JP3165377B2 - Novel polysaccharide derivative, method for producing the same, and cosmetic containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

On the other hand, for example, JP-A-55-110103 and JP-A-56-801 disclose long-chain alkyl groups having 10 to 24 carbon atoms in a part of nonionic water-soluble cellulose ethers. It has been disclosed that a hydrophobized nonionic cellulose derivative into which is introduced a small amount of water shows a relatively high viscosity when mixed with water. In addition, JP-A-3-24001, JP-A-3-41210, JP-A-3-41214, JP-A-3-218316, as seen in JP-A-3-218316, topical pharmaceuticals for these alkyl-substituted cellulose derivatives, cosmetics Attempts have been made to apply it to such applications. However, although these alkyl-substituted cellulose derivatives exhibit excellent viscosity increase compared to the above-mentioned cellulose ethers, they have poor water solubility and require a long time to be uniformly dissolved when blended into products, Problems such as poor viscosity stability.

[0005]

The ideal thickeners used in cosmetics and toiletry products are those which dissolve easily and have an excellent thickening effect, and the addition of coexisting metal salts, surfactants, oils and other additives. It has little influence on viscosity due to changes in temperature, temperature, and pH, and has little change in viscosity over time, low stickiness and the like, excellent feeling in use, and excellent microbial resistance. However, the above-mentioned cellulose ethers and alkyl-substituted cellulose derivatives have not sufficiently satisfied all of these required properties.

Accordingly, the present invention exhibits a high viscosity at a low concentration, and the viscosity is controlled by the inorganic metal salt, the organic metal salt, the temperature and the pH.
Novel polysaccharide derivatives that are less susceptible to the effects of, for example, cosmetics and toiletries, have a good feeling of use, exhibit excellent viscosity and emulsion stability, a method for producing the same, and a cosmetic containing the same. The purpose is to provide fees.

[0007]

Under such circumstances, the present inventors have conducted intensive studies, and as a result, the hydrogen atom of the hydroxyl group of the polysaccharide was replaced with a specific hydrophobic substituent and a substituent containing a sulfonic acid group. A novel polysaccharide derivative obtained by substitution,
It is excellent in water solubility, its aqueous solution shows high viscosity at low concentration, and it is hardly affected by inorganic metal salts, organic metal salts, pH, temperature, etc. In addition, they found that when used in cosmetics and toiletry products, they had a good feeling of use, and completed the present invention.

That is, the present invention relates to a polysaccharide or a derivative thereof in which some or all of the hydrogen atoms of the hydroxyl group are
(A) and (B) (A) A linear or branched group having 10 to 40 carbon atoms which may be substituted with a hydroxyl group and may be inserted with an oxycarbonyl group (—COO— or —OCO—). An alkyl group, an alkenyl group or an acyl group (B) having 1 to 5 carbon atoms which may be substituted by the hydroxyl group;
The average degree of substitution per constituent monosaccharide residue by the substituent (A) is 0.001 to 1.0, and the average degree of substitution per constituent monosaccharide residue by the substituent (B) is 0.001 to 1.0. It is intended to provide a novel polysaccharide derivative having a substitution degree of 0.01 to 2.0, a method for producing the same, and a cosmetic containing the same.

The novel polysaccharide derivative of the present invention comprises a polysaccharide or a derivative thereof comprising (a) a linear or branched saturated or unsaturated epoxide, halide, halohydrin, acyl halide having 10 to 40 carbon atoms, and 10 to 40 carbon atoms. A hydrophobizing agent selected from esters having an acyl group of -40 and carboxylic anhydrides, and (b) vinyl sulfonic acid, halo C ₁ -C ₅ alkane sulfonic acid optionally substituted with a hydroxyl group, and salts thereof Can be produced by reacting with a sulfonating agent selected from

[0010]

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

[0011]

Embedded image

Wherein R is the same or different, and (1): a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, etc., (2): a hydrophobic substituent (A), (3) ):
Sulfoalkyl group which may be substituted by a hydroxyl group (B)
Wherein A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, and a, b and c are the same or different and represent a number of 0 to 10. The AO group, R group, a, b and c may be the same or different within the repeating unit or between the repeating units, but the substitution per each of the constituent monosaccharide residues of the substituents (A) and (B) The average is 0.001 for the substituent (A).
To 1.0, the substituent (B) is 0.01 to 2.0, and the remainder is the group (1). ]

In the polysaccharide derivative of the present invention, R in the repeating unit represented by the above general formula contains a hydrophobic substituent (A) and a sulfoalkyl group (B) which may be substituted by a hydroxyl group. . However, (A) and (B) need not necessarily be present in the same repeating unit. It is sufficient that (A) and (B) are introduced as substituents when viewed as a whole molecule. On average, the degree of substitution is 0.001 to 1.0 for (A) and 0.01 to 2.0 for (B) per repeating unit. The remaining R is hydrogen, methyl, ethyl, hydroxyethyl, hydroxypropyl or the like.

