JP3180111B2 - New polysaccharide derivatives - Google Patents

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 a low concentration, has little viscosity change in aqueous solution viscosity due to temperature change, and has extremely good emulsion stability. The present invention relates to a novel polysaccharide derivative having a property 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, a gelling agent, an excipient, an emulsion stabilizer, and a flocculant for cosmetics and the like.

[0002]

2. Description of the Related Art Thickeners are one of the important constituents of cosmetics, tray products, external medicines, water-soluble paints and the like. Ideal thickeners used in cosmetics and toiletry products have excellent thickening effect, little change in viscosity due to metal salts, surfactants, oils or other additives, and little change in viscosity over time. And low stickiness, etc., and excellent use feeling, and excellent microbial resistance.

Conventionally, cellulose ethers have been widely used as thickeners, gelling agents, excipients, emulsion stabilizers, and flocculants. Examples of the cellulose ethers include water-soluble nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and ethylhydroxyethylcellulose; ionic celluloses such as carboxymethylcellulose, cationized cellulose and cationized hydroxyethylcellulose. Ethers and the like are commercially available and used.

[0004] These cellulose ethers are relatively excellent in viscosity stability of an aqueous solution in the presence of inorganic metal salts and organic metal salts as compared with polyacrylic acid-based thickeners such as Carbopol.

However, cellulose ethers have a lower viscosity in aqueous solutions at the same concentration than polyacrylic acid-based thickeners, and especially when used as a thickener or an emulsion stabilizer for cosmetics and toiletry products. In order to make full use of the properties of cellulose ethers, it was necessary to increase the amount used. Then, a problem occurs on the touch surface such as stickiness or film feeling, and further, there is a drawback that a viscosity change accompanying a temperature change is large, and it is 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 a nonionic water-soluble cellulose ether has a relatively high viscosity (Japanese Patent Publication No. Hei. JP-A-28041 and JP-B-1-28042), and attempts have been made to apply the same to external medicines and cosmetics (Japanese Patent Laid-Open No. 3-1).
2401, JP-A-3-141210, JP-A-3-141214, and JP-A-3-218316.

[0007] However, although these alkyl-substituted celluloses exhibit a higher viscosity than conventional cellulose ethers, they have low solubility in water and require a long time to be uniformly dissolved when blended in products. And the viscosity stability over time is poor.

[0008]

Accordingly, an object of the present invention is to provide a compound having a high solubility in water, exhibiting a high viscosity in an aqueous solution, and further having an inorganic metal salt, an organic metal salt or a pH value.
Another object of the present invention is to provide a polysaccharide derivative which is not easily affected by such factors as cosmetics and toiletry products, has a good feeling in use, and exhibits excellent effects of thickening and stabilizing emulsion.

[0009]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors have conducted intensive studies to obtain an ideal thickener.
A novel polysaccharide derivative in which a hydrogen atom of at least two hydroxyl groups of a polysaccharide or a derivative thereof is substituted with a glyceryl ether group having a long-chain alkyl and / or alkenyl group and a carboxymethyl group, respectively, has a good solubility in water. When used in aqueous solutions, it exhibits a high viscosity, is not easily affected by inorganic metal salts, organic metal salts, or pH, and exhibits a stable viscosity.In addition, when used in cosmetics and toiletry products, it has a good feeling of use. It has been found that they have excellent effects on thickening and emulsification stabilization, and have completed the present invention.

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

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polysaccharide derivative of the present invention includes, for example, those represented by the following formula.

