JP2001181301A - Polysaccharide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polysaccharide derivative that shows a high thickening effect at a low content even in the presence of a surfactant and can be used as a thickening agent for cleaning. SOLUTION: A polysaccharide derivative is provided wherein all or part of the hydrogen atoms in the hydroxyl groups of a polysaccharide or a derivative thereof is replaced with group A: an amide group-containing hydrophobic group and/or group B: an anionic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polysaccharide derivative useful as a thickener for a detergent and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Cellulose ethers, polyacrylic acids and the like are known as aqueous thickeners. Among them, JP-A-9-235301 and JP-A-10-25301
And JP-A-10-292001 disclose that a polysaccharide derivative obtained by introducing a long-chain alkyl group and a sulfoalkyl group having 10 to 40 carbon atoms into a nonionic water-soluble cellulose derivative exhibits a high viscosity in a small amount. Have been.

[0003]

However, these thickeners have a problem that the viscosity is extremely reduced in a surfactant. An object of the present invention is to provide a polysaccharide derivative which exhibits high viscosity even in a small amount even in a surfactant, and a method for producing the same.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polysaccharide derivative in which part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof has been substituted with an A group or a B group, a thickener comprising the same, and a thickener comprising the same. Provide a manufacturing method. Group A: Amide group-containing hydrophobic group Group B: Ionic group

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the polysaccharide derivative of the present invention, when a cellulose is used as a polysaccharide or a derivative thereof, its repeating unit is exemplified by the general formula (5).

[0006]

Embedded image

[Wherein Z is the same or different and represents a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, etc .;
Represents a group. However, at least one of the Z groups is an A group, and at least one is a B group. Q 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. QO group, Z
The groups 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 group A or B may be further substituted with another group A or B. . The group A is preferably represented by the general formula (1). —E ¹ —CONH—R (1) wherein E ¹ may have a hydroxyl group or an oxo group, or has an oxycarbonyl group (—COO— or —OCO—) or an ether bond inserted. And represents a linear or branched alkylene group having 1 to 20 carbon atoms which may be substituted. R represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms which may be substituted by a hydroxyl group. ]

[0008] In the polysaccharide derivative of the present invention, Z in the constituent monosaccharide residue represented by the general formula (5) includes an A group and a B group. And that the B group must be present,
The group A and the group B need only be introduced when viewed as a whole molecule. The remaining Z is a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group or the like as described above.

In the group represented by the general formula (1), the E ¹ group is preferably a straight-chain or branched-chain alkylene group having 3 to 15, particularly 6 to 10 carbon atoms, and more preferably a straight-chain alkylene group. E ¹ may be, in addition to these alkylene groups, those having a hydroxy group or an oxo group, or those having an oxycarbonyl group (—COO— or —OCO—) or an ether bond inserted therein. Are preferred. Specifically, the E ¹ group is preferably a 2-hydroxyalkylene group or a 2-hydroxy-4-oxaalkylene group.

In the group represented by the general formula (1), R is
A linear or branched alkyl group having 6 to 24, particularly 8 to 18 carbon atoms is preferable, and a linear alkyl group is more preferable. R
May be substituted with a hydroxy group in addition to these alkyl groups. R is, specifically, an octyl group,
Decyl, dodecyl, tetradecyl, hexadecyl and octadecyl are preferred.

The group A may be substituted not only with the hydrogen atom of the hydroxyl group directly bonded to the polysaccharide molecule, but also with the hydrogen atom of the hydroxyl group of the hydroxyethyl group or hydroxypropyl group bonded to the polysaccharide molecule. . The degree of substitution by these A groups ranges from 0.001 to 0.1 per constituent monosaccharide residue.
Is preferable.

The group B is a sulfoalkyl group having 1 to 5 carbon atoms which may be substituted by a hydroxyl group or a salt thereof (B ¹
Group), 1 to 1 carbon atoms which may be substituted by a hydroxyl group
And at least one group selected from the group consisting of a carboxyalkyl group or a salt thereof (B ² group) and a group represented by the general formula (2) (B ³ group).