As the alkyl group and alkenyl group having 10 to 40 carbon atoms in the hydrophobic substituent (A), straight-chain alkyl groups such as decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl Group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henycosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, nonacosyl group, triacontyl group, hentriacontyl group, dotriacontyl Group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group, nonatriacontyl group and a tetracontyl group,
As branched alkyl groups, methylundecyl group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group, 2-octyldodecyl, 2-heptylundecyl group, 2-
Decyltetradecyl group, 2-dodecylhexadecyl group, 2-
Tetradecyl octadecyl group, 2-tetradecyl behenyl group, etc., as alkenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group Henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacosenyl group, hexacosenyl group, heptacosenyl group, octacosenyl group, nonacosenyl group, triacontenyl group, oleyl group, linoleyl group, linolenyl group and the like. Among them, straight-chain or branched 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 straight-chain alkyl groups, are preferred. Examples of the hydrophobic substituent (A) include, in addition to these alkyl groups and alkenyl groups, 2-hydroxyalkyl groups, 1-hydroxymethylalkyl groups, 2-hydroxyalkenyl groups, and 1-hydroxymethylalkenyl groups in which a hydroxyl group has been substituted. A 1-oxoalkyl group substituted with an oxo group at the 1-position,
Examples thereof include a 1-oxoalkenyl group (that is, an acyl group) and a group in which an oxycarbonyl group is inserted, and an alkyl group, an alkenyl group, and an acyl group which may be substituted with a hydroxyl group are preferable. From the viewpoint of stability and production, a 2-hydroxyalkyl group is preferred.

These hydrophobic substituents (A) include not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule,
It may be substituted with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to the polysaccharide molecule. The degree of substitution by these hydrophobic substituents (A) can be appropriately adjusted within the range of 0.001 to 1.0 per constituent monosaccharide residue,
It is preferably in the range of 0.003 to 0.5, particularly 0.004 to 0.1 per constituent monosaccharide residue.

Examples of the sulfoalkyl group (B) which may be substituted by a hydroxyl group include 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group and 2-sulfo-1- (hydroxymethyl ) Ethyl group and the like, and 3-sulfo-2-hydroxypropyl group is preferable from the viewpoint of stability and production. All or some of these substituents (B) may be N
It may be a salt with an alkali metal such as a or K, an alkaline earth metal such as Ca or Mg, an organic cation group such as an amine, or an ammonium ion. These substituents (B) also
Not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule but also the hydrogen atom of the hydroxyl group of the hydroxyethyl group or hydroxypropyl group bonded to the polysaccharide molecule may be substituted. The degree of substitution by these substituents (B) is
Within the range of 0.01 to 2.0 per constituent monosaccharide residue, it can be appropriately adjusted depending on the amount of the hydrophobic substituent (A) to be introduced, but is preferably 0.02 to 1.5, more preferably 0.1 to 0.7, particularly 0.2 to 0.5 per constituent monosaccharide residue.
Is preferable.

The novel polysaccharide derivative of the present invention is obtained by partially hydrophobizing (introducing a hydrophobic substituent (A)) or sulfonating (substituent having a sulfonic acid group) the hydrogen atom of the hydroxyl group of the polysaccharide or its derivative. (Introduction of (B)), it is obtained by sulfonating or hydrophobizing all or some of the hydrogens of the remaining hydroxyl groups, or by simultaneously performing hydrophobization and sulfonation.

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, Examples thereof include hydroxypropylmethyl guar gum and hydroxypropylmethyl starch, and among them, cellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, hydroxypropylcellulose, and especially hydroxyethylcellulose are preferable. Further, the substituents such as methyl group, ethyl group, hydroxyethyl group and hydroxypropyl group of these polysaccharides may be substituted with a single substituent or may be substituted with a plurality of substituents. The degree of substitution per constituent monosaccharide residue is preferably from 0.1 to 10, particularly preferably from 0.5 to 5. The weight average molecular weight of these polysaccharides or derivatives thereof is 10,000 to 1000
It is preferably in the range of 100,000 to 100,000 to 5,000,000, especially 500 to 2,000,000.