[0012]

Embedded image

Wherein R ¹ , R ² and R ³ are the same or different and are (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, etc., wherein A ¹ , A ² and A ³ are the same or different and have the same number of carbon atoms. Represents 2 to 4 alkylene groups,
a, b and c are the same or different and each represent 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. Where R ¹ , R ² and R
^At least two of the 3n 3 groups are a hydrophobic substituent (1) and a carboxymethyl group (2), respectively. ]

As the above-mentioned hydrophobic substituent (1), 2-
Hydroxy-3-alkoxypropyl group, 2-alkoxy-3-hydroxypropyl group, 2-hydroxy-3-
Alkenyloxypropyl group, 2-alkenyloxy-
Examples thereof include a 3-hydroxypropyl group, which 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 by these hydrophobic substituents (1) is 0.01 per constituent monosaccharide residue.
It is preferably adjusted appropriately within the range of 1.0 to 1.0, and more preferably 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 its content is in the range of 3.0% by weight to 50% by weight, 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, a sufficient viscosity increasing and emulsion stabilizing effect can be obtained, and when the content is less than 50% by weight, water solubility is improved, which is preferable. The carboxyl group in the carboxymethyl group is entirely or partially 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, 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 amount of the hydrophobic substituent to be introduced, and is preferably 0.01 to 2.0, particularly 0.05 to 1.0 per constituent monosaccharide residue.
Is preferable. 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, for example, reacting a polysaccharide or a derivative thereof with a glycidyl ether having an alkyl and / or alkenyl group having 8 to 40 carbon atoms in a water-soluble alcohol solvent in the presence of an alkali. Let
(Hereinafter, referred to as "hydrophobicization reaction") Then, it is produced by reacting a monohalogenated acetic acid or a salt thereof in the presence of an 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 which 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 preferred, and hydroxyethyl cellulose, methyl cellulose and hydroxypropyl starch are particularly preferred. 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 substituted with a plurality of substituents. Furthermore, these polysaccharides may be used alone or as a mixture. Further, the weight average molecular weight of the polysaccharide or a derivative thereof used in the present invention is 350,000 to 10,000,000, and more preferably 40,000.
It is desirable to be in the range of 10,000 to 5,000,000. Significant thickening effects can be obtained by increasing the molecular weight above 350,000, and those greater than 10 million are not common.

Hereinafter, a method for producing the polysaccharide derivative of the present invention will be described.
The hydrophobization reaction and the carboxymethylation reaction will be described separately. (Hydrophobic reaction) Hydrophobic reaction of polysaccharide or its derivative is as follows:
It is carried out by dissolving or dispersing a polysaccharide or a derivative thereof in a water-soluble alcohol solvent, and reacting 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 a glyceryl ether group (1) of the polysaccharide derivative of the present invention.
The alkyl and alkenyl groups have 8 to 40 carbon atoms. In addition, these alkyl groups and alkenyl groups may be linear or branched, and the position of branching in the case of branching and the number and position of unsaturated bonds in the alkenyl group are not particularly limited. Specific examples of the alkyl group herein include n-octyl group as straight-chain 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-
Octakosyl group, n-nonakosyl group, n-triacontyl group, n-hentriacontyl group, n-dotriacontyl group, n-tritriacontyl group, n-tetratriacontyl group, n-pentatriacontyl group, n- Hexatriacontyl group, n-heptatriacontyl group, n-octatriacontyl group, n-nonatriacontyl group and n-tetracontyl group are represented by the formula:
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 include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, henicocenyl, Examples include a tocosenyl group, a tricosenyl group, a tetracosenyl group, a pentacosenyl group, a hexacosenyl group, a heptacosenyl group, an octacosenyl group, a nonacosenyl group, a triacontenyl group, an oleyl group, a linoleyl group, and a linolenyl group. Of these, alkyl groups and alkenyl groups having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms, are preferred, and from the viewpoint of stability, alkyl groups, particularly linear alkyl groups, are preferred. 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 alkenyl glycidyl ether used can be appropriately adjusted depending on the desired amount of the hydrophobic substituent to be introduced into the polysaccharide or a derivative thereof. 0.1 to 10 equivalents per residue, especially 0.1 to 10 equivalents.
A range of 2 to 5 equivalents is preferred.

