JPH1112303A - Novel polysaccharide derivative and cosmetic containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polysaccharide derivative that forms an aqueous solution of high transparency, manifests excellent thickening effect with a reduced amount of addition, gives extremely stable emulsion with reduced viscosity change due to the presence of salts and to temperature and can be widely used as thickener, gelling agent, excipient, emulsion stabilizer, coagulation agent, dispersing agent and the like. SOLUTION: This polysaccharide derivative is prepared by reaction of a polysaccharide or its derivative with (a) an agent to increase the hydrophobicity of the product selected from a 10-40C alkyl or alkenyl group-bearing glycidyl ethers, epoxides, halides and halohydrin and a 10-40C acyl group-having esters, acid halides, or carboxylic anhydrides and (B) a sulfonating agent selected from vinyl sulfonic acids, halo-1-5C alkane sulfonic acids which may be substituted with hydroxyl group(s) and their salts.

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 and good fluidity, and a cosmetic containing the same.

[0002]

2. Description of the Related Art As one of important constituents of cosmetics, toiletry products, external medicines, water-soluble paints, building materials, etc., various cellulose ethers are used as thickeners, gelling agents, excipients, emulsions. Widely used as stabilizers and flocculants. 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, The viscosity was low at the same aqueous solution concentration, and when it was incorporated into a product as a thickener or dispersion stabilizer, there was a drawback that the viscosity change accompanying the temperature change was large.

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 non-ionic cellulose derivative into which is introduced a relatively high viscosity with a small mixing amount. In addition, JP-A-3-24001, JP-A-3-41210, JP-A-3-41214, JP-A-3-218316, as seen in JP-A-3-218316, topical pharmaceuticals for these alkyl-substituted cellulose derivatives, cosmetics Attempts have been made to apply it to such applications. 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 properties required for the thickener used in the above-mentioned fields include easy dissolution and excellent thickening effect, coexisting metal salts, surfactants and oils. Other additives, temperature, and the effect on viscosity due to changes in pH are small, and there is little change in viscosity over time.Excellent microbial resistance. Building materials have a high dispersion stabilizing ability and do not impair the fluidity of the building materials. However, the above-mentioned cellulose ethers and alkyl-substituted cellulose derivatives have not sufficiently satisfied all of these required properties.

Accordingly, an object of the present invention is to provide a novel polysaccharide derivative which sufficiently satisfies the above-mentioned properties and can be a thickener which can be suitably used for cosmetics, toiletry products, building materials and the like.

[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,
Excellent water solubility, its aqueous solution shows high viscosity at low concentration, and has little effect on viscosity such as inorganic metal salt, organic metal salt, pH, temperature, etc.
Furthermore, they have found that they have a good usability when used in cosmetics and toiletry products, and that they show good fluidity when used in building materials, and have completed the present invention.

That is, the present invention relates to a method for preparing a polysaccharide or a derivative thereof comprising (a) a glycidyl ether having 10 to 40 carbon atoms having a linear or branched alkyl group or alkenyl group, an epoxide, a halide and a halohydrin; 40 straight-chain or branched esters having a saturated or unsaturated acyl group, a hydrophobizing agent selected from acid halides and carboxylic anhydrides, and (b) vinyl sulfonic acid, a halo optionally substituted by a hydroxyl group there is provided a C ₁ -C ₅ new polysaccharide derivatives obtained by reacting an alkane sulfonic acid and a sulfonating agent selected from salts thereof and cosmetics containing the same.

[0009]

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.

[0010]

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 substituent (A) And an oxycarbonyl group (-
(COO- or -OCO-) or a linear or branched alkyl group, alkenyl group or acyl group having 10 to 43 carbon atoms into which an ether bond may be inserted], (3): substituent (B) [hydroxyl group Represents an optionally substituted sulfoalkyl group having 1 to 5 carbon atoms or a salt thereof], A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, a, b and c Represents the same or different numbers from 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, and the hydroxyl group of the above-mentioned substituents (A) and (B) may be further substituted with another substituent.
(A) or (B) may be substituted. ]

As the alkyl group and alkenyl group having 10 to 43 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, tetracontyl group, etc.
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. 2-hydroxy-3-alkoxypropyl group, 2-alkoxy-3-hydroxypropyl group, 2-hydroxy-3-alkenyloxypropyl group, 2-alkenyloxy-3-hydroxypropyl group into which an ether bond is inserted Groups,
Examples thereof include a 1-oxoalkyl group and a 1-oxoalkenyl group substituted with an oxo group at the 1-position (that is, an acyl group), and a group having an oxycarbonyl group inserted therein. Good alkyl group,
An alkenyl group, an alkoxypropyl group, an alkenyloxypropyl group, and an acyl group are preferable, and a 2-hydroxyalkyl group and an alkoxyhydroxypropyl group are particularly preferable in terms of stability and production.

These hydrophobic substituents (A) include not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule,
It may be replaced with a hydrogen atom of a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group bonded to the polysaccharide molecule, or a hydroxyl group of another substituent (A) or (B). The degree of substitution by these hydrophobic substituents (A) varies depending on the application, but the degree of substitution per constituent monosaccharide residue
It is preferably in the range of 0.0001 to 1.0, especially when used for cosmetics and toiletry products, 0.00 0.00 per component monosaccharide residue.
The range is preferably from 1 to 1.0, more preferably from 0.003 to 0.5, particularly preferably from 0.004 to 0.1.
The range of 0001 to 0.001 is preferred.

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, or another substituent (A) or (B) May be substituted with the hydrogen atom of the hydroxyl group of The degree of substitution by these substituents (B) varies depending on the intended use, but is preferably in the range of 0.01 to 2.0 per constituent monosaccharide residue, especially when used in cosmetics and toiletry products.
The range is preferably from 0.02 to 1.5, more preferably from 0.1 to 0.7, and particularly preferably from 0.2 to 0.5.
The range of 01 to 1.0, particularly 0.02 to 0.5 is preferred.