Hereinafter, the hydrophobization reaction and the sulfonation reaction will be described separately. As described above, either of the hydrophobizing reaction and the sulfonating reaction may be performed first, or may be performed simultaneously. However, it is more preferable that the hydrophobizing is performed and then the sulfonating is performed.

<Hydrophobic Reaction> The hydrophobizing reaction of the polysaccharide or the sulfonated polysaccharide is performed by dissolving or dispersing the polysaccharide or the sulfonated polysaccharide derivative in a suitable solvent, and
0 linear or branched saturated or unsaturated epoxides, halides, halohydrins, acyl halides and 10 carbon atoms
The reaction is performed by reacting with a hydrophobizing agent selected from an ester having an acyl group of 40 and a carboxylic anhydride.

Among the above hydrophobizing agents, epoxides, halides and acyl halides are particularly preferable, and these hydrophobizing agents can be used alone or in combination of two or more. The amount of the hydrophobizing agent can be appropriately adjusted depending on the desired amount of the hydrophobic substituent to be introduced into the polysaccharide or the derivative thereof. Preferred is a range of 10 equivalents, especially 0.003 to 1 equivalent.

The hydrophobizing reaction is preferably carried out in the presence of an alkali, if necessary. Such an alkali is not particularly limited, but may be an alkali metal or alkaline earth metal hydroxide, carbonate, bicarbonate or the like. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of alkali used is
0.01 to 10 times the molar amount of the hydrophobizing agent used, especially 0.1 to 1
A molar amount of 0 gives good results and is preferred.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of swelling the polysaccharide or the sulfonated polysaccharide and increasing 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 the lower alcohol is used. May be used to carry out the reaction.

The reaction temperature is preferably in the range of 0 to 200 ° C, particularly preferably 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, sulfuric acid, hydrochloric acid, inorganic acids such as phosphoric acid,
Organic acids such as acetic acid can be used. Further, the following reaction may be performed without neutralization in the middle.

When the hydrophobized polysaccharide thus obtained is subsequently used for a sulfonation reaction, it can be used as it is without neutralization, and if necessary, it can be separated by filtration, etc. It can be used after washing with aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted hydrophobizing agent or salts produced as a result of neutralization or the like. If the sulfonation reaction has already been performed before the hydrophobization reaction, after separation by filtration or the like, washing and neutralization are performed as necessary, and then drying is performed to obtain the novel polysaccharide derivative of the present invention. be able to.

<Sulfonation Reaction> The sulfonation reaction of the polysaccharide or the hydrophobized polysaccharide is carried out by dissolving or dispersing the polysaccharide or the hydrophobized polysaccharide in an appropriate solvent and reacting with a sulfonating agent.

Among the sulfonating agents, the substituted halogen atom in the halo C ₁ -C ₅ alkanesulfonic acid which may be substituted by a hydroxyl group is a fluorine atom, a chlorine atom,
And a bromine atom. As the sulfonating agent, vinylsulfonic acid, 3-halo-2-hydroxypropanesulfonic acid, and 3-halopropanesulfonic acid are preferable, and these sulfonating agents can be used alone or in combination of two or more. The amount of the sulfonating agent used can be appropriately adjusted depending on the desired amount of a sulfonic acid group to be introduced into the polysaccharide or a derivative thereof, and is usually 0.1 to 10 equivalents per constituent monosaccharide residue of the polysaccharide or the hydrophobized polysaccharide. And particularly preferably in the range of 0.2 to 5 equivalents.

The sulfonation reaction is preferably carried out in the presence of an alkali, if necessary. Such alkali is not particularly limited, and hydroxides, carbonates, bicarbonates and the like of alkali metals or alkaline earth metals may be used. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is 1.0 to 3.0 mole times the sulfonating agent used,
In particular, 1.05 to 1.5 times the molar amount gives good results and is preferable.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. Further, for the purpose of increasing the reactivity of the polysaccharide or the hydrophobized polysaccharide and the sulfonating agent, a lower alcohol,
The reaction may be carried out using a mixed solvent containing 0.1 to 100% by weight, more preferably 1 to 50% by weight of water.

[0030] The reaction temperature is preferably in the range of 0 to 150 ° C, particularly 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, sulfuric acid, hydrochloric acid, inorganic acids such as phosphoric acid,
Organic acids such as acetic acid can be used. The following reaction may be performed without neutralization in the middle.

