JPH10330401A - Novel polysaccharide derivative and method for producing the same - Google Patents

Abstract

(57) Abstract: A part or all of hydrogen atoms of a hydroxyl group of a polysaccharide or a derivative thereof is (A) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or A polysaccharide derivative which is substituted with its salt (substituent (A)) so that the average degree of substitution per constituent monosaccharide residue is 0.01 to 2.0, and the remaining hydroxyl groups are optionally crosslinked with polyol polyglycidyl ethers And its manufacturing method. [Effect] Since this compound gives excellent dispersion stability and good fluidity even in the presence of salts, it can be used as a building material, a water-soluble paint, a soil modifying material, cosmetics, toiletry products, and external medicines.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative, and more particularly, to a novel polysaccharide derivative which has excellent transparency when formed into an aqueous solution, has little change in aqueous solution viscosity due to coexistence of metal salts and changes in temperature, and has good fluidity. The present invention relates to a novel polysaccharide derivative and a production method thereof.

[0002]

2. Description of the Related Art As one of the important constituents of building materials, water-soluble paints, cosmetics, toiletry products, external medicines, 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, There is a drawback that when the viscosity is low at the same aqueous solution concentration and the product is incorporated as a thickener or a dispersion stabilizer in a product, the viscosity change accompanying the temperature change is 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 nonionic cellulose derivative into which is introduced a small amount of water shows a relatively high viscosity when mixed with water. In addition, JP-A-3-24001, JP-A-3-41210, JP-A-3-41214, JP-A-3-218316, as seen in JP-A-3-218316, topical pharmaceuticals for these alkyl-substituted cellulose derivatives, cosmetics Attempts have been made to apply it to such applications. However, although these alkyl-substituted cellulose derivatives exhibit excellent viscosity increase compared to the above-mentioned cellulose ethers, they have poor water solubility and require a long time to be uniformly dissolved when blended into products, Problems such as poor viscosity stability.

[0005]

As an ideal thickener used for building materials and water-soluble paints, it easily dissolves, has a high dispersion stabilizing ability, and impairs the flowability of building materials. It does not have any influence on the viscosity due to the absence of metal salts, surfactants and other additives, and changes in temperature and pH, and has excellent microbial resistance. However, the above-mentioned cellulose ethers and alkyl-substituted cellulose derivatives have not sufficiently satisfied all of these required properties.

Accordingly, the present invention is effective in that the viscosity is hardly affected by inorganic metal salts, organic metal salts, temperature, pH, etc., and when used for building materials, etc., shows good fluidity and dispersion stability. An object of the present invention is to provide a novel polysaccharide derivative that exerts its effect and a method for producing the same.

[0007]

Under such circumstances, the inventors of the present invention have conducted intensive studies, and as a result, substituted a hydrogen atom of a hydroxyl group of a polysaccharide with a substituent containing a specific sulfonic acid group, and optionally substituted In addition, a novel polysaccharide derivative cross-linked with polyol polyglycidyl ethers is excellent in water solubility, is not easily affected by inorganic metal salts, organic metal salts, pH, temperature, etc., shows stable thickening, and has excellent dispersion stabilization When it is used for building materials and water-soluble paints,
They have found that they have both good dispersion stability and fluidity, and have completed the present invention.

That is, the present invention relates to a polysaccharide or a derivative thereof, wherein part or all of the hydrogen atoms of the hydroxyl group are (A) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by the hydroxyl group or a salt thereof. A novel polysaccharide derivative, which is substituted with (Substituent (A)) and has an average degree of substitution per constituent monosaccharide residue by the substituent (A) of 0.01 to 2.0, and a method for producing the same. Is what you do.

The present invention also relates to a polysaccharide or a derivative thereof, wherein part or all of the hydrogen atoms of the hydroxyl group are (A) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a sulfoalkyl group thereof. A salt (substituent (A)), the substituent (A) has an average degree of substitution per constituent monosaccharide residue of 0.01 to 2.0, and the remaining hydroxyl group is a polyol polyglycidyl ether. (Here, the polyol polyglycidyl ether may be cross-linked by a substituent (A) on its hydroxyl group) and a method for producing the same. .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The novel polysaccharide derivative of the present invention has a repeating unit represented by the following general formula, or an example in which cellulose is used as a polysaccharide or a derivative thereof. It is exemplified as a crosslinked product by polyol polyglycidyl ethers.