Embedded image [In the formula, D ¹ represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group. R ¹ , R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group. X ^- is a hydroxy ion,
It represents an anion such as a halogen ion or an organic acid ion. Further, the hydrogen atom of the hydroxyl group of the groups A and B may be further substituted with the groups A and B.

The degree of substitution by the B group is preferably in the range of 0.05 to 1.0 per constituent monosaccharide residue.

As the B ¹ group, a 2-sulfoethyl group, 3-
A sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, a 2-sulfo-1- (hydroxymethyl) ethyl group, and the like. Among them, a 3-sulfo-2-hydroxypropyl group is preferred from the viewpoint of stability and production. All or part of the B ¹ group may be a salt with a Group 1 or Group 2 element such as Na, K, Ca, and Mg, an organic cation such as an amine, and ammonium.

Examples of the B ² group include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a carboxybutyl group and a carboxypentyl group. Of these, a carboxymethyl group is preferred from the viewpoint of stability and production. The B ² group includes Na, K, C
a, a salt with a Group 1 or Group 2 element such as Mg, an amine, or an organic cation such as ammonium.

D ¹ in the B ³ group is preferably a linear or branched alkylene group having 2 or 3 carbon atoms, specifically, an ethylene group, a propylene group, a trimethylene group,
Hydroxytrimethylene, 1-hydroxymethylethylene group and the like are preferable.

Specific examples of R ¹ , R ² and R ³ in the B ³ group include a methyl group, an ethyl group, a propyl group and a 2-hydroxyethyl group, among which a methyl group and an ethyl group are preferred.

[0018] X in B ³ groups ^- as the anion represented by hydroxy ion; chloride, bromide, halide ions such as iodide _{^{ions; CH 3 COO -, CH 3}} C
Organic acid ions such as H ₂ COO ⁻ and CH ₃ (CH ₂ ) ₂ COO ⁻ are exemplified. X ^- as is, hydroxy ion,
Chloride and bromide ions are preferred.

The ratio of the degree of substitution between group A and group B (degree of substitution of group A) / (degree of substitution of group B) is 0.0
01 to 2 is preferable, and 0.01 to 0.1 is more preferable.

The polysaccharide derivative of the present invention is obtained, for example, by reacting a polysaccharide or a derivative thereof with an agent (a), one or more agents selected from agents (b), (c) and (d). , Can be manufactured. (A) Agent: General formula (3) E ² —CONH—R (3) wherein E ² represents an oxycarbonyl group (—COO— or —O
CO-) or an epoxyalkyl group having 3 to 20 carbon atoms into which an ether bond may be inserted, or a hydroxyl or oxo group having 1 to 20 carbon atoms having a halogen atom, which may be substituted It represents a linear or branched alkyl group or a carboxylic acid derivative having 1 to 20 carbon atoms. R represents a linear or branched alkyl group having 4 to 30 carbon atoms which may be substituted by a hydroxyl group. (B) agent: a sulfonating agent selected from vinylsulfonic acid, haloalkanesulfonic acids having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and salts thereof (c) agent: Carboxylating agent selected from halogenated carboxylic acids having 2 to 6 carbon atoms which may be substituted by a hydroxyl group and salts thereof (d) Agent: the following general formula (4)

Embedded image [Wherein, D ² represents an epoxidized alkyl group having 3 to 6 carbon atoms, or a linear or branched halogenated alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group. R ¹ , R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group. X ^- is a hydroxy ion,
It represents an anion such as a halogen ion or an organic acid ion. A cationizing agent represented by

The polysaccharide derivative of the present invention can be obtained by partially introducing a hydrogen atom of a hydroxyl group of a polysaccharide or a derivative thereof into an A group and introducing at ^{least one} of B ^{1 to} B ³ groups. These hydrophobization and sulfonation, carboxylation or cationization may be performed in any order.
Reaction 4 can be carried out simultaneously, but it is preferred to carry out a sulfonation reaction, a carboxymethylation reaction or a cationization reaction following the hydrophobicization.