When the sulfonated polysaccharide thus obtained is subsequently used in a hydrophobic reaction, it can be used as it is without neutralization, or it can be separated by filtration or the like, if necessary, It can be used after washing with aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted alkylating agent or salts produced as a result of neutralization or the like. In the case where a hydrophobic reaction has already been performed before the sulfonation reaction, after separation by filtration or the like, washing and neutralization are performed as necessary, and then drying is performed to obtain the novel polysaccharide derivative of the present invention. be able to.

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

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

When the novel polysaccharide derivative of the present invention is used in hair cosmetics, surfactants, other thickeners, oil gelling agents, metal oxides, organic ultraviolet rays generally used as hair cosmetic ingredients are used. Absorbents, inorganic metal salts, organic metal salts,
It can be blended with a pearlizing agent, an antioxidant, a preservative, a medicinal ingredient, a pigment, a fragrance, and other components in any combination. In 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 use, an emulsion, a suspension, a gel, a transparent solution,
Hair cosmetics in various dosage forms such as aerosols, such as preshampoos, shampoos, hair rinses, hair treatments, hair conditioners, conditioning blowing agents and the like can be used.

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

Examples of the metal oxide include titanium oxide, zinc oxide, iron oxide, zirconium oxide and cerium oxide. Silica treatment, alumina treatment, silica / alumina treatment, metal soap treatment, fatty acid treatment, amino acid treatment, silicone It may have been subjected to a treatment, an alkyl phosphoric acid treatment, a fluorine treatment or the like. Further, two or more of these, or a composite of these with another organic or inorganic powder may be used. The 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 5
0% by weight, especially 0.005 to 30% by weight, is preferred.

Among the organic ultraviolet absorbers, oil-soluble ultraviolet absorbers include benzoic acid-based ones such as paraaminobenzoic acid (hereinafter abbreviated as “PABA”), glyceryl PABA, ethyldihydroxypropyl PABA, and N-ethoxylate. PABA
Ethyl ester, N-dimethyl PABA ethyl ester, N-dimethyl PABA butyl ester, N-dimethyl PABA amyl ester, octyl dimethyl PABA and the like; and anthranilic acid-based ones such as homomenthyl-N-acetylanthranilate; As a salicylic acid type, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate,
Benzyl salicylate, p-isopropanol phenyl salicylate and the like; cinnamic acid-based 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; benzophenone-based 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;
Others include 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-norbonylidene) -3-pentane-2
-On, benzene bis-1,3 described in JP-A-2-212579
-Diketone derivatives, benzoylpinacone derivatives described in JP-A-3-220153, and the like.

Examples of the water-soluble UV absorber include diethanolamine p-methoxycinnamate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate, tetrahydroxybenzophenone, methylherperidine,
Sodium hydroxy-4-methoxycinnamate, sodium ferulate, urocanic acid and the like, and extracts of animals and plants such as yarrow, aloe, below mallow, burdock, salvia and the like, which have an ultraviolet absorbing effect, may be mentioned.

These organic ultraviolet absorbents can be used alone or in combination of two or more, and the amount of the organic ultraviolet absorber 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 preferably 0.001 to 30% by weight, particularly preferably 0.005 to 20% by weight.

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

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

[0043]

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

In the following examples, the degree of substitution of the hydrophobic substituent of the novel polysaccharide derivative of the present invention was measured using NMR (solvent: deuterated DMSO). The substitution degree of the sulfone group was determined by a colloid titration method. That is, a thickener solution of known concentration is prepared, and under stirring, a known weight of N / 20 is prepared.
0 Methyl glycol chitosan solution (Wako Pure Chemicals, for colloid titration) was added, and a few drops of toluidine blue indicator solution (Wako Pure Chemicals, for colloid titration) were added. This was back titrated with an N / 400 polyvinyl potassium sulfate solution (Wako Pure Chemical, colloid titration), and the degree of substitution was calculated from the titer. In the following examples, “degree of substitution” indicates the average number of substituents per constituent monosaccharide residue.

Example 1 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 2.2 g of 1,2-epoxyoctadecane was added thereto and reacted at 80 ° C. for 8 hours to effect hydrophobicity. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of 80% acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours to obtain 49.4 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
A slurry liquid was prepared by charging 10.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 80.0 g of isopropyl alcohol and 0.33 g of a 48% aqueous sodium hydroxide solution in a 00 ml glass separable reaction vessel, and stirring at room temperature under a nitrogen stream. For 30 minutes. A mixture of 12.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 5.4 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water was added to the reaction solution, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day, and dried with 2-hydroxyoctadecyl and 3-sulfo-2-hydroxypropyl groups. Then, 7.2 g of the hydroxyethyl cellulose derivative (Compound 1 of the present invention) substituted with was obtained.