The alkali used in the hydrophobizing reaction is not particularly limited, and examples thereof include hydroxides, carbonates and bicarbonates of alkali metals or alkaline earth metals. Among them, sodium hydroxide, potassium hydroxide, Calcium hydroxide, magnesium hydroxide and the like are preferred. The amount of the alkali used is preferably 0.01 to 10 mol times, particularly 0.1 to 5 mol times the alkyl glycidyl ether or alkenyl glycidyl ether to be used, and it is preferable to give good results.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of swelling the polysaccharide or a derivative thereof to increase the reactivity with the hydrophobizing agent, a mixed solvent obtained by adding 1 to 50% by weight, 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 from 0 to 200 ° C., especially from 30 to 10 ° C.
A 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 as it is for carboxymethylation, but if necessary, it can be washed with hot water, aqueous isopropyl alcohol, aqueous acetone solvent, etc. It is also possible to remove the used salts before use.

(Carboxymethylation) The carboxymethylation reaction is carried out by dissolving or dispersing the (hydrophobized) polysaccharide in a suitable solvent and reacting with a monohalogenated acetic acid and / or a salt thereof in the presence of an alkali. Done. As monohalogenated acetic acid and monohalogenated acetate, specifically, monochloroacetic acid, sodium monochloroacetate,
Potassium monochloroacetate, sodium monobromoacetate,
Examples thereof include potassium monobromoacetate, with preference given to monochloroacetic acid and its sodium salt. The amount of the monohalogenated acetic acid to be used may be appropriately selected depending on the degree of substitution of the carboxymethyl group, and is usually 0.1 to 10 moles per mole of the monosaccharide residue constituting the hydrophobized polysaccharide. In particular,
A range of 0.2 to 5 mole times is preferred. The alkali used in this reaction is preferably an alkali hydroxide, and specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide. The amount of the alkali hydroxide to be used is 1.0 to 3.0 times the molar amount of the monohalogenated acetic acid and / or a salt thereof, particularly 1.05 times.
The amount is preferably 1.5 to 1.5 molar times. These monohalogenated acetic acids and salts thereof can be used alone or in combination of two or more.

As the solvent to be used, isopropyl alcohol, tert-butyl alcohol and the like can be mentioned. In order to increase the reactivity between the hydrophobized polysaccharide and the monohalogenated acetic acid, a mixture of isopropyl alcohol or tert-butyl alcohol and 0.1 to 100% by weight, more preferably 1 to 50% by weight of water is added. A solvent may be used.
The reaction temperature of the carboxymethylation is preferably from 0C to 150C, particularly preferably from 30C to 100C. After completion of the reaction, the alkali is neutralized using an acid. As the acid used here,
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, unreacted alkylating agent or salts produced as a by-product by neutralization or the like can be removed by washing with aqueous isopropyl alcohol or aqueous acetone solvent, and then dried and used.

The polysaccharide derivative of the present invention is obtained by partially substituting the hydrogen atom of the hydroxyl group of the polysaccharide or a derivative thereof with a hydrophobic substituent as described above, and then completely or partially hydrogenating the remaining hydroxyl group. It can be obtained by substituting an atom with a carboxymethyl group, but after substituting the carboxymethyl group, it may be substituted with a hydrophobic substituent or both may be performed simultaneously.

When the polysaccharide derivative of the present invention is used in cosmetics, the amount of the polysaccharide derivative is not particularly limited.
% By weight, especially 0.05 to 3% by weight.

When the polysaccharide derivative of the present invention is used in skin cosmetics, surfactants, oils, moisturizers, film-forming agents, oil gelling agents generally used as skin cosmetic ingredients,
Any combination with components such as metal oxides, organic ultraviolet absorbers, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, pigments, fragrances, etc. By blending, various forms such as oil / water, water / oil type emulsified cosmetic, cream, cosmetic emulsion, lotion, oily lotion, lipstick, foundation, skin cleanser 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 ultraviolet absorbers generally used as hair cosmetic ingredients are used. It can be combined with components such as an agent, an inorganic metal salt, an organic metal salt, a pearling agent, an antioxidant, a preservative, a medicinal component, a coloring matter, a fragrance and the like, in any combination. 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 the hair cosmetic is not particularly limited, and depending on the application, various types of hair cosmetics such as emulsions, suspensions, gels, transparent solutions, and aerosols, such as preshampoos, shampoos, hair rinses, hair treatments, etc.
It can be a hair conditioner, a conditioning blowing agent or the like.