Examples of the 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 a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, and the like. These substituents can be substituted in the constituent monosaccharide residue singly or in a combination of two or more.Examples of the polysaccharide derivative 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, starch, 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 to form, for example, a polyoxyethylene chain, so that the degree of substitution exceeds 3.0 per constituent monosaccharide. The degree of substitution per constituent monosaccharide residue is from 0.1 to 1
0.0, particularly preferably 0.5 to 5.0. The weight average molecular weight of these polysaccharides or derivatives thereof is 10,000 to 10
The range is preferably from 100,000 to 100,000 to 5,000,000, particularly from 300,000 to 2,000,000.

<Introduction of Group A> The introduction of Group A is carried out by dissolving or dispersing a polysaccharide or a derivative thereof in an appropriate solvent, and reacting with the agent (a) represented by the general formula (3). Will be

Among the groups represented by E ² in the general formula (3), the epoxidized alkyl group preferably has 5 to 15, particularly preferably 6 to 10, carbon atoms, and preferably has an ether bond inserted. The straight-chain or branched-chain alkyl group substituted by a halogen atom has 2 to 15 carbon atoms, particularly 5 to 1 carbon atoms.
0 is preferable, and an oxycarbonyl group or an ether bond may be inserted. The carboxylic acid derivative preferably has 2 to 15 carbon atoms, particularly preferably 4 to 10 carbon atoms, and may have an oxycarbonyl group or an ether bond inserted, and may be substituted with a hydroxyl group or an oxo group. Examples of the carboxylic acid derivative include a carboxyalkyl group and its derivatives, such as methyl ester, ethyl ester, acid halide, tosyl, mesylate, and anhydride. Specifically, 7-oxa-9, 10-epoxydecyl group, 6-oxa-8, 9-epoxynonyl group, 5
-Oxa-7,8-epoxyoctyl group, 7,8-epoxyoctyl group, 6-chlorohexyl group, 7-oxa-
8-oxo-10-chloroformyldecyl, 4-chloroformylbutyl and the like are preferred.

R in the general formula (3) has 8 to 2 carbon atoms.
4, particularly preferably 10 to 18. Specifically, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, isostearyl and the like are preferred.

The hydrophobizing agent represented by the general formula (3) is obtained, for example, by reacting a compound obtained by reacting an alkylamine with a lactone with epichlorohydrin. Alternatively, a compound having an epoxy group at the terminal can be obtained by oxidizing a compound obtained from an unsaturated fatty acid having a double bond at the terminal and an alkylamine. Alternatively, it can be obtained by reacting a compound obtained from an alkylamine and a lactone with an acid anhydride, and further converting the terminal to an acid chloride. Further, it can be obtained by reacting a compound obtained from an alkylamine and a lactone with thionyl chloride. Preferred amines are octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, isostearylamine and the like. Preferred lactones are butyrolactone, valerolactone, caprolactone.

The agent (a) represented by the general formula (3) can be used alone or in combination of two or more. The amount used depends on the desired amount of the group A introduced into the polysaccharide or its derivative. Although it can be appropriately prepared, it is usually preferably in the range of 0.0001 to 10 equivalents, particularly preferably 0.00015 to 5 equivalents, per monosaccharide residue constituting the polysaccharide or its derivative.