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) a hydrogen atom of a hydroxyl group of a polysaccharide or a derivative thereof. (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 raw material polysaccharides or derivatives thereof used in the present invention include polysaccharides such as cellulose, guar gum and starch; and derivatives obtained by substituting these with methyl, ethyl, hydroxyethyl, hydroxypropyl and the like. Can be These substituents can be substituted in the constituent monosaccharide residue singly or in a combination of a plurality. Examples of polysaccharide derivatives include 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, etc. Is mentioned. Among these polysaccharides or derivatives thereof, cellulose, hydroxyethyl cellulose, methyl cellulose,
Ethyl cellulose and hydroxypropyl cellulose are preferred, and hydroxyethyl cellulose is particularly preferred.
Further, the substituent of the polysaccharide derivative is further substituted with a hydroxyl group of a hydroxyethyl group or a hydroxypropyl group, for example, by forming a polyoxyethylene chain or the like,
A degree of substitution of more than 3.0 per constituent monosaccharide residue is also possible,
The degree of substitution per constituent monosaccharide residue is 0.1 to 10.0, especially 0.5
~ 5.0 is preferred. The weight average molecular weight of these polysaccharides or derivatives thereof is preferably in the range of 10,000 to 10,000,000, 100,000 to 5,000,000, and particularly preferably in the range of 500,000 to 2,000,000.

Hereinafter, the hydrophobization reaction and the sulfonation reaction will be described separately. As described above, any of the hydrophobization reaction and the sulfonation reaction may be performed first, or may be performed simultaneously.

<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 an appropriate solvent, and (a) dissolving the polysaccharide or the sulfonated polysaccharide in an appropriate solvent.
Glycidyl ethers, epoxides, halides and halohydrins having 0 linear or branched alkyl or alkenyl groups, and esters, acid halides and carboxylic acids having 10 to 40 carbon atoms having a linear or branched saturated or unsaturated acyl group It is carried out by reacting with a hydrophobizing agent selected from acid anhydrides.

Among the above hydrophobizing agents, glycidyl ether, epoxide, halide and acid halide 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, and is usually 0.0001 to 0.0001 to the constituent monosaccharide residue of the polysaccharide or the derivative thereof. 10.0 equivalents,
Particularly, a range of 0.0005 to 1.0 equivalent is preferable.

The hydrophobization 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 alkali used is
The amount is preferably 0.01 to 1000 times the molar amount of the hydrophobizing agent used.

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 can be neutralized with an acid, if necessary. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and 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. 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. In the case where the sulfonation reaction has already been performed before the hydrophobization reaction, neutralization, separation by filtration, etc., washing and the like as necessary, and drying are performed to obtain the novel polysaccharide derivative of the present invention. Obtainable.

<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,
Examples thereof include a bromine atom and the like, and examples of these salts include alkali metal salts such as a sodium salt and a potassium salt, alkaline earth metal salts such as a calcium salt and a magnesium salt, and ammonium salts. 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 can be appropriately adjusted depending on the desired amount of the sulfonic acid group to be introduced into the polysaccharide or a derivative thereof, but is usually 0.01 to 10.0 equivalents per constituent monosaccharide residue of the polysaccharide or the hydrophobized polysaccharide. In particular, a range of 0.03 to 5.0 equivalents is preferable.

The sulfonation 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 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.

[0028] 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 can be neutralized with an acid, if necessary. As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used. The following reaction may be performed without neutralization in the middle.

When the thus obtained sulfonated polysaccharide is subsequently used for 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 sulfonating agent or salts produced as a result of neutralization or the like. If the hydrophobization reaction has already been performed before the sulfonation reaction, neutralization, separation by filtration, etc., washing and the like as necessary, and then drying are performed to obtain the novel polysaccharide derivative of the present invention. Obtainable.

As described above, the substituents (A) and (B) in the polysaccharide derivative of the present invention obtained as described above include not only the hydroxyl group of the polysaccharide or its derivative used as a raw material, but also other hydroxyl groups. The hydroxyl group contained in the substituent (A) or the substituent (B) may be substituted, and such substitution may occur in a superimposed manner. That is, only the hydrogen atom of the hydroxyl group of the polysaccharide or a derivative thereof has the substituents (A) and (B)
In addition to the compound substituted with, when sulfonated after hydrophobization, the substituent (A) is further substituted with the substituent (A) or (B), and the substituent (B) is further substituted with the substituent (B ) May be included, and when hydrophobized after sulfonation, the substituent (A) is further substituted with the substituent (A), and
(B) may further include those substituted with the substituent (B) or (A) .If the hydrophobization and sulfonation are performed simultaneously, the substituent (A) may further include a substituent (A). Or (B) is substituted, the substituent (B) may further include those substituted with the substituent (A) or (B), and further substitution with other substituents occurs in an overlapping manner Things may be included. Therefore, the present invention includes any of such polysaccharide derivatives.

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 commonly used as skin cosmetics components , Any combination with organic ultraviolet absorbers, inorganic metal salts, organic metal salts, alcohols, chelating agents, pH adjusters, preservatives, other thickeners, medicinal ingredients, pigments, fragrances, etc. Thus, various forms, for example, oil / water, water / oil type emulsified cosmetics, creams, emulsions, lotions, oily lotions, lipsticks, foundations, skin cleansers and the like can be obtained.

When the novel polysaccharide derivative of the present invention is used in hair cosmetics, surfactants, other thickeners, oil gelling agents, metal oxides, organic ultraviolet rays generally used as hair cosmetic ingredients. 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 cosmetics of the present invention exhibit 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 para-aminobenzoic 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, benzenebis-1,3- described in JP-A-2-212579
Diketone derivatives and benzoylpinacone derivatives described in JP-A-3-220153 are exemplified.