The degree of substitution of the 2-hydroxyoctadecyl group in the obtained hydroxyethyl cellulose derivative was 0.015, 3-
The degree of substitution of the sulfo-2-hydroxypropyl group was 0.30.

Example 2 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Example 1 (1), 160 g of isopropyl alcohol and 25% vinyl were placed in a 500 ml glass separable reaction vessel equipped with a stirrer, thermometer and cooling tube. Aqueous sodium sulfonate solution 36.
0 g was charged to prepare a slurry liquid. This was stirred at room temperature for 30 minutes under a nitrogen stream, and then 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and further stirred at room temperature for 60 minutes under a nitrogen stream. The temperature of the slurry was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. 80% product
3 times with 500 g of acetone (20% water), then 500 g of acetone
And dried at 70 ° C. for one day and night under reduced pressure to obtain a hydroxyethylcellulose derivative (compound 2 of the present invention) substituted with a 2-hydroxyoctadecyl group and a 2-sulfoethyl group.
g was obtained.

The substitution degree of the 2-hydroxyoctadecyl group in the obtained hydroxyethyl cellulose derivative was 0.015,
The degree of substitution of the sulfoethyl group was 0.32.

Example 3 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 1 (1), 160 g of 90% isopropyl alcohol and 48 g A slurry was prepared by adding 13.1 g of a 10% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. After further cooling the reaction solution to 10 ° C or less under ice cooling,
30.0 g of sodium 3-bromopropanesulfonate was charged and stirred at 10 ° C. or lower for 60 minutes. Further, the reaction solution was heated to 80 ° C., and stirred at 80 ° C. for 2 hours to perform sulfonation. After completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product was washed three times with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and then reduced under reduced pressure to 70 ° C.
For one day to obtain 8.9 g of a hydroxyethyl cellulose derivative (Compound 3 of the present invention) substituted with a 2-hydroxyoctadecyl group and a 3-sulfopropyl group.

The degree of substitution of the 2-hydroxy-n-octadecyl group of the obtained hydroxyethyl cellulose derivative was 0.015,
The degree of substitution of the sulfopropyl group was 0.20.

Example 4 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with a weight average molecular weight of about 1.5 million,
Hydroxyethyl cellulose (HEC-QP100M, manufactured by Union Carbide) with a degree of substitution of hydroxyethyl groups of 1.8 50
g, 400 g of 88% isopropyl alcohol and 4.7 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 4.8 g of 1-chlorooctadecane was added, and the mixture was reacted at 80 ° C. for 8 hours to hydrophobize. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. Reaction product 80% acetone
It was washed twice with 500 g and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours to obtain 48.7 g of a hydrophobized hydroxyethylcellulose derivative.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
In a 00 ml glass separable reaction vessel, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in (1), 80 g of isopropyl alcohol, and 0.33 g of a 48% aqueous sodium hydroxide solution
Was prepared to prepare a slurry liquid, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. A mixture of 12.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 5.4 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water was added to the reaction solution, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. 80% acetone (water
20%) After washing three times with 500 g and then twice with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day and night, and a hydroxyethyl cellulose derivative substituted with an octadecyl group and a 3-sulfo-2-hydroxypropyl group (the compound of the present invention) 4) 8.2 g was obtained.

The degree of substitution of the octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.010, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.31.

Example 5 (1) A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP100M) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8. , Union Carbide) 50g,
A slurry liquid was prepared by charging 800 g of isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes at room temperature under a nitrogen stream. 3-chloro-2 in the reaction solution
-Sodium hydroxypropanesulfonate 32.8g, 48
A mixed solution consisting of 17.3 g of a 1% aqueous sodium hydroxide solution and 200 g of water was added, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product was washed twice with 500 g of 80% acetone (20% water) and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for 24 hours.
Sulfonated hydroxyethyl cellulose derivative 52
g was obtained.

(2) 1 equipped with a stirrer, thermometer and cooling pipe
In a 000 ml glass separable reaction vessel, 10.0 g of the sulfonated hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by adding 80.0 g of 88% isopropyl alcohol and 0.73 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 0.44 g of stearoyl chloride 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 neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product is 80% acetone (water 20
%) After washing twice with 100 g and then twice with 100 g of acetone,
After drying at 70 ° C under reduced pressure for one day, the stearoyl group and 3-sulfo
8.5 g of a hydroxyethyl cellulose derivative (Compound 5 of the present invention) substituted with a 2-hydroxypropyl group was obtained.

The degree of substitution of the stearoyl group in the obtained hydroxyethylcellulose derivative was 0.014, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.20.

