.15. This hydroxypropyl starch derivative is 0.5
% Transparently dissolved in an aqueous solution with a viscosity of 10,250 cp
Met.

Example 14 In the same manner as in Example 9, the amount of stearyl glycidyl ether was changed from 7.5 g to 9.8 g, and the amount of sodium chlorochloroacetate was changed from 14.6 g to 29.2 g, and the reaction was carried out to obtain a hydroxypropyl starch derivative. Got Table 1 shows the results.

Comparative Example 1 Using the hydroxyethyl cellulose used in Example 1, the amount of stearyl glycidyl ether was changed from 3.5 g to 0.9 g and reacted to obtain a hydroxyethyl cellulose derivative having a low degree of substitution of stearyl glyceryl ether group. Obtained. Table 2 shows the results.

Comparative Example 2 The hydroxyethyl cellulose used in Example 1 was reacted with stearyl glycidyl ether to synthesize a hydroxyethyl cellulose derivative substituted only with a stearyl glyceryl ether group without carboxymethylation. Table 2 shows the results.

Comparative Example 3 The hydroxyethyl cellulose used in Example 1 was used to synthesize a hydroxyethyl cellulose derivative which was carboxymethylated only without being hydrophobized. Table 2 shows the results.

Comparative Example 4 The hydroxyethyl cellulose used in Example 1 was used as it was as a comparative example. Table 2 shows the results.

Comparative Example 5 In the same manner as in Example 6, the amount of stearyl glycidyl ether was changed from 8.0 g to 1.0 g and the reaction was carried out to obtain a methylcellulose derivative hydrophobized with stearyl glyceryl ether groups. Table 2 shows the results.

Test Example 1 (Thickening Test) A test sample (1.0 g) was dissolved in 200 ml of ion-exchanged water with stirring at room temperature, and the viscosity of the aqueous solution after standing overnight was measured. The viscosity was measured using a Brookfield viscometer (rotor No. 4, 12 rpm, room temperature). The results are shown in Tables 1 and 2.

[0062]

[Table 1]

[0063]

[Table 2]

As can be seen from the above thickening test results, the polysaccharide derivative of the present invention exhibits excellent thickening properties and excellent water solubility, and is thus useful in the fields of cosmetics and toiletries.

Test Example 2 (Emulsion Stability Test) An emulsion having the following composition was prepared, and the emulsion stability when stored at 50 ° C. immediately after emulsification was visually evaluated. The case where the emulsion was uniformly emulsified was marked with ◯, and the case where it was separated was marked with x. Table 3 shows the results.

<Emulsion composition> Vaseline 50% by weight Lanolin 8% by weight Polyoxyethylene (5) lauryl ether 0.5% by weight Test sample 0.2% by weight Purified water balance

Test Example 3 (Foam Stability Test) A foam stability test solution having the following composition was prepared to study the foam stabilization of the polysaccharide derivative of the present invention. The amount of foaming is
It measured at 40 degreeC by the loss miles method, and measured the foaming amount 10 seconds after foaming and 120 seconds after foaming. Table 3 shows the results.

<Foam Stability Test Solution> Sodium lauryl ether sulfate 1.0% by weight Lanolin 0.5% by weight Test sample 0.1% by weight Water (4 ° DH) balance

[0069]

[Table 3]

From the results of the emulsion stability test and foam stability test in Table 3, the polysaccharide derivative of the present invention has excellent emulsion stability and foam stability and is useful in the fields of cosmetics and toiletries. I understand.

Example 15 Emulsion An inventive emulsion 1 and a comparative emulsion 1 having the following compositions were prepared, and their viscosities, emulsion stability and sensations during use were compared. The emulsion stability was visually evaluated immediately after storage at 50 ° C, 1 week and 1 month later, and the feeling of use was the result of a sensory test by 10 expert panelists comparing the two. The case where 10 people answered good was evaluated as ◯, and the case where the number of people who answered good was 2 or less was evaluated as x. Table 4 shows the results.