Examples of the water-soluble ultraviolet 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 absorbers can be used alone or in combination of two or more, and the 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 3 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.

When the novel polysaccharide derivative of the present invention is used for a building material such as mortar, the amount thereof is not particularly limited, but is preferably 0.0001 to 3% by weight, particularly preferably 0.001 to 0.5% by weight.

[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 (A) of the novel polysaccharide derivative of the present invention was determined in Example 1.
-20 are measured using NMR (solvent: deuterated DMSO), and in Examples 21 to 28, the substituent (A) does not have an oxo group at the 1-position (when forming an ether). The Zeisel method (DG Anderson, Anal. Chem., 43, 894)
(1971)), when the substituent (A) has an oxo group at the 1-position (forms an ester), the sample is hydrolyzed with an acid, neutralized, and then esterified with diazomethane. Performed and quantified by gas chromatography.

The substitution degree of the sulfoalkyl group (B) was determined by a colloid titration method. That is, a thickener solution with a known concentration is prepared, and a N / 200 methyl glycol chitosan solution with a known weight is added to the solution under stirring (Wako Pure Chemical Industries, for colloid titration)
And a toluidine blue indicator solution (Wako Pure Chemical,
(For colloid titration) was 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 hydroxyethyl cellulose (HEC-QP4400, HEC-QP4400, having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl group of 1.8) was placed in a 1000 ml glass separable reaction vessel equipped with a stirrer, thermometer and cooling tube. Union Carbide) 50g,
A slurry was prepared by adding 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen atmosphere. To this, 5.4 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was 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. To the reaction mixture was added a mixture of 6.4 g of sodium 3-chloro-2-hydroxypropanesulfonate, 2.7 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 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 a 3-stearyloxy-2-hydroxypropyl group and sulfo-2-one. 7.2 g of a hydroxyethyl cellulose derivative (the present compound 1) substituted with a hydroxypropyl group was obtained.

The substitution degree of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.030, and the substitution degree of the sulfo-2-hydroxypropyl group was 0.15.

Example 2 After hydrophobization was carried out in the same manner as in Example 1 except that the amount of stearyl glycidyl ether was changed to 10.8 g, the amount of sodium 3-chloro-2-hydroxypropanesulfonate was reduced.
9.6 g, 2.7 g of 48% aqueous sodium hydroxide solution 4.0 g
Sulfonation was carried out in the same manner as above to obtain a hydroxyethyl cellulose derivative (Compound 2 of the present invention).

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.058, and the degree of substitution of the sulfo-2-hydroxypropyl group was 0.20.

Example 3 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 1 (1), 160 g of isopropyl alcohol and 25% vinyl sulfone were placed in a 500-ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. Aqueous sodium acid solution 18.
0 g was charged to prepare a slurry liquid. After stirring at room temperature for 30 minutes under a nitrogen stream, 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and the mixture was 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
After drying twice at 70 ° C. under reduced pressure, 8.9 g of a hydroxyethylcellulose derivative (compound 3 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfoethyl group was obtained.

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.030, and the degree of substitution of the sulfoethyl group was 0.18.

Example 4 The hydrophobized hydroxycellulose used in Example 2 was sulfonated in the same manner as in Example 3 except that the amount of a 25% aqueous solution of sodium vinyl sulfonate was 36.0 g, and 3-stearyloxy was added.
A hydroxyethyl cellulose derivative (the present compound 4) substituted with a 2-hydroxypropyl group and a sulfoethyl group was obtained.

The substitution degree of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.058, and the substitution degree of the sulfoethyl group was 0.34.

Example 5 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 1 (1), 160 g of 90% isopropyl alcohol and 48% A slurry solution was prepared by adding 7.2 g of an aqueous sodium hydroxide solution, and 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,
Charge 15.0 g of sodium bromopropanesulfonate
The mixture was 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) 3
After washing twice with 500 g of acetone twice and drying under reduced pressure at 70 ° C. for one day, 8.9 g of a hydroxyethyl cellulose derivative (compound 5 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfopropyl group. I got

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.030, and the degree of substitution of the sulfopropyl group was 0.10.

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,
A slurry was prepared by adding 400 g of 88% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, followed by stirring at room temperature for 30 minutes under a nitrogen atmosphere. 8.5 g of palmityl glycidyl ether was added thereto, and the mixture was reacted at 80 ° C. for 9 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 one day to obtain 50.3 g of a hydrophobized hydroxyethyl cellulose 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), 160 g of isopropyl alcohol and 36.0 g of a 25% sodium vinyl sulfonate aqueous solution were prepared to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream. After stirring for 30 minutes, 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and the mixture was 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. 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 night, and hydroxyethyl cellulose derivatives substituted with palmityl glyceryl ether and sulfoethyl groups. (Compound 6 of the present invention) 8.9
g was obtained.

The degree of substitution of the palmityl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.06.
0, the degree of substitution of the sulfoethyl group was 0.35.

Example 7 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with methylcellulose having a weight average molecular weight of about 400,000 and a methyl group substitution degree of 1.8 (Metroze SM-TM).
800, manufactured by Shin-Etsu Chemical Co., Ltd.), 50 g of isopropyl alcohol, and 4.5 g of a 48% aqueous sodium hydroxide solution.
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 6.0 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. 80% reaction product
The resultant was washed twice with 500 g of acetone and then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 48.5 g of hydrophobized methyl cellulose.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
A slurry solution was prepared by charging 10.0 g of the hydrophobized methylcellulose 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 at room temperature. Stirred for minutes. To the reaction mixture was added a mixture consisting of 7.7 g of sodium 3-chloro-2-hydroxypropanesulfonate, 3.2 g of a 48% aqueous solution of sodium hydroxide, and 20.0 g of water.
Sulfonation was performed at 0 ° C. for 8 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 a 3-stearyloxy-2-hydroxypropyl group and sulfo-2-one. 8.3 g of a methylcellulose derivative (the present compound 7) substituted with a hydroxypropyl group was obtained.