Example 6 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP4400, HEC-QP4400, having a weight average molecular weight of about 800,000 and a substitution degree of hydroxyethyl groups of 1.8). Union Carbide) 50g, 88%
400 g of isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution were added to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 0.9 g of 1,2-epoxy-n-octadecane was added thereto, and the mixture was reacted at 80 ° C. for 8 hours to perform hydrophobic treatment. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product is washed with 500 g of 80% acetone 2
Twice, then with acetone (500 g) twice.
It was dried day and night to obtain 48.4 g of a hydrophobized hydroxyethyl cellulose derivative.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
A 100 ml glass separable reaction vessel was charged with 10.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 80.0 g of isopropyl alcohol, and 0.33 g of a 48% aqueous sodium hydroxide solution to prepare a slurry liquid, and cooled to room temperature under a nitrogen stream. For 30 minutes. To the reaction mixture was added a mixture of 12.8 g of sodium 3-chloro-2-hydroxypropanesulfonate, 5.4 g of a 48% aqueous sodium hydroxide solution and 20.0 g of water, and sulfonation was performed at 50 ° C. for 9 hours. After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration. The product is washed three times with 500 g of 80% acetone (20% water) and then with 500 g of acetone.
After washing twice, it was dried under reduced pressure at 70 ° C for one day and night.
6.9 g of a hydroxyethylcellulose derivative (product 6 of the present invention) substituted with -octadecyl group and sulfo-2-hydroxypropyl group was obtained.

The substitution degree of the 2-hydroxy-n-octadecyl group of the obtained hydroxyethyl cellulose derivative was 0.004,
The degree of substitution of the sulfo-2-hydroxypropyl group was 0.30.

Example 7 (1) 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Example 6 (1), 160 g of isopropyl alcohol, and 500 g of a separable glass reaction vessel equipped with a stirrer, a thermometer, and a cooling tube were added. A slurry liquid was prepared by charging 36.0 g of a 25% aqueous solution of sodium vinyl sulfonate. This was stirred at room temperature under a nitrogen stream for 30 minutes, and then 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and further stirred at room temperature under a nitrogen stream for 60 minutes. The temperature of the slurry was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After the reaction is completed, the reaction solution is
The solution was cooled to neutralization with acetic acid and the product was filtered off. 80 products
3 times with 500 g of 20% acetone (water 20%), then 500 g of acetone
After drying twice at 70 ° C. under reduced pressure, 8.5 g of a hydroxyethylcellulose derivative (Product 7 of the present invention) substituted with a 2-hydroxy-n-octadecyl group and a sulfoethyl group was obtained.

The degree of substitution of the 2-hydroxy-n-octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.004,
The degree of substitution of the sulfoethyl group was 0.31.

Example 8 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Example 6 (1), 160 g of 90% isopropyl alcohol, and 48 g of the hydrophobized hydroxyethyl cellulose obtained in Example 6 (1) were placed in a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. A slurry was prepared by adding 13.1 g of a 10% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. After further cooling the reaction solution to 10 ° C or less under ice cooling,
30.0 g of sodium 3-bromopropanesulfonate was charged and stirred at 10 ° C. or lower for 60 minutes. Further, the temperature of the reaction solution was raised to 80 ° C., and the mixture was stirred at 80 ° C. for 2 hours to perform sulfonation. After completion of the reaction, the reaction solution was cooled to 60 ° C., neutralized with acetic acid, and the product was separated by filtration. The product is mixed with 500 g of 80% acetone (20% water)
And then twice with 500 g of acetone, and then 1
After drying day and night, 8.8 g of a hydroxyethylcellulose derivative (Product 8 of the present invention) substituted with a 2-hydroxy-n-octadecyl group and a sulfopropyl group was obtained.

The degree of substitution of the 2-hydroxy-n-octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.004,
The degree of substitution of the sulfopropyl group was 0.20.

Comparative Example 1 The same hydroxyethylcellulose (HEC-QP100M, manufactured by Union Carbide) as used in Examples 1 to 5 was used as it was to make Comparative Compound 1.

Comparative Example 2 Carboxymethylcellulose (CMC2280, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight: about 1,000,000, degree of carboxymethylation
0.78) was used as it was as Comparative Compound 2.

Comparative Example 3 Comparative compound 3 was prepared using sodium polyacrylate (Carbopol 941, manufactured by Goodrich) as it was.