[0011]

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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., and (2): a sulfoalkyl which may be substituted by a hydroxyl group. Represents a group selected from the group (A),
A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, and a, b and c are the same or different and represent a number of 0 to 10. The AO group, R group, a, b and c may be the same or different within the repeating unit or between the repeating units, but the degree of substitution per constituent monosaccharide residue of the substituent (A) is, on average, 0.01
2.02.0, and the remainder is group (1). ]

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

The sulfoalkyl group (A) which may be substituted with a hydroxyl group includes 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 (A) 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 (A) are
Not only the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule but also the hydrogen atom of the hydroxyl group of the hydroxyethyl group or hydroxypropyl group bonded to the polysaccharide molecule may be substituted. The degree of substitution by these substituents (A) is
It can be adjusted appropriately within the range of 0.01 to 2.0 per constituent monosaccharide residue, but is preferably in the range of 0.01 to 0.5 per constituent monosaccharide residue.

Further, the polysaccharide derivative of the present invention crosslinked with a polyol polyglycidyl ether is one in which a part of the hydroxyl groups in the repeating unit is crosslinked with a polyol polyglycidyl ether. Examples of the cross-linking group include the groups shown below and groups in which the above-mentioned substituent (A) is substituted on a hydroxyl group in the following formula.

[0016]

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(Wherein m and n are each m = 2 to 50)
0, n = 2 to 20; the arrow indicates that this part is bonded to the oxygen atom of the hydroxyl group of the sugar residue)

The cross-linking group may be an intra-molecular cross-link or an inter-molecular cross-link of the polysaccharide derivative, but is preferably mainly an inter-molecular cross-link. The crosslinking ratio, that is, the ratio of the cross-linked hydroxyl groups is 0.001% of the total hydroxyl groups of the compound before cross-linking in terms of viscosity increase and solubility in water.
To 5% is preferable, and 0.001 to 1% is particularly preferable.

Among the polysaccharide derivatives of the present invention, compounds having a substituent (A) include, for example, polysaccharides or derivatives thereof obtained by (a) vinyl sulfonic acid or halo C ₁ -C _{5 which} may be substituted with a hydroxyl group. It is produced by reacting with a sulfonating agent selected from alkanesulfonic acids and salts thereof (sulfonation reaction).

Compounds cross-linked with polyol polyglycidyl ethers include, for example, polysaccharides or derivatives thereof obtained by (a) vinyl sulfonic acid or halo C ₁ -C ₅ alkane sulfonic acid optionally substituted by a hydroxyl group. And a salt thereof, and a sulfonating agent selected from the salts thereof, and (b) a polyol polyglycidyl ether. Here, the reaction with the sulfonating agent (sulfonation reaction) and the reaction with the polyol polyglycidyl ethers (crosslinking reaction) may be performed simultaneously, or the crosslinking reaction may be performed after the sulfonation reaction. Alternatively, a sulfonation reaction may be performed after the crosslinking reaction. Here, when the sulfonation reaction and the cross-linking reaction are performed simultaneously, or when the sulfonation reaction is performed after the cross-linking reaction, sulfonation occurs on the hydroxyl group of the cross-linked polyol polyglycidyl ether, and the substituent (A) is Replace.

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

Hereinafter, the sulfonation reaction and the crosslinking reaction will be described separately. When a polysaccharide derivative is obtained as a crosslinked product as described above, either the crosslinking reaction or the sulfonation reaction may be performed first, or may be performed simultaneously.

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

Among the sulfonating agents, the substituted halogen atom in the halo C ₁ -C ₅ alkanesulfonic acid which may be substituted by a hydroxyl group is a fluorine atom, a chlorine atom,
And a bromine atom. As the sulfonating agent, vinylsulfonic acid, 3-halo-2-hydroxypropanesulfonic acid, and 3-halopropanesulfonic acid are preferable, and these sulfonating agents can be used alone or in combination of two or more. The amount of the sulfonating agent used can be appropriately adjusted depending on the desired amount of the sulfonic acid group to be introduced into the polysaccharide or its derivative, but usually, 0.01 to 10.0 equivalents per monosaccharide residue constituting the polysaccharide or the cross-linked polysaccharide. Is preferred.

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

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. Further, for the purpose of enhancing the reactivity of the polysaccharide or cross-linked polysaccharide and the sulfonating agent, for 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.

[0027] The reaction temperature is preferably in the range of 0 to 150 ° C, particularly 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, sulfuric acid, hydrochloric acid, inorganic acids such as phosphoric acid,
Organic acids such as acetic acid can be used. The following reaction may be performed without neutralization in the middle.