<Inventive Emulsion 1 (Comparative Emulsion 1)> Polysaccharide Derivative of Example 6 (or Comparative Example 1) 0.5 wt% Squalane 3.0 wt% Methylcyclopolysiloxane 15.0 wt% Methylpolysiloxane 1 0.0 wt% glycerin 3.0 wt% Water balance

[0073]

[Table 4]

Example 16 Milky lotion The milky lotion 2 of the present invention and the comparative milky lotion 2 having the following compositions were prepared, and their viscosity, emulsion stability and feeling upon use were compared. The emulsion stability was visually evaluated immediately after storage at 50 ° C, 1 week and 1 month later, and the feeling of use was the result of a sensory test by 10 expert panelists comparing the two. The case where 10 people answered good was evaluated as ◯, and the case where the number of people who answered good was 2 or less was evaluated as x. Table 5 shows the results.

<Inventive Emulsion 2 (Comparative Emulsion 2)> Polysaccharide Derivative of Example 4 (or Comparative Example 1) 0.6 wt% Squalane 3.0 wt% Methylcyclopolysiloxane 12.0 wt% Methylpolysiloxane 1 0.0 wt% 2-Ethylhexyl paramethoxycinnamate 5.0 wt% Silicone-coated zinc oxide 3.0 wt% Glycerin 2.0 wt% Water balance

[0076]

[Table 5]

Example 17 Emulsion An inventive emulsion 3 and a comparative emulsion 3 having the following compositions were prepared, and their viscosities, emulsion stability and usability were compared. The emulsion stability was visually evaluated immediately after storage at 50 ° C, 1 week and 1 month later, and the feeling of use was the result of a sensory test by 10 expert panelists comparing the two. , The number of people who answered better. Table 6 shows the results.

<Inventive Emulsion 3 (Comparative Emulsion 3)> Polysaccharide Derivative of Example 5 (or Comparative Example 1) 0.25 wt% Water (or water 53.3 wt% + L-algin 0.25 wt%) 53.55 wt% Ethanol (55v / v%) 10.0 wt% Glycerin 2.0 wt% 2-Ethylhexyl paramethoxycinnamate 3.0 wt% Methylpolysiloxane 5.0 wt% Methylcyclopolysiloxane 25.0 wt% Zinc sulfocarbolate 0 0.2% by weight Self-emulsifying glycerol monostearate 0.7% by weight Sorbitan monostearate 0.3% by weight

[0079]

[Table 6]

Example 18 Lotion 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 Glycerine 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 Example 1 Polysaccharide derivative of 0.2% by weight water balance

Example 19 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% by weight Olive oil 8.0% by weight Jojoba oil 1.0% by weight Polyoxyethylene hydrogenated castor oil (10EO) 1.0% by weight Sorbitan monostearate 1.0% by weight Polysaccharide derivative of Example 7. 5% by weight Butylparaben 0.1% by weight Methylparaben 0.1% by weight Ethanol 5.0% by weight Glycerin 3.0% by weight Perfume 0.05% by weight Water balance

Example 20 Lotion 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 Glycerine 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 Example 1 Polysaccharide derivative of 0.15% by weight Zinc p-phenolsulfonate 0.2% by weight Water balance

Example 21 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. Dimethyl siloxane methyl (polyoxy ethylene) siloxane polymer 2.0 wt% Polyoxyethylene (20EO) sorbitan monooleate 0.5 wt% Methyl polysiloxane (5cs) 7.0 wt% Methyl phenyl polysiloxane 2.0 Weight% Jojoba oil 2.0 weight% Dextrin palmitate 0.5 weight% Octyldimethyl PABA 4.0 weight% Silicone-coated particulate titanium oxide 5.0 weight% Acidic heteropolysaccharide 0.03 weight% Magnesium sulfate 0.5 Wt% glycerin 5.0 wt% dibutylhydroxytoluene 0.05 wt% polysaccharide derivative of Example 3 0.5 wt% water balance