The cosmetic composition of the present invention exhibits excellent feeling in use and viscosity stability. However, when used in combination with metal oxides, inorganic metal salts, organic metal salts, etc., particularly good feeling in use and viscosity stability are obtained. 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 metal oxides used in cosmetics include titanium oxide, zinc oxide, iron oxide, zirconium oxide, and cerium oxide. Silica treatment, alumina treatment, silica / alumina treatment, metal soap treatment, fatty acid treatment, Amino acid treatment, silicone treatment, alkyl phosphoric acid treatment, fluorine treatment and the like may be applied. In addition, these 2
More than one or a combination of these and other organic or inorganic powders may be used. 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 content of these metal oxides is 0.001 to 50% by weight, particularly 0.005 to 30% by weight.
% By weight is preferred.

Among the organic UV absorbers, oil-soluble UV absorbers include benzoic acid-based ones such as paraaminobenzoic acid (hereinafter abbreviated as "PABA"), glyceryl PABA, ethyldihydroxypropyl PABA, and N-ethoxylate. PA
BA ethyl ester, N-dimethyl PABA ethyl ester,
N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA, and the like; anthranilic acid-based homomenthyl-N-acetylanthranilate, and the like; salicylic acid-based amyl salicylate Menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc .;
Octylcinnamate, ethyl-4-isopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, 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;
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; 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, dibenzarazin, dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane, 5- (3,3-dimethyl-2-norbonylidene)-
Examples thereof include 3-pentan-2-one, benzenebis-1,3-diketone derivatives described in JP-A-2-221579, and benzoylpinacolone derivatives described in JP-A-3-220153.

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., Achillea millefolium, aloe, below mallow, burdock, salvia And the like, which have an ultraviolet absorbing effect.

These organic ultraviolet absorbers can be used alone or in combination of two or more, and the compounding amount is preferably 0.001 to 50% by weight, particularly preferably 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 from 0.001 to
30% by weight, especially 0.005 to 20% by weight, is preferred.

Other thickening agents 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; 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,
Hydroxy acids such as ethyl 1-hydroxyundecanoate and salts thereof; 1- (2-hydroxyethylamino) -3-
Isostearyloxy-2-propanol, 1- (2-
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 determined by preparing an aqueous solution of the carboxymethylated hydrophobized polysaccharide derivative, adding a certain amount of hydrochloric acid, and then adding an aqueous 0.1N potassium hydroxide solution to titrate the carboxymethyl group. It was determined by quantifying the content. 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 measurements were taken at 25 ° C unless otherwise noted.
Was carried out.

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

(2) After completion of the hydrophobization reaction, the reaction solution
Cooled to 48 ° C. and 15.8% aqueous 48% sodium hydroxide solution.
g, 24.5 g of sodium monochloroacetate, and 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 completion of the reaction, 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 washed 5 times with 1000 ml of 80% acetone (20% water) and twice with 1000 ml of acetone, and dried under reduced pressure to obtain 53.4 g of a hydroxyethylcellulose derivative substituted with stearyl glyceryl ether and carboxymethyl groups. Obtained. The degree of substitution of the stearyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.04 (hydrophobic substituent content: 4.7% by weight), and the degree of substitution of the carboxymethyl group was 0.3. This hydroxyethyl cellulose derivative was transparently dissolved in a 0.5% aqueous solution, and its viscosity was 4,500 cp. FIG. 1 shows the infrared absorption spectrum of this compound.