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

<Cross-Linking Reaction> The cross-linking reaction of a polysaccharide or a sulfonated polysaccharide is carried out without a solvent or by dissolving or dispersing the polysaccharide or the sulfonated polysaccharide in an appropriate solvent and reacting with a polyol polyglycidyl ether. It is performed by

The amount of the polyol polyglycidyl ether can be appropriately adjusted depending on the desired degree of crosslinking to the polysaccharide or a derivative thereof, but is 0.001 to 20 mol%, preferably 0.001 to 20 mol%, based on all hydroxyl groups of the compound before crosslinking. ~ 5 mol% is preferred.

The crosslinking reaction can be carried out in the presence of an alkali catalyst or in the presence of an acid catalyst. However, by using an alkali catalyst having a common sulfonation reaction, both reactions can be carried out without purification and isolation. Can be performed continuously or simultaneously.

Examples of the alkali include, but are not particularly limited to, hydroxides, carbonates, and bicarbonates of alkali metals or alkaline earth metals. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, water Magnesium oxide and the like are preferred. The amount of the alkali used is preferably 0.01 to 1.0 times the molar amount of the crosslinking agent used to give a good result,
Preferably, when used in combination with the sulfonation reaction, it may be adjusted to the amount of alkali used in the sulfonation reaction.

This reaction can be carried out without a solvent. However, when a sulfonated polysaccharide is used, or when sulfonation is carried out simultaneously or when sulfonation is carried out after the cross-linking reaction of the polysaccharide, the polysaccharide is not reacted. It is desirable to use a solvent for the purpose of improving the reactivity.

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 sulfonated polysaccharide and the crosslinking agent, for 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.

[0035] The reaction temperature is preferably in the range of 0 to 150 ° C, particularly 30 to 100 ° C. After completion of the reaction, the alkali is neutralized using an acid. As the acid, sulfuric acid, hydrochloric acid, inorganic acids such as phosphoric acid,
Organic acids such as acetic acid can be used. The following reaction may be performed without neutralization in the middle.

When the cross-linked polysaccharide thus obtained is subsequently used for a sulfonation 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 crosslinking agent or salts produced as a result of neutralization or the like. If the sulfonation reaction has already been performed before the crosslinking reaction, after separation by filtration or the like, washing and neutralization are performed as necessary, and then drying to obtain the novel polysaccharide derivative of the present invention. Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a cooling tube was charged with hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8. ) 30 g, 300 g of 70% isopropyl alcohol (30% water) and 2.1 g of a 48% aqueous sodium hydroxide solution were added to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 3-chloro
Sodium 2-hydroxypropanesulfonate (Tokyo Chemical) 6.14 g was added, followed by 2.59 g of 48% NaOH,
Stirred at C for 3 hours. After cooling, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product was washed twice with 340 g of 70% isopropyl alcohol (30% water), twice with 150 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. for 8 hours to obtain 24.1 g of a sulfonated polysaccharide (Product 1 of the present invention). I got The degree of sulfonation of the resulting sulfonated polysaccharide was 0.143 by a colloid titration method.

Example 2 A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer, and a cooling tube was charged with hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8. 30 g, 300 g of 70% isopropyl alcohol (30% water) and 2.1 g of a 48% aqueous sodium hydroxide solution were added to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 3-chloro
1.54 g of sodium 2-hydroxypropanesulfonate (Tokyo Kasei) was added, and 0.64 g of 48% NaOH was added.
Stirred at C for 3 hours. After cooling, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product was washed twice with 340 g of 70% isopropyl alcohol (30% water), then twice with 150 g of isopropyl alcohol, and dried under reduced pressure at 70 ° C. for 8 hours to obtain 23.5 g of a sulfonated polysaccharide (Product 2 of the present invention). I got The degree of sulfonation of the resulting sulfonated polysaccharide was 0.029 by a colloid titration method.

Example 3 A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8. ) 30 g, 1.0 g of diethylene glycol diglycidyl ether (SR-2EG, manufactured by Sakamoto Yakuhin), 70% isopropyl alcohol (water 30%) 3
00g and 2.1 g of a 48% aqueous sodium hydroxide solution,
Stirred at 10 ° C. for 10 hours. To this, 6.14 g of sodium 3-chloro-2-hydroxypropanesulfonate (Tokyo Kasei) was added, and 2.59 g of 48% NaOH was further added, followed by stirring at 50 ° C. for 3 hours. After cooling, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. The product is 70% isopropyl alcohol (water 30%) 34
Wash twice with 0 g, then 150 g of isopropyl alcohol
, And dried under reduced pressure at 70 ° C for 8 hours to obtain 26.2 g of a cross-linked sulfonated polysaccharide (Product 3 of the present invention). The sulfonation degree of the obtained sulfonated polysaccharide was determined to be 0.
It was 101.