This reaction is preferably carried out in the presence of an alkali or an acid, if necessary. Examples of the alkali include hydroxides, carbonates, bicarbonates of Group 1 or Group 2 elements,
Organic bases such as a tertiary amine are exemplified, and among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, pyridine and the like are preferable. The use amount of the alkali is preferably in the range of 1.0 to 3.0 mole times, particularly 1.05 to 1.5 mole times the amount of the hydrophobizing agent represented by the general formula (3) used. Is preferable. Examples of the acid include mineral acids and organic acids, among which sulfuric acid, hydrochloric acid, p
-Toluenesulfonic acid, methanesulfonic acid and the like are preferred. The acid is used in an amount of 0.01 to 0.5 times, especially 0.1 to 0.5 times the amount of the hydrophobizing agent represented by the general formula (3) used.
A range of 0.3 molar times gives good results and is preferred.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. Further, in order to increase the reactivity between the polysaccharide or a derivative thereof and the hydrophobizing agent represented by the general formula (3),
A mixed solvent obtained by adding 0.1 to 100% by weight, more preferably 1 to 50% by weight of water to the lower alcohol may be used.

The reaction temperature is from 0 to 150 ° C., especially from 30 to 10 ° C.
A range of 0 ° C. is preferred. After completion of the reaction, neutralization can be performed using an acid or an alkali. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid, and examples of the alkali include hydroxides of Group 1 or 2 elements such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide. Can be Further, the following reaction may be performed without neutralization.

<Introduction of B ¹ Group> The sulfonation reaction of the polysaccharide or its derivative is carried out by dissolving the polysaccharide or its derivative in an appropriate solvent and reacting it with the agent (b).

In the agent (b), examples of the substituted halogen atom in the haloalkanesulfonic acid having 1 to 5 carbon atoms which may be substituted by a hydroxyl group include a fluorine atom, a chlorine atom and a bromine atom. As salt,
Examples thereof include salts of Group 1 or Group 2 elements such as sodium salt, potassium salt, calcium salt and magnesium salt, and ammonium salts. Examples of the sulfonating agent include vinylsulfonic acid, 3-halo-2-hydroxypropanesulfonic acid, and 3
-Halopropanesulfonic acid is preferred, and these sulfonating agents can be used alone or in combination of two or more, and the amount thereof can be appropriately adjusted depending on the desired amount of the B ¹ group to be introduced into the polysaccharide or its derivative. Usually, it is preferably in the range of 0.005 to 10 equivalents, particularly preferably 0.01 to 5 equivalents, per monosaccharide residue constituting the polysaccharide or its derivative.

The sulfonation reaction is preferably carried out in the presence of an alkali or an acid, if necessary. Examples of the alkali include hydroxides, carbonates and bicarbonates of Group 1 or 2 elements. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is 0.1 to 3.0 mole times, especially 0.5 to 1.5 times the amount of the sulfonating agent used.
A molar amount range is preferable because it gives good results.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of enhancing the reactivity between the polysaccharide or its derivative and the sulfonating agent, a mixed solvent obtained by adding 0.1 to 100% by weight, more preferably 1 to 50% by weight of water to the lower alcohol is used. You may.

The reaction temperature is 0 to 150 ° C., especially 30 to 10 ° C.
A range of 0 ° C. is preferred. After completion of the reaction, the reaction can be neutralized with an acid. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid. Further, the following reaction may be performed without neutralization.

<Introduction of B ² Group> The carboxylation reaction of the polysaccharide or its derivative is carried out by dissolving or dispersing the polysaccharide or its derivative in a suitable solvent, and adding (c)
The reaction is performed by reacting with an agent.

Specific examples of the agent (c) include monochloroacetic acid, sodium monochloroacetate, potassium monochloroacetate, sodium monobromoacetate and potassium monobromoacetate. These agents (c) can be used alone or in combination of two or more, and the amount thereof can be appropriately adjusted depending on the desired amount of the B ² group to be introduced into the polysaccharide or a derivative thereof. 0.005 to 10 equivalents per constituent monosaccharide residue of the derivative, particularly 0.0
A range of 1 to 5 equivalents is preferred.