Test Example 1 Viscosity Test 1.0 g of each of the compound of the present invention and the comparative compound was stirred and dissolved in 200 ml of ion-exchanged water, left at room temperature for 24 hours, and the viscosity of each aqueous solution was measured. Further, 1.0 g of each of the compound of the present invention and the comparative compound was dissolved in 200 ml of a 1.0% by weight aqueous solution of calcium chloride with stirring, left at room temperature for 24 hours, and the viscosity of each aqueous solution was measured. The viscosity was measured using a Brookfield viscometer (12
rpm, 25 ° C.). Table 1 shows the results.

[0069]

[Table 1]

The novel polysaccharide derivative of the present invention not only gives an aqueous solution having high transparency, but also exhibits an excellent viscosity increase as shown in Table 1, and also has an excellent salt resistance.

Test Example 2 Emulsion Stability Test An emulsion having the following composition was prepared, and the emulsion stability immediately after emulsification and when stored at 50 ° C. for 1 week or 2 weeks was visually evaluated. In addition, when the emulsion is uniformly emulsified,
The case where they were separated was designated as x. Table 2 shows the results.

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

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

Test Example 3 Foam Stability Test A foam stability test solution having the following composition was prepared, and the foam stability of the novel polysaccharide derivative of the present invention was examined. The foaming amount was measured at 40 ° C by the Ross Miles method, and 10 seconds after foaming and
The foaming amount for 120 seconds was measured. Table 2 shows the results.

<Foam stability test solution> Sodium lauryl ether sulfate 1.0% by weight Lanolin 0.5% by weight Compound of the present invention or comparative compound 0.1% by weight Water (4 ° DH) Balance

[0076]

[Table 2]

As is clear from Table 2, the novel polysaccharide derivative of the present invention has excellent foam stability and foam increasing properties.

Example 6 Emulsion Emulsion 1 of the present invention and Comparative Emulsion 1 having the following compositions were prepared, and their viscosities, emulsion stability, and usability were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 3 shows the results.

<Emulsion 1 of the Present Invention (Comparative Emulsion 1)> Compound 1 of the Present Invention (or Comparative Compound 2) 0.5% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 15.0% by weight Methylpolysiloxane 1.0% by weight Glycerin 3.0% by weight Water balance

[0080]

[Table 3]

Example 7 Emulsion Emulsion 2 of the present invention and Comparative Emulsion 2 having the following composition were prepared, and their viscosities, emulsion stability, and usability were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 4 shows the results.

<Emulsion 2 of the Present Invention (Comparative Emulsion 2)> Compound 2 of the Present Invention (or Comparative Compound 3) 0.6% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 12.0% by weight Methylpolysiloxane 1.0% by weight 2-Ethylhexyl paramethoxycinnamate 5.0% by weight Silicone coated zinc oxide 3.0% by weight Glycerin 2.0% by weight Water balance

[0083]

[Table 4]

Example 8 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 Compound of the present invention 1 0.2% by weight Water balance

Example 9 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 Compound of the present invention 1 0.5% by weight Butyl paraben 0.1% by weight Methyl paraben 0.1% by weight Ethanol 5.0 Glycerin 3.0% by weight Fragrance 0.05% by weight Water balance

Example 10 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 Glycerin 3.0% by weight Polyethylene glycol 1500 4.0% by weight Polyoxyethylene oleyl ether (20EO) 0.3% by weight Polyoxyethylene hydrogenated castor oil (30EO) 0.2% by weight Compound of the present invention 1 0.15% by weight zinc p-phenolsulfonate 0.2% by weight water balance

Example 11 Sun care cream A sun care cream was prepared according to the following formulation. This sun care cream was stable at 50 ° C. for one month or more, and had a good feeling upon use. Dimethylsiloxane / methyl (polyoxyethylene) siloxane polymer 2.0% by weight Polyoxyethylene (20EO) sorbitan monooleate 0.5% by weight Methylpolysiloxane (5cs) 7.0% by weight Methylphenylpolysiloxane 2.0% by weight Jojoba oil 2.0% by weight Palmitin Acid dextrin 0.5% by weight Octyl dimethyl PABA 4.0% by weight Silicone coated fine particles 5.0% by weight Acidic heteropolysaccharide 0.03% by weight Magnesium sulfate 0.5% by weight Glycerin 5.0% by weight Dibutylhydroxytoluene 0.05% by weight Compound 3 of the present invention 0.5% by weight Water balance