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

Example 3 The reaction was carried out in the same manner as in Example 1 except that the amount of stearyl glycidyl ether was changed from 3.5 g to 8.8 g 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 condenser was charged with hydroxyethyl cellulose (HEC-QP4400, union) having a weight average molecular weight of about 800,000 and a molar substitution degree of hydroxyethyl of 1.8. Carbide) 50 g, tert-butanol 400 g, 48%
3.5 g of aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, 6.2 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After completion of the hydrophobization reaction, the reaction solution is heated to 40 ° C.
Cooled to 7.0 g of a 48% aqueous sodium hydroxide solution,
Add 12.3 g of sodium monochloroacetate, and add
After stirring for 1 hour at 80 ° C., the mixture was further reacted at 80 ° C. for 2 hours to carry out carboxymethylation. After the completion of the reaction,
After cooling to ℃, acetic acid was added to neutralize the excess alkali, and the cake was obtained by filtration.

The cake obtained was washed with 80% acetone (water 20
%) 5 times with 1000 ml 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 the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.07 (the content of the hydrophobic substituent was 8.2% by weight), and the degree of substitution of the carboxymethyl group was 0.15. This hydroxyethylcellulose derivative has 0.5
% Aqueous solution and its viscosity was 16500 cp.

Example 5 A reaction was carried out in the same manner as in Example 4 except that stearyl glycidyl ether was replaced with palmityl glycidyl ether to obtain a hydroxyethyl cellulose derivative hydrophobized with palmityl glyceryl ether groups. Table 1 shows the results.

Example 6 A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with methyl cellulose (Metroze SM-800, Shin-Etsu, having a weight average molecular weight of about 400,000 and a degree of substitution of methyl groups of 1.8). 50 g, isopropyl alcohol (400 g) and a 48% aqueous sodium hydroxide 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 the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After completion of the hydrophobization reaction, the reaction solution was cooled to 40 ° C., 20.3 g of a 48% aqueous sodium hydroxide solution and 31.5 g of sodium monochloroacetate were added, and the mixture was stirred at 40 ° C. for 1 hour.
Further, the reaction was carried out at 80 ° C. for 2 hours to carry out carboxymethylation. After the completion of the reaction, 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 with 80% acetone (water 20
%) 5 times with 1000 ml and twice with 1000 ml of acetone, followed by drying 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 the stearyl glyceryl ether group of the obtained methyl cellulose derivative was 0.0
7 (the content of the hydrophobic substituents was 10.3% by weight), and the degree of substitution of the carboxymethyl group 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, the reaction was performed by replacing stearyl glycidyl ether with isostearyl glycidyl ether 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 palmityl glyceryl ether group. Table 1 shows the results.

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

Example 10 In the same manner as in Example 6, 8.0 g of stearyl glycidyl ether was replaced with 3.0 g of isostearyl glycidyl ether.
The reaction was performed in place of the above to obtain a methylcellulose derivative substituted with an isostearyl glyceryl ether group. 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 performed in place of the above to obtain a methylcellulose derivative substituted with an isostearyl glyceryl ether group. Table 1 shows the results.

Example 12 The procedure of Example 6 was repeated, except that 8.0 g of stearyl glycidyl ether was replaced with 10.0 g of behenyl glycidyl ether to obtain a methylcellulose derivative substituted with a behenyl glycidyl ether group. Table 1 shows the results.

Example 13 A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxypropyl starch (Matsuya Chemical Co., Ltd.) having a weight average molecular weight of about 5,000,000 and a molar substitution degree of hydroxypropyl group of 0.6. 50 g, isopropyl alcohol 400 g, and 48% aqueous sodium hydroxide 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 completion of the hydrophobization reaction, the reaction solution was cooled to 40 ° C., 8.6 g of a 48% aqueous sodium hydroxide solution and 14.6 g of sodium monochloroacetate were added, and the mixture was stirred at 40 ° C. for 1 hour.
Further, the reaction was carried out at 80 ° C. for 2 hours to carry out carboxymethylation. After the completion of the reaction, 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 with 80% acetone (water 20
%) 5 times with 1000 ml and twice with 1000 ml of acetone, and dried under reduced pressure to obtain 50.3 g of a hydroxypropyl starch derivative substituted with a stearyl glyceryl ether group and a carboxymethyl group. The degree of substitution of the stearyl glyceryl ether group of the obtained hydroxypropyl starch derivative was 0.07 (the content of the hydrophobic substituent was 9.3% by weight), and the degree of substitution of the carboxymethyl group was 0.15. This hydroxypropyl starch derivative has 0.5
% Aqueous solution, its viscosity is 10,250cp
Met.