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained methylcellulose derivative was 0.02.
7. The degree of substitution of the sulfo-2-hydroxypropyl group was 0.15.

Example 8 10.0 g of the hydrophobized methylcellulose obtained in Example 7 (1) and 160 g of isopropyl alcohol were placed in a 500-ml separable glass reactor equipped with a stirrer, a thermometer and a cooling tube.
And 21.6 g of a 25% aqueous solution of sodium vinyl sulfonate were charged to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes. Thereafter, 1.5 g of a 48% aqueous sodium hydroxide solution was charged, and further at room temperature under a nitrogen stream for 60 minutes. Stirred. 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% acetone (20% water)
After washing three times with 500 g and then twice with 500 g of acetone, the resultant was dried under reduced pressure at 70 ° C. for one day to obtain 9.6 g of a methylcellulose derivative (compound 8 of the present invention) substituted with a stearyl glyceryl ether group and a sulfoethyl group.

The degree of substitution of the resulting methylcellulose derivative with a 3-stearyloxy-2-hydroxypropyl group was 0.02.
7. The degree of substitution of the sulfoethyl group was 0.17.

Example 9 In a 500-ml separable reaction vessel made of glass equipped with a stirrer, a thermometer and a condenser, 16.2 g of cellulose powder (manufactured by Merck), 250 g of tert-butyl alcohol and 52.0 g of a 25% aqueous solution of sodium vinyl sulfonate were placed. Was added to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes. Further, 8.0 g of powdered sodium hydroxide was added, and the mixture was stirred at room temperature for 60 minutes. The reaction temperature was raised to 80 ° C., and the mixture was further stirred at 80 ° C. for 2 hours to perform sulfonation. After cooling the reaction solution to 60 ° C, water 21.0
g, and further 3.2 g of stearyl glycidyl ether
Was added to the mixture, and the mixture was heated to 80 ° C., and stirred at 80 ° C. for 8 hours to hydrophobize. After 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. 80% acetone (20% water) 50
After washing 5 times with 0 g and then 2 times with 500 g of acetone,
After drying at 70 ° C. for one day, 10.3 g of a cellulose derivative (compound 9 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfoethyl group was obtained.

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained cellulose derivative was 0.025, and the degree of substitution of the sulfoethyl group was 0.53.

Example 10 A reaction was carried out in the same manner as in Example 9 except that the amount of stearyl glycidyl ether was changed to 6.4 g, and a cellulose derivative substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfoethyl group ( The compound of the present invention 10) was obtained.

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained cellulose derivative was 0.049, and the degree of substitution of the sulfoethyl group was 0.53.

Example 11 (1) A 1,000 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 having a degree of substitution of hydroxyethyl group of 1.8 (HEC-QP100M, manufactured by Union Carbide) 50 g, 88
A slurry liquid was prepared by adding 400 g of 100% isopropyl alcohol and 3 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 1.5 g of octadecyl glycidyl ether was added thereto, and the mixture was reacted at 80 ° C. for 7 hours to effect hydrophobicity. After completion of the hydrophobization reaction, the reaction solution was neutralized with hydrochloric acid, and the reaction product was filtered. 80% acetone 50
Wash twice with 0 g and then twice with 500 g of acetone.
Drying was carried out at 24 ° C. for one day to obtain 44.3 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 solution was added a mixed solution consisting 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 0 ° C. for 8 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was filtered. The product was washed three times with 500 g of 80% acetone (20% of water) and then twice with 600 g of acetone, dried under reduced pressure at 70 ° C. for one day, and dried with 3-octadecyloxy-2-hydroxypropyl group and 3-sulfo- 7.5 g of a hydroxyethyl cellulose derivative (the present compound 11) substituted with a 2-hydroxypropyl group was obtained.

The degree of substitution of the 3-octadecyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.007, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.31.

Example 12 (1) A 1,000 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 having a degree of substitution of hydroxyethyl group of 1.8 (HEC-QP100M, manufactured by Union Carbide) 50 g, 88
A slurry liquid was prepared by adding 400 g of 100% isopropyl alcohol and 3 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, 1.0 g of octadecyl glycidyl ether was added and reacted at 80 ° C. for 7 hours to effect hydrophobicity. After completion of the hydrophobization reaction, the reaction solution was neutralized with hydrochloric acid, and the reaction product was filtered. 80% acetone 50
Wash twice with 0 g and then twice with 500 g of acetone.
Drying at ℃ for 24 hours gave 45.1 g of hydrophobized hydroxyethylcellulose 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 8 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was filtered. 80% product
After washing three times with 500 g of acetone (20% of water) and then twice with 500 g of acetone, it was dried under reduced pressure at 70 ° C. for one day and night, and 3-octadecyloxy-2-hydroxypropyl group and 3-sulfo-2-hydroxypropyl group were obtained. 7.6 g of the hydroxyethyl cellulose derivative (Compound 12 of the present invention) substituted with was obtained.

The degree of substitution of 3-octadecyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.004, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.31.

Example 13 (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 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 13 of the present invention) substituted with was obtained.

The substitution degree 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 14 In a 500 ml glass separable reaction vessel equipped with a stirrer, thermometer and cooling tube, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 13 (1), 160 g of isopropyl alcohol and 25% vinyl sulfone Aqueous sodium acid solution 36.
0 g was charged to prepare a slurry liquid. After stirring at room temperature for 30 minutes under a nitrogen stream, 1.2 g of a 48% aqueous sodium hydroxide solution was charged, and the mixture was 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 then dried at 70 ° C. under reduced pressure for one day and night, and hydroxyethyl cellulose derivative substituted with 2-hydroxyoctadecyl group and 2-sulfoethyl group (Compound 14 of the present invention) 8.9
g was obtained.