Example 12 Foundation A foundation was prepared according to the following formulation. This foundation was stable at 50 ° C. for one month or more, and had a good usability. Compound of the present invention 1 0.2% by weight α-monoisostearyl glyceryl ether 2.0% by weight Aluminum diisostearate 0.2% by weight Liquid paraffin 10.0% by weight Neopentyl glycol dioctanoate 5.0% by weight Methylphenyl polysiloxane (14cs) 5.0% by weight p- 2-ethylhexyl methoxycinnamate 3.0% by weight 2-hydroxy-4-methoxybenzophenone 1.0% by weight Silicone-coated fine particles of titanium oxide 5.0% by weight Silicone-coated fine particles of zinc oxide 1.0% by weight Sericite 2.0% by weight Talc 2.0% by weight Bengala 0.4% by weight % Iron yellow oxide 0.7% by weight Black iron oxide 0.1% by weight Magnesium sulfate 1.0% by weight Methyl paraben 0.2% by weight Fragrance Trace water Balance

Example 13 Lipstick A lipstick was prepared according to the following formulation. This lipstick was stable at 50 ° C. for one month or more and had a good feeling upon use. Castor oil 52.0% by weight Lanolin 5.0% by weight Liquid lanolin 5.0% by weight Beeswax 4.0% by weight Ozokerite 7.0% by weight Candelilla wax 2.0% by weight Carnauba wax 1.0% by weight Dodecyl-modified silicone 10.0% by weight Compound of the present invention 4 0.2% by weight homomenthyl salicylate 7.8% by weight Titanium oxide 1.0% by weight Red No. 201 1.0% by weight Red No. 202 2.0% by weight Yellow 4 aluminum lake 1.0% by weight Red No. 223 0.1% by weight Fragrance trace amount Butylated hydroxytoluene 0.1% by weight Propyl paraben 0.3% by weight

[0090]

Industrial Applicability The novel polysaccharide derivative of the present invention gives a highly transparent aqueous solution and shows an excellent thickening effect with a small amount of addition.
Emulsions that exhibit little change in viscosity due to coexistence of salts and temperature and have extremely excellent stability. Therefore, the novel polysaccharide derivatives of the present invention can be widely used as thickeners, gelling agents, excipients, emulsion stabilizers, flocculants and the like for cosmetics and toiletry products.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A61K 7/02 A61K 7/02 Z 7/027 7/027 7/42 7/42 C08B 3/00 C08B 3/00 11/02 11/02 11/04 11/04 11/08 11/08 31/04 31/04 31/10 31/10 31/12 31/12 37/00 37/00 Z (58) Fields studied (Int.Cl . ^7, DB name) C08B 11/12 A61K 7/00 A61K 7/02 A61K 7/027 A61K 7/42 C08B 3/00 C08B 11/02 C08B 11/04 C08B 11/08 C08B 31/04 C08B 31/10 C08B 31/12 C08B 37/00 CA (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof may be substituted with the following groups (A) and (B) (A): (—COO— or —OCO—) a linear or branched alkyl group, alkenyl group or acyl group having 10 to 40 carbon atoms which may be inserted; (B) 1 carbon atom which may be substituted by a hydroxyl group; ~ 5
The average degree of substitution per constituent monosaccharide residue by the substituent (A) is 0.001 to 1.0, and the average degree of substitution per constituent monosaccharide residue by the substituent (B) is 0.001 to 1.0. A novel polysaccharide derivative having a substitution degree of 0.01 to 2.0. 2. The substituent (A) is one or two selected from a linear or branched alkyl group, alkenyl group or acyl group having 12 to 36 carbon atoms which may be substituted by a hydroxyl group.
Or more, and the substituent (B) is a 2-sulfoethyl group, 3
The novel polysaccharide derivative according to claim 1, which is one or more selected from -sulfopropyl group, 3-sulfo-2-hydroxypropyl group and 2-sulfo-1- (hydroxymethyl) ethyl group. 3. The polysaccharide or a derivative thereof is cellulose,
Guar gum, starch, hydroxyethyl cellulose,
Hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, 3. The novel polysaccharide derivative according to claim 1, which is selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylmethylguar gum and hydroxypropylmethylstarch. 4. A polysaccharide or a derivative thereof is produced by:
-40 linear or branched saturated or unsaturated epoxides, halides, halohydrins, acyl halides, and carbon numbers
A hydrophobizing agent selected from esters and carboxylic anhydrides having 10 to 40 acyl groups, and (b) vinyl sulfonic acid, halo C _{1 to} C _{5 which} may be substituted with a hydroxyl group.
The method for producing a novel polysaccharide derivative according to any one of claims 1 to 3, wherein the reaction is carried out with a sulfonating agent selected from alkanesulfonic acids and salts thereof. 5. A cosmetic comprising the novel polysaccharide derivative according to claim 1. 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.