The alkali used in this reaction includes sodium hydroxide, potassium hydroxide, calcium hydroxide,
Magnesium hydroxide and the like. The amount of the alkali used is 1.0 to 3.0 times the molar amount of the agent (c) used,
Particularly, a range of 1.05 to 2.5 mole times is preferable.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of enhancing the reactivity between the polysaccharide or its derivative and the carboxylating agent, a mixed solvent obtained by adding 0.1 to 100% by weight, more preferably 1 to 50% by weight of water to the lower alcohol is used. You may.

The reaction temperature is 0 to 150 ° C., especially 30 to 10 ° C.
A range of 0 ° C. is preferred. After the reaction, if necessary,
The acid can be used to neutralize the alkali. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid. Further, the following reaction may be performed without neutralization.

<Introduction of B ³ Group> The cationization reaction of the polysaccharide or its derivative is carried out by dissolving or dispersing the polysaccharide or its derivative in an appropriate solvent and reacting with the agent (d).

Among the groups represented by D ² groups in the general formula (4), the epoxidized alkyl group having 3 to 6 carbon atoms includes 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5 -Epoxypentyl group, 5,6-epoxyhexyl group, and the like. Examples of a straight-chain or branched-chain halogenated alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group include 2-chloroethyl group, 3 -Chloropropyl group, 4-chlorobutyl group, 6-chlorohexyl group, 2-bromoethyl group, 2-hydroxy-3-chloropropyl group, 1-hydroxymethyl-2-chloroethyl group and the like. Preferred examples of D ² include:
2,3-epoxypropyl group, 2-chloroethyl group, 3
-Chloropropyl group, 2-hydroxy-3-chloropropyl group and the like. These (d) agents can be used alone or
The polysaccharides or derivatives thereof can be used in combination, and the amount thereof can be appropriately adjusted depending on the desired introduction amount of the B ³ group into the polysaccharide or a derivative thereof. 0.005 to 10 equivalents, especially 0.01 to
A range of 5 equivalents is preferred.

The cationization reaction is preferably carried out in the presence of an alkali or an acid, if necessary. Examples of the alkali include hydroxides, carbonates, bicarbonates and the like of Group 1 or 2 elements. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is preferably in the range of 1.0 to 3.0 mole times, particularly 1.05 to 1.5 mole times the amount of the agent (d) to be used, and good results are obtained.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. In order to enhance the reactivity between the polysaccharide or its derivative and the agent (d),
0.1 to 100% by weight, more preferably 1 to 50% by weight
May be used.

The reaction temperature is 0 to 150 ° C., especially 30 to 10 ° C.
A range of 0 ° C. is preferred. After completion of the reaction, the alkali can be neutralized using an acid. Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, and organic acids such as acetic acid.
Further, the following reaction may be performed without neutralization.

When the polysaccharide derivative obtained in each of the above reactions is subsequently used in another reaction, it can be used as it is without neutralization, and if necessary, it can be separated by filtration or the like. It may be used after washing with water-containing isopropyl alcohol, water-containing acetone, etc. to remove unreacted (a), (b), (c) or (d) agents and salts produced as a result of neutralization and the like. it can. When the introduction of the objective substituent is completed, the polysaccharide derivative of the present invention can be obtained by neutralizing, separating by filtration or the like, washing or the like as necessary, and then drying. .

The polysaccharide derivative of the present invention can be suitably used as a thickener for washing.

[0048]

EXAMPLES In the following examples, the degree of substitution of the substituent (A) of the polysaccharide derivative of the present invention was determined by the Zeisel method [D. G. Anders
on, Anal. Chem. , 43, 894 (1971)], the degree of substitution of the ionic group (B) [sulfoalkyl group (B ¹ ), carboxyalkyl group (B ² ) and cationic group (B ³ )] was determined by colloid titration. Was. In the following examples, "degree of substitution" indicates the average number of substituents per constituent monosaccharide residue.