Example 14 The reaction was carried out in the same manner as in Example 9, except that the amount of stearyl glycidyl ether was changed from 7.5 g to 9.8 g and the amount of sodium morphochloroacetate was changed from 14.6 g to 29.2 g. I 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 a reaction was carried out 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 performing carboxymethylation. Table 2 shows the results.

Comparative Example 3 Using the hydroxyethylcellulose used in Example 1, a hydroxyethylcellulose derivative was synthesized which was subjected to only carboxymethylation without hydrophobization. Table 2 shows the results.

Comparative Example 4 A comparative example was prepared using the hydroxyethyl cellulose used in Example 1 as it was. Table 2 shows the results.

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

Test Example 1 (Viscosity test) 1.0 g of a test sample was dissolved in 200 ml of ion-exchanged water with stirring at room temperature, and the viscosity of the aqueous solution after standing for one day 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 results of the above viscosity increase test, the polysaccharide derivative of the present invention exhibits excellent viscosity increase and excellent water solubility, and is useful in the cosmetics and toiletry fields.

Test Example 2 (Emulsion Stability Test) An emulsion having the following composition was prepared, and immediately after emulsification, the emulsion stability when stored at 50 ° C. was visually determined. In addition, the case where the emulsion was uniformly emulsified was evaluated as ○, and the case where the emulsion was separated was evaluated as ×. 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, and the foam stability of the polysaccharide derivative of the present invention was examined. The foaming amount is
The measurement was carried out at 40 ° C. by the Rossmiles method, and the foaming amount was measured 10 seconds and 120 seconds after foaming. Table 3 shows the results.

<Foam Stability Test Solution> 1.0% by weight of sodium lauryl ether sulfate 0.5% by weight of lanolin 0.1% by weight of test sample Water (4 ° DH) Balance

[0069]

[Table 3]

From the results of the emulsion stability test and the foam stability test shown 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. You can see that.

Example 15 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. The emulsification stability was determined by visually observing the state of the emulsion immediately after storage at 50 ° C., one week and one month later, and the feeling of use was the result of a comparison between the two by a sensory test of 10 expert panelists. When 10 persons answered that it was good, it was evaluated as ○, and when two or less persons answered that it was good, it was evaluated as x. Table 4 shows the results.

<Emulsion 1 of the Present Invention (Comparative Emulsion 1)> The polysaccharide derivative of Example 6 (or Comparative Example 1) 0.5% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 15.0% by weight Methylpolysiloxane 1 Glycerin 3.0% by weight Water balance

[0073]

[Table 4]

Example 16 Emulsion Emulsion 2 of the present invention and Comparative Emulsion 2 having the following compositions were prepared, and their viscosities, emulsion stability, and usability were compared. The emulsification stability was determined by visually observing the state of the emulsion immediately after storage at 50 ° C., one week and one month later, and the feeling of use was the result of a comparison between the two by a sensory test of 10 expert panelists. When 10 persons answered that it was good, it was evaluated as ○, and when two or less persons answered that it was good, it was evaluated as x. Table 5 shows the results.