The degree of substitution 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 15 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 13 (1), 160 g of 90% isopropyl alcohol and 48% A slurry solution was prepared by adding 13.1 g of an aqueous sodium hydroxide solution, followed by stirring 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 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 1 day to obtain 8.9 g of a hydroxyethyl cellulose derivative (Compound 15 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 in the obtained hydroxyethyl cellulose derivative was 0.015,
The degree of substitution of the sulfopropyl group was 0.20.

Example 16 (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 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. 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) 16) 8.2 g were 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 17 (1) A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP100M, 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 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 substituted with a 2-hydroxypropyl group (Compound 17 of the present invention) was obtained.

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

Example 18 (1) A 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with hydroxyethyl cellulose (HEC-QP4400) having a weight average molecular weight of about 800,000 and a degree of substitution 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 solution, 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 hydroxyethyl cellulose derivative (compound 18 of the present invention) substituted with -octadecyl group and sulfo-2-hydroxypropyl group was obtained.

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

Example 19 (1) 10.0 g of the hydrophobized hydroxyethylcellulose obtained in Example 18 (1), 160 g of isopropyl alcohol and 25 g of a hydrophobized hydroxyethyl cellulose obtained in Example 18 (1) were placed in a 500-ml separable reaction vessel made of glass equipped with a stirrer, a thermometer and a condenser. A slurry liquid was prepared by charging 36.0 g of an aqueous sodium vinyl sulfonate solution. 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 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
And dried at 70 ° C. under reduced pressure for one day and night, and a hydroxyethyl cellulose derivative substituted with a 2-hydroxy-n-octadecyl group and a sulfoethyl group (Compound 19 of the present invention) 8.
5 g were obtained.

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

Example 20 In a 500-ml separable glass reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethyl cellulose obtained in Example 18 (1), 160 g of 90% isopropyl alcohol and 48% A slurry liquid was prepared by adding 13.1 g of an 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 is mixed with 500 g of 80% acetone (20% water)
And then twice with 500 g of acetone, and then 1
It was dried day and night to obtain 8.8 g of a hydroxyethyl cellulose derivative (Compound 20 of the present invention) substituted with a 2-hydroxy-n-octadecyl group and a sulfopropyl group.

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.

Example 21 (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 80
g, 640 g of 80% isopropyl alcohol and 5.5 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. To this, 0.84 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then acetone 5
After washing twice with 00 g and drying under reduced pressure at 70 ° C. for one day and night, 72.8 g of a hydrophobized hydroxyethyl cellulose derivative was obtained.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
In a 00 ml glass separable reaction vessel, 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 70%
A slurry liquid was prepared by charging 200 g of isopropyl alcohol and 1.37 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 4.09 g of sodium 3-chloro-2-hydroxypropanesulfonate and 1.7 g of a 48% aqueous sodium hydroxide solution were added to the reaction solution, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is 70% isopropyl alcohol
Once with 340 g, then 2 with 120 g of isopropyl alcohol
After washing twice, the mixture was dried under reduced pressure at 70 ° C. for one day and night, and 18.3 g of a hydroxyethylcellulose derivative (compound 21 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a 3-sulfo-2-hydroxypropyl group was added. Obtained.

In the obtained hydroxyethyl cellulose derivative, the degree of substitution of 3-stearyloxy-2-hydroxypropyl group was 0.00098, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.078.

Example 22 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling pipe 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 80
g, 640 g of 80% isopropyl alcohol and 5.5 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. To this, 0.42 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was washed twice with 500 g of isopropyl alcohol at 50 ° C., and then acetone 5
After washing twice with 00 g and drying under reduced pressure at 70 ° C. for one day, 68.23 g of a hydrophobized hydroxyethyl cellulose derivative was obtained.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
In a 00 ml glass separable reaction vessel, 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 70%
A slurry liquid was prepared by charging 200 g of isopropyl alcohol and 1.37 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 2.05 g of sodium 3-chloro-2-hydroxypropanesulfonate and 0.86 g of a 48% aqueous sodium hydroxide solution were added to the reaction solution, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is 70% isopropyl alcohol
Once with 340 g, then 2 with 120 g of isopropyl alcohol
After washing twice, it was dried under reduced pressure at 70 ° C. for one day and night, and 17.64 g of a hydroxyethylcellulose derivative (compound 22 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a 3-sulfo-2-hydroxypropyl group was added. Obtained.

In the obtained hydroxyethyl cellulose derivative, the degree of substitution of 3-stearyloxy-2-hydroxypropyl group was 0.00052, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.037.

Example 23 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in Example 21 (1), 160 g of isopropyl alcohol and 25% A slurry liquid was prepared by charging 8.3 g of an aqueous solution of sodium vinyl sulfonate. 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 stirred at room temperature for 60 minutes under a nitrogen stream. Further, the temperature of the slurry liquid is raised to 80 ° C.
Sulfonation was performed by stirring for hours. 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 170 g of 70% isopropyl alcohol and then twice with 60 g of isopropyl alcohol, and then reduced under reduced pressure to 70 ° C.
For one day and night to obtain 8.9 g of a hydroxyethyl cellulose derivative (compound 23 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfoethyl group.

The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained hydroxyethyl cellulose derivative was 0.00098, and the degree of substitution of the sulfoethyl group was 0.082.

Example 24 In a 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser, 10.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in Example 21 (1), 160 g of 90% isopropyl alcohol and 48% sodium hydroxide aqueous solution
A slurry liquid was prepared by charging 5.4 g, and stirred at room temperature for 30 minutes under a nitrogen stream. After the reaction solution was cooled to 10 ° C. or less under ice cooling, 12.0 g of sodium 3-bromopropanesulfonate was charged and stirred at 10 ° C. or less for 60 minutes. Further, the reaction solution was
The mixture 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 is washed three times with 170 g of 70% isopropyl alcohol and then with 60 g of isopropyl alcohol
After drying twice at 70 ° C. under reduced pressure for one day, 8.9 g of a hydroxyethyl cellulose derivative (compound 24 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a sulfopropyl group was obtained.