Synthesis Example 1 Synthesis of N-dodecyl-6- (2,3-epoxypropyloxy) -hexaneamide (compound of Synthesis Example 1) 1) 19.0 g of dodecylamine and 1 part of toluene in a reaction vessel
00g and 0.5 g of 27% sodium methoxide were added thereto, and 11.7 g of ε-caprolactone was added thereto at 25 ° C.
Was added. Thereafter, the temperature was raised to 100 ° C., and the reaction was carried out for 4 hours. After completion of the reaction, the reaction product was separated by filtration, and toluene 10
The resultant was washed twice with 0 g and then twice with 100 g of hexane, and dried under reduced pressure at 70 ° C. overnight to obtain 27.7 g of N-dodecyl-6-hydroxyhexaneamide. 2) 20.0 g of N-dodecyl-6-hydroxyhexanamide obtained in 1), 16.7 g of epichlorohydrin
g, 100 g of n-hexane, and 0.5 g of tetrabutylammonium bromide were charged into a reaction vessel, and 27 g of 48% NaOH was added dropwise at 40 to 50 ° C. for 1 hour. afterwards,
The temperature was raised and the reaction was carried out under reflux for 4 hours. After completion of the reaction, the product was separated by filtration, washed with 100 g of hexane, dissolved in 100 g of chloroform, washed with water, dehydrated with Na ₂ SO ₄ , and the solvent was removed with an evaporator to obtain Compound 2 of Synthesis Example 1.
6.0 g were obtained.

Example 1 (1) 80 g of hydroxyethyl cellulose (hereinafter referred to as HEC) having a weight average molecular weight of about 1.5 million was placed in a reaction vessel.
% Isopropyl alcohol (hereinafter referred to as IPA) 640
g and 5.5 g of 48% NaOH were added and stirred for 30 minutes. 12.0 g of the compound of Synthesis Example 1 was added thereto,
For 8 hours to effect hydrophobization. After completion of the 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 IPA and once with 500 g of acetone, dried under reduced pressure at 70 ° C. for one day, and hydrophobized HE was obtained.
69.8 g of the C derivative were obtained. The degree of substitution of the amide group-containing hydrophobic substituent of the obtained HEC derivative was 0.015. (2) The HEC derivative obtained in (1) in a reaction vessel.
0 g, 300 g 70% IPA and 1.6% 48% NaOH
g and stirred at 25 ° C. for 30 minutes. 3-
16.2 g of sodium chloro-2-hydroxypropanesulfonate and 6.4 g of 48% NaOH were added, and sulfonation was performed at 50 ° C. for 3 hours. After the completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. 70% IPA product
After washing three times with 340 g and then twice with 120 g of IPA,
It was dried at 70 ° C. under reduced pressure for one day to obtain 18.0 g of an HEC derivative (the present compound 1) having an amide group-containing hydrophobic substituent and a sulfonic acid group. The degree of substitution of the sulfonic acid group in the obtained HEC derivative was 0.29.

Example 2 35.5 g of the hydrophobized HEC derivative obtained in Example 1, (1), 350 g of 70% IPA and 48% NaOH
2.4 g were mixed and stirred in a reaction vessel to prepare a slurry liquid, and the mixture was stirred at 25 ° C. for 30 minutes in a nitrogen atmosphere. 25.1 g of sodium monochloroacetate and 48% NaO
H18.0 g was added, and carboxymethylation was performed at 50 ° C. for 5 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 400 g of 70% IPA,
After washing twice with 300 g of IPA, it was dried under reduced pressure at 70 ° C. for one day to obtain 33.8 g of an HEC derivative (compound 2 of the present invention) having an amide group-containing hydrophobic substituent and a carboxymethyl group. The degree of carboxymethylation of the obtained HEC derivative was 0.48.

Example 3 35.5 g of the hydrophobized HEC derivative obtained in (1) of Example 1, 350 g of 70% IPA and 48% NaOH
2.4 g were mixed and stirred in a reaction vessel to prepare a slurry liquid, and the mixture was stirred at 25 ° C. for 30 minutes in a nitrogen atmosphere. The reaction solution was mixed with 7.0 g of a 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride aqueous solution and 