<Emulsion 2 of the Present Invention (Comparative Emulsion 2)> Polysaccharide derivative of Example 4 (or Comparative Example 1) 0.6% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 12.0% by weight Methylpolysiloxane 1 0.0% 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

[0076]

[Table 5]

Example 17 Emulsion An emulsion 3 of the present invention and a comparative emulsion 3 having the following compositions were prepared, and their viscosity, emulsification stability and usability were compared. The emulsification stability was determined by visually observing the state of the emulsion immediately after storage at 50 ° C., one week and one month later, and the feeling of use was the result of a comparison between the two by a sensory test of 10 expert panelists. , The number of people who answered better. Table 6 shows the results.

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

[0079]

[Table 6]

Example 18 Toner 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 Example 1 Polysaccharide derivative 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 0. 5% by weight butyl paraben 0.1% by weight methyl paraben 0.1% by weight ethanol 5.0% by weight glycerin 3.0% by weight Fragrance 0.05% by weight Water balance

Example 20 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 Example 1 Polysaccharide derivative 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. 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 Wt% Jojoba oil 2.0 wt% Dextrin palmitate 0.5 wt% Octyldimethyl PABA 4.0 wt% Silicone coated fine particle titanium oxide 5.0 wt% Acidic heteropolysaccharide 0.03 wt% Magnesium sulfate 0.5 % By weight Glycerin 5.0% by weight Dibutylhydroxytoluene 0.05% by weight Polysaccharide derivative of Example 3 0.5% by weight Water balance

Example 22 Foundation A foundation was prepared according to the following formulation. This foundation was stable at 50 ° C. for one month and had a good feeling upon 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 Methylphenylpolysiloxane (14cs) 5.0% by weight 2-Ethylhexyl p-methoxycinnamate 3.0% by weight 1.0% by weight 2-hydroxy-4-methoxybenzophenone 1.0% by weight Silicone-coated fine particle titanium oxide 5.0% by weight Silicone Coated fine particle zinc oxide 1.0 wt% Sericite 2.0 wt% Talc 2.0 wt% Bengala 0.4 wt% Yellow iron oxide 0.7 wt% Black iron oxide 0.1 wt% Magnesium sulfate 1.0 % By weight Methyl paraben 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 one month 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 0.0% by weight Polysaccharide derivative of Example 4 0.2% by weight Homomenthyl salicylate 7.8% by weight Titanium oxide 1.0% by weight Red 201 No. 1.0% by weight Red No. 202 2.0% by weight Yellow 4 No. aluminum lake 1.0% by weight Red No. 223 0.1% by weight Fragrance minute amount Butylated hydroxytoluene 0.1% by weight Propyl paraben 0.3% by weight

[0086]

The polysaccharide derivative of the present invention gives a highly transparent aqueous solution, exhibits an excellent thickening effect when added in a small amount, has little change in viscosity due to coexistence of salts and temperature, and has extremely excellent 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 view 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 Research Institute (58) Field surveyed (Int.Cl. ⁷ , DB name) C08B 11/193 A61K 7 / 00 A61K 7/48 C08B 37/00 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A glyceryl ether group (1) having a linear or branched alkyl and / or alkenyl group having 8 to 40 carbon atoms, wherein at least two hydroxyl groups of a polysaccharide or a derivative thereof have a hydrogen atom. In the polysaccharide derivative or salt thereof each substituted with the group (2), the degree of substitution of the glyceryl ether group (1) is 0.01 to 1.0 per constituent monosaccharide residue, and the carboxymethyl group (2)
A polysaccharide derivative or a salt thereof, wherein 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. 2. The polysaccharide or a derivative thereof is cellulose,
Guar gum, starch, hydroxyethyl cellulose,
2. The composition according to claim 1, wherein the composition is selected from the group consisting of 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. Polysaccharide derivatives or salts thereof. 3. The polysaccharide derivative or a salt thereof according to claim 1, wherein the polysaccharide or a derivative thereof 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 a water-soluble alcohol solvent in the presence of an alkali. The method for producing a polysaccharide derivative or a salt thereof according to any one of claims 1 to 3, wherein a monohalogenated acetic acid or a salt thereof is reacted in the presence of. 5. A cosmetic comprising 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.
6. The cosmetic according to claim 5, which comprises at least one species.