In the obtained hydroxyethyl cellulose derivative, the degree of substitution of 3-stearyloxy-2-hydroxypropyl group was 0.00098, and the degree of substitution of sulfopropyl group was 0.077.

Example 25 (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 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. To this, 0.21 g of 1,2-epoxyoctadecane was added, and the mixture was reacted at 80 ° C. for 8 hours to perform hydrophobization. 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 isopropyl alcohol at 50 ° C., and then with 500 g of acetone.
And dried at 70 ° C. under reduced pressure for one day to obtain 48.8 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 derivative obtained in (1), 70%
A slurry liquid was prepared by charging 100 g of isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 2.1 g of sodium 3-chloro-2-hydroxypropanesulfonate and 0.88 g of a 48% aqueous sodium hydroxide solution were 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 is 70% isopropyl alcohol
170 g three times, then isopropyl alcohol 60 g two
After washing twice, it was dried under reduced pressure at 70 ° C. for one day to obtain 7.2 g of a hydroxyethyl cellulose derivative (compound 25 of the present invention) substituted with a 2-hydroxyoctadecyl group and a 3-sulfo-2-hydroxypropyl group.

The degree of substitution of the 2-hydroxyoctadecyl group of the obtained hydroxyethyl cellulose derivative was 0.00080,
The degree of substitution of the -sulfo-2-hydroxypropyl group was 0.078.

Example 26 (1) A 1,000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling pipe 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% of 88% isopropyl alcohol and 3.6 g of 48% aqueous sodium hydroxide solution to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 0.4 g of 1-chlorooctadecane was added thereto, and the mixture was 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 isopropyl alcohol at 50 ° C., then twice with 500 g of acetone, and dried under reduced pressure at 70 ° C. for one day to obtain 48.7 g of a hydrophobized hydroxyethyl cellulose 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 derivative obtained in (1), 70%
A slurry liquid was prepared by charging 100 g of isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 2.1 g of sodium 3-chloro-2-hydroxypropanesulfonate and 0.88 g of a 48% aqueous sodium hydroxide solution were 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 hydrochloric acid, and the product was separated by filtration. The product is 70% isopropyl alcohol
170 g three times, then isopropyl alcohol 60 g two
After washing twice, it was dried under reduced pressure at 70 ° C. for one day and night, and a hydroxyethylcellulose derivative substituted with an octadecyl group and a 3-sulfo-2-hydroxypropyl group (the present compound 26) 8.2
g was obtained.

The degree of substitution of the octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.00071, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.080.

Example 27 (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, 70% isopropyl alcohol 500g and 48% sodium hydroxide aqueous solution 3.5g to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen stream for 30 minutes. 3-chloro-2 in the reaction solution
10.5 g of sodium hydroxypropanesulfonate and 4
4.4 g of an 8% aqueous sodium hydroxide solution 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 is washed three times with 850 g of 70% isopropyl alcohol and then with 300 g of isopropyl alcohol
After drying twice at 70 ° C. under reduced pressure for 1 day, 50.0 g of a sulfonated hydroxyethyl cellulose derivative was obtained.

(2) 5 equipped with a stirrer, thermometer and cooling pipe
In a 00 ml glass separable reaction vessel, 10.0 g of the sulfonated hydroxyethyl cellulose derivative obtained in (1),
A slurry liquid was prepared by charging 80.0 g of 88% isopropyl alcohol and 0.01 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, 0.03 g of stearoyl chloride was added, and the mixture was reacted at 80 ° C. for 8 hours to hydrophobize. After completion of the hydrophobization reaction, the reaction solution is neutralized with acetic acid,
The reaction product was filtered off. The reaction product was washed three times with 170 g of 70% isopropyl alcohol and then twice with 60 g of isopropyl alcohol, dried under reduced pressure at 70 ° C. for 24 hours, and substituted with 1-oxooctadecyl group and 3-sulfo-2-hydroxypropyl group. 8.5 g of the obtained hydroxyethyl cellulose derivative (Compound 27 of the present invention) was obtained.

The degree of substitution of the 1-oxooctadecyl group of the obtained hydroxyethyl cellulose derivative was 0.00093, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.081.

Example 28 (1) A hydroxyethyl cellulose (HEC-QP4400) having a weight average molecular weight of about 800,000 and a degree of substitution of hydroxyethyl group of 1.8 was placed in a 1000 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a condenser. , Union Carbide) 50g,
A slurry was prepared by adding 400 g of 80% isopropyl alcohol and 3.5 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature for 30 minutes under a nitrogen atmosphere. To this, 0.39 g of stearyl glycidyl ether was added, and the mixture was 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 isopropyl alcohol at 50 ° C., and then with 500 g of acetone.
And dried at 70 ° C. under reduced pressure for 24 hours to obtain 44.3 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 derivative obtained in (1), 70%
A slurry liquid was prepared by charging 100 g of isopropyl alcohol and 0.67 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 2.11 g of sodium 3-chloro-2-hydroxypropanesulfonate and 0.88 g of a 48% aqueous sodium hydroxide solution were added to the reaction solution, and sulfonation was performed at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is 70% isopropyl alcohol
Once with 170 g, then 2 with 60 g of isopropyl alcohol
After washing twice, the mixture was dried under reduced pressure at 70 ° C. for one day and night to obtain 8.8 g of a hydroxyethyl cellulose derivative (compound 28 of the present invention) substituted with a 3-stearyloxy-2-hydroxypropyl group and a 3-sulfo-2-hydroxypropyl group. Obtained.

In the obtained hydroxyethyl cellulose derivative, the degree of substitution of 3-stearyloxy-2-hydroxypropyl group was 0.00081, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.079.