Example 22 Foundation A foundation was prepared according to the following formulation. This foundation was stable at 50 ° C for 1 month and had a good feeling in use. Polysaccharide derivative of Example 3 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 wt% 2-Ethylhexyl p-methoxycinnamate 3.0 wt% 2-Hydroxy-4-methoxybenzophenone 1.0 wt% Silicone coated fine particle titanium oxide 5.0 wt% Silicone Coated fine particles Zinc oxide 1.0% by weight Sericite 2.0% by weight Talc 2.0% by weight Red iron oxide 0.4% by weight Yellow iron oxide 0.7% by weight Black iron oxide 0.1% by weight Magnesium sulfate 1.0 Weight% Methylparaben 0.2% by weight Fragrance Fine water balance

Example 23 Lipstick A lipstick was prepared according to the following formulation. This lipstick was stable at 50 ° C for 1 month and had a good feeling in use. Castor oil 52.0 wt% lanolin 5.0 wt% liquid lanolin 5.0 wt% beeswax 4.0 wt% ozokerite 7.0 wt% candelilla wax 2.0 wt% carnauba wax 1.0 wt% dodecyl modified silicone 10 0.0 wt% Polysaccharide derivative of Example 4 0.2 wt% Homomenthyl salicylate 7.8 wt% Titanium oxide 1.0 wt% Red 201 1.0 wt% Red 202 2.0 wt% Yellow 4 Aluminum lake 1.0% by weight Red 223 0.1% by weight Fragrance Small amount Butylated hydroxytoluene 0.1% by weight Propylparaben 0.3% by weight

[0086]

INDUSTRIAL APPLICABILITY The polysaccharide derivative of the present invention gives an aqueous solution having high transparency, exhibits an excellent thickening effect even when added in a small amount, has little viscosity change due to coexistence of salts and temperature, and is extremely excellent in stability. Give an emulsion. Therefore, the polysaccharide derivative of the present invention is a thickener for cosmetics and toiletry products,
It can be widely used as a gelling agent, excipient, emulsion stabilizer, flocculant and the like.

[Brief description of the drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a polysaccharide derivative of the present invention (Example 1).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihito Abe 2-1-3 Bunka, Sumida-ku, Tokyo Kao Corporation Stock Research Institute

Claims (6)

[Claims] 1. A glyceryl ether group (1) in which at least two hydrogen atoms of a hydroxyl group of a polysaccharide or a derivative thereof have a linear or branched alkyl and / or alkenyl group having 8 to 40 carbon atoms and carboxymethyl. In the polysaccharide derivative or salt thereof each substituted with the group (2), the substitution degree of the glyceryl ether group (1) is 0.01 to 1.0 per constituent monosaccharide residue, and the carboxymethyl group (2)
The degree of substitution is 0.01 to 2.0 per constituent monosaccharide residue, and the content of the glyceryl ether group (1) in the polysaccharide derivative is 3.0 to 50% by weight or a salt thereof. 2. The polysaccharide or its derivative is cellulose,
Guar gum, starch, hydroxyethyl cellulose,
The hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum and hydroxypropyl starch selected from the group consisting of claim 1. Polysaccharide derivative or salt thereof. 3. The polysaccharide derivative or its salt according to claim 1 or 2, wherein the polysaccharide or its derivative has a weight average molecular weight of 350,000 to 10,000,000. 4. A polysaccharide or a derivative thereof is reacted with a glycidyl ether having a linear or branched alkyl and / or alkenyl group having 8 to 40 carbon atoms in the presence of an alkali in a water-soluble alcohol solvent, and then an alkali is used. The method for producing a polysaccharide derivative or a salt thereof according to any one of claims 1 to 3, wherein the monohalogenated acetic acid or a salt thereof is reacted in the presence of 5. A cosmetic containing the polysaccharide derivative according to claim 1 or a salt thereof. 6. A compound selected from the group consisting of metal oxides, organic ultraviolet absorbers, inorganic metal salts and organic metal salts.
The cosmetic according to claim 5, which comprises one kind or two or more kinds.