Example 4 A 500 ml glass separable reaction vessel equipped with a stirrer, a thermometer and a cooling tube was charged with hydroxyethyl cellulose (HEC-QP100MH, manufactured by Union Carbide Co., Ltd.) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8. 30 g, 300 g of 70% isopropyl alcohol (30% water) and 2.1 g of a 48% aqueous sodium hydroxide solution were added to prepare a slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 1.5 g of polyethylene glycol diglycidyl ether (SR-8EG, manufactured by Sakamoto Yakuhin) and 3.00 g of sodium 3-chloro-2-hydroxypropanesulfonate (Tokyo Chemical) were added, followed by 48% Na
2.59 g of OH was added, and the mixture was stirred at 70 ° C. for 12 hours. After cooling down,
The reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. 70 products
After washing twice with 340 g of 30% isopropyl alcohol (30% water) and then twice with 150 g of isopropyl alcohol, it was dried under reduced pressure at 70 ° C. for 8 hours to obtain 20.8 g of a sulfonated polysaccharide (Product 4 of the present invention). The degree of sulfonation of the resulting sulfonated polysaccharide was 0.077 by a colloid titration method.

Test Example 1 Mortar Fluidity, Dispersion Stability Test A mortar was prepared according to the following formulation, and the aggregate dispersion stability at the time of preparation was visually observed, and the fluidity (flow) was measured by flow distance (JIS R 5201). It was measured.

[0043]

[Table 1] Mortar prescription water 350 g Cement 700 g Sand 1850 g Dispersant (Kao Mighty 3000S) 11.9 g Invention products 1-4 0.14 g

As a comparative product, a mortar using hydroxyethylcellulose (HEC-QP100MH) instead of the product of the present invention was prepared. Table 2 shows the results.

The fluidity was evaluated according to the following criteria. Flow distance: 60 cm or more ... good 55 cm or more and less than 60 cm ... somewhat good less than 55 cm ... insufficient

[0046]

[Table 2]

As is clear from Table 2, the novel polysaccharide derivative of the present invention can exhibit excellent solubility, dispersion stability and good fluidity even under high ionic strength, and exhibit excellent performance as a thickening dispersant. Have.

[0048]

Industrial Applicability The novel polysaccharide derivative of the present invention gives excellent dispersion stability and good fluidity even in the coexistence of salts, so that it can be used for building materials, water-soluble paints, soil modifying materials and cosmetics, toiletry products, and external use. It can be widely used as pharmaceuticals.

Claims (7)

[Claims] 1. A method according to claim 1, wherein part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof is (A) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by the hydroxyl group or a salt thereof (substituent (A)) a polysaccharide derivative having an average degree of substitution per constituent monosaccharide residue by the substituent (A) of 0.01 to 2.0. 2. A method according to claim 1, wherein a part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof is (A) a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by the hydroxyl group or a salt thereof (substituent (A)), the average degree of substitution per constituent monosaccharide residue by the substituent (A) is 0.01 to 2.0, and the remaining hydroxyl group is a polyol polyglycidyl ether (here, The polyol polyglycidyl ether has the substituent (A) on its hydroxyl group.
Which may be substituted). 3. The substituent (A) is one selected from a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group and a 2-sulfo-1- (hydroxymethyl) ethyl group. 3. The polysaccharide derivative according to claim 1, which is a combination of two or more. 4. The polysaccharide derivative according to claim 1, wherein the substituent (A) is a 3-sulfo-2-hydroxypropyl group. 5. The polysaccharide or a derivative thereof is cellulose,
Guar gum, starch, hydroxyethyl cellulose,
Hydroxyethyl guar gum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum, hydroxypropyl starch, hydroxyethyl methyl cellulose, hydroxyethyl methyl guar gum, hydroxyethyl methyl starch, The polysaccharide derivative according to any one of claims 1 to 4, which is selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylmethylguar gum, and hydroxypropylmethylstarch. 6. A polysaccharide or a derivative thereof is obtained by (a) vinyl sulfonic acid or halo C optionally substituted with a hydroxyl group.
₁ -C ₅ alkanoic acid and a manufacturing method of the polysaccharide derivative according to claim 1, wherein the reaction with a sulfonating agent selected from the salts thereof. 7. A polysaccharide or a derivative thereof is prepared by (a) vinyl sulfonic acid or halo C which may be substituted with a hydroxyl group.
₁ -C ₅ alkanoic acid and a sulfonating agent selected from the salts thereof, and (b) the production method of the polysaccharide derivative according to claim 2, wherein the reaction with a polyol polyglycidyl ethers.