Comparative Example 1 In Example 1, stearyl glycidyl ether 5.4
was hydrophobized by using 4.5 g of octyl glycidyl ether instead of g, and sulfonation was further performed in the same manner as in Example 3 to obtain a hydroxyethyl cellulose derivative having an octyl glyceryl ether group and a sulfoethyl group (Comparative Compound 1). .

The degree of substitution of the octyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.032,
The degree of substitution of the sulfoethyl group was 0.18.

Comparative Example 2 The hydroxyethylcellulose derivative substituted with a 3-stearyloxy-2-hydroxypropyl group synthesized in Example 1 (1) was used as it was (degree of substitution of 3-stearyloxy-2-hydroxypropyl group 0.030). ) And Comparative Compound 2.

Comparative Example 3 The same hydroxyethylcellulose (HEC-QP4400, manufactured by Union Carbide) as used in Examples 1 to 6, 18 to 20 and 28 was treated with sulfone in the same manner as in Example 3 without hydrophobization. Then, a hydroxyethyl cellulose derivative substituted with a sulfoethyl group (substitution degree of sulfoethyl group: 0.18) (Comparative Compound 3) was obtained.

Comparative Example 4 The same hydroxyethylcellulose (HEC-QP4400, manufactured by Union Carbide) as used in Examples 1 to 6, 18 to 20 and 28 was used as it was to make Comparative Compound 4.

Comparative Example 5 The same hydroxyethylcellulose (HEC-QP100M, manufactured by Union Carbide) as used in Examples 11 to 17 and 21 to 27 was used as it was to obtain Comparative Compound 5.

Comparative Example 6 Carboxymethylcellulose (CMC2280, manufactured by Daicel Chemical Industries, Ltd., weight average molecular weight: about 1,000,000, carboxymethylation degree)
0.78) was used as it was as Comparative Compound 6.

Comparative Example 7 Comparative compound 7 was prepared using sodium polyacrylate (Carbopol 941, manufactured by Goodrich).

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 or 1.0% by weight of an aqueous solution of sodium chloride with stirring, left at room temperature for 24 hours, and the viscosity of each aqueous solution was measured. In addition,
The viscosity was measured using a Brookfield viscometer (12 rpm, 25 ° C.). The results are shown in Tables 1 and 2.

[0126]

[Table 1]

[0127]

[Table 2]

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 evident from Tables 1 and 2, and is also excellent in 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 3 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 3, 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 3 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

[0134]

[Table 3]

As is clear from Table 3, the novel polysaccharide derivative of the present invention has excellent foam stability and foam increasing properties.

Example 29 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 4 shows the results.

<Emulsion 1 of the Present Invention (Comparative Emulsion 1)> Compound 4 of the Present Invention (or Comparative Compound 1) 0.6% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 12.0% by weight Methylpolysiloxane 1.0% by weight 2-Ethylhexyl paramethoxycinnamate 5.0% by weight Zinc oxide treated with silicone 3.0% by weight Glycerin 2.0% by weight Water balance

[0138]

[Table 4]

Example 30 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 5 shows the results.

<Emulsion 2 of the Present Invention (Comparative Emulsion 2)> Compound 6 of the Present Invention (or Comparative Compound 6) 0.25 wt% Water (or 53.3 wt% of water + 0.25 wt% of L-Algin) 53.55 wt% Ethanol (55 v / v%) 10.0% by weight Glycerin 2.0% by weight 2-ethylhexyl paramethoxycinnamate 3.0% by weight Methylpolysiloxane 5.0% by weight Methylcyclopolysiloxane 25.0% by weight Zinc sulfocarbonate 0.2% by weight Self-emulsifying glycerol monostearate 0.7% by weight Sorbitan monostearate 0.3% by weight

[0141]

[Table 5]

Example 31 Emulsion Emulsion 3 of the present invention and Comparative Emulsion 3 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 6 shows the results.

<Emulsion 3 of the Present Invention (Comparative Emulsion 3)> Compound 13 of the Present Invention (or Comparative Compound 6) 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

[0144]

[Table 6]

Example 32 Emulsion Emulsion 4 of the present invention and Comparative Emulsion 4 having the following compositions were prepared, and their viscosity, emulsion stability, and usability were compared. In addition, the emulsion stability was evaluated immediately after storage at 50 ° C., 1 week and 1 month later, by visual inspection of the state of the emulsion. , The number of people who answered better.
Table 7 shows the results.

<Emulsion 4 of the Present Invention (Comparative Emulsion 4)> Compound 14 of the Present Invention (or Comparative Compound 7) 0.6% by weight Squalane 3.0% by weight Methylcyclopolysiloxane 12.0% by weight Methylpolysiloxane 1.0% by weight 2-ethylhexyl paramethoxycinnamate 5.0% by weight Zinc oxide treated with silicone 3.0% by weight Glycerin 2.0% by weight Water balance

[0147]

[Table 7]

Example 33 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 34 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 4 0.5% by weight 0.1% by weight butylparaben 0.1% by weight methylparaben Ethanol 5.0 Glycerin 3.0% by weight Fragrance 0.05% by weight Water balance

Example 35 Toner A lotion was prepared according to the following formulation. This lotion is 1 at 50 ℃
It was stable for months and had a good usability. Ethanol 5.0% by weight Glycerin 3.0% by weight Polyethylene glycol 1500 4.0% by weight Polyoxyethylene oleyl ether (20EO) 0.3% by weight Polyoxyethylene hydrogenated castor oil (30EO) 0.2% by weight Compound 1 of the present invention 0.15% by weight zinc p-phenolsulfonate 0.2% by weight water balance

Example 36 Sun care cream A sun care cream was prepared according to the following formulation. This sun care cream was stable at 50 ° C. for one month or more, and had a good feeling upon use. Dimethylsiloxane / methyl (polyoxyethylene) siloxane polymer 2.0% by weight Polyoxyethylene (20EO) sorbitan monooleate 0.5% by weight Methylpolysiloxane (5cs) 7.0% by weight Methylphenylpolysiloxane 2.0% by weight Jojoba oil 2.0% by weight Palmitin Acid dextrin 0.5% by weight Octyldimethyl PABA 4.0% by weight Silicone-coated fine particle titanium oxide 5.0% by weight Acidic heteropolysaccharide 0.03% by weight Magnesium sulfate 0.5% by weight Glycerin 5.0% by weight Dibutylhydroxytoluene 0.05% by weight Compound of the present invention 6 0.5% by weight Water balance

Example 37 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 38 Lipstick A lipstick was prepared according to the following formulation. This lipstick was stable at 50 ° C. for one month or more and had a good feeling upon use. Castor oil 52.0% by weight Lanolin 5.0% by weight Liquid lanolin 5.0% by weight Beeswax 4.0% by weight Ozokerite 7.0% by weight Candelilla wax 2.0% by weight Carnauba wax 1.0% by weight Dodecyl-modified silicone 10.0% by weight The present compound 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

Example 39 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 13 0.2% by weight Water balance

Example 40 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 13 of the present invention 13 0.5% by weight Butylparaben 0.1% by weight Methylparaben 0.1% by weight Ethanol 5.0 Glycerin 3.0% by weight Fragrance 0.05% by weight Water balance

Example 41 Toner A lotion was prepared according to the following formulation. This lotion is 1 at 50 ℃
It was stable for months and had a good usability. Ethanol 5.0% by weight Glycerin 3.0% by weight Polyethylene glycol 1500 4.0% by weight Polyoxyethylene oleyl ether (20EO) 0.3% by weight Polyoxyethylene hydrogenated castor oil (30EO) 0.2% by weight Compound 13 of the present invention 13 0.15% by weight zinc p-phenolsulfonate 0.2% by weight water balance

Example 42 Sun care cream A sun care cream was prepared according to the following formulation. This sun care cream was stable at 50 ° C. for one month or more, and had a good feeling upon use. Dimethylsiloxane / methyl (polyoxyethylene) siloxane polymer 2.0% by weight Polyoxyethylene (20EO) sorbitan monooleate 0.5% by weight Methylpolysiloxane (5cs) 7.0% by weight Methylphenylpolysiloxane 2.0% by weight Jojoba oil 2.0% by weight Palmitin Acid dextrin 0.5% by weight Octyldimethyl PABA 4.0% by weight Silicon-coated fine particle titanium oxide 5.0% by weight Acidic heteropolysaccharide 0.03% by weight Magnesium sulfate 0.5% by weight Glycerin 5.0% by weight Dibutylhydroxytoluene 0.05% by weight Compound of the present invention 15 0.5% by weight Water balance

Example 43 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 13 of the present invention 0.2% by weight α-monoisostearyl glyceryl ether 2.0% by weight Aluminum diisostearate 0.2% by weight Liquid paraffin 10.0% by weight Neopentyl glycol dioctanoate 5.0% by weight Methylphenyl polysiloxane (14cs) 5.0% by weight p- 2-ethylhexyl methoxycinnamate 3.0% by weight 2-hydroxy-4-methoxybenzophenone 1.0% by weight Silicone-coated fine particles of titanium oxide 5.0% by weight Silicone-coated fine particles of zinc oxide 1.0% by weight Sericite 2.0% by weight Talc 2.0% by weight Bengala 0.4% by weight % Iron yellow oxide 0.7% by weight Black iron oxide 0.1% by weight Magnesium sulfate 1.0% by weight Methyl paraben 0.2% by weight Fragrance Trace water Balance

Example 44 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 16 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

Example 45 Mortar A mortar was prepared according to the following formulation. This mortar was excellent, having excellent dispersion stability of the aggregate at the time of preparation and having high fluidity. Water 350g Cement 700g Sand 1850g Dispersant (Mighty 3000s, manufactured by Kao Corporation) 11.9g Compound of the present invention 21 0.14g

[0161]

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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI // A61K 7/025 A61K 7/025 7/035 7/035 7/42 7/42

Claims (7)

[Claims] 1. A polysaccharide or a derivative thereof is produced by:
Glycidyl ethers, epoxides, halides and halohydrins having a linear or branched alkyl or alkenyl group of from 40 to 40, and esters, acid halides and the like having a linear or branched saturated or unsaturated acyl group having 10 to 40 carbon atoms. A hydrophobizing agent selected from carboxylic anhydrides, and (b)
A novel polysaccharide derivative obtained by reacting with a sulfonating agent selected from vinyl sulfonic acid, halo C ₁ -C ₅ alkane sulfonic acid optionally substituted with a hydroxyl group and salts thereof. 2. The novel polysaccharide derivative according to claim 1, which is obtained by reacting a polysaccharide or a derivative thereof with (a) a hydrophobizing agent and then (b) a sulfonating agent. 3. The novel polysaccharide derivative according to claim 1, which is obtained by reacting a polysaccharide or a derivative thereof with (b) a sulfonating agent and then reacting with (a) a hydrophobizing agent. 4. The novel polysaccharide derivative according to claim 1, which is obtained by reacting a polysaccharide or a derivative thereof simultaneously with (a) a hydrophobizing agent and (b) a sulfonating agent. 5. The raw material polysaccharide or 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. 2. The composition according to claim 1, wherein the composition is selected from the group consisting of: hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, hydroxypropyl methyl cellulose, hydroxypropyl methyl guar gum, and hydroxypropyl methyl starch.
5. The novel polysaccharide derivative according to any one of items 1 to 4. 6. A cosmetic comprising the novel polysaccharide derivative according to claim 1. 7. A compound selected from the group consisting of metal oxides, organic ultraviolet absorbers, inorganic metal salts and organic metal salts.
7. The cosmetic according to claim 6, comprising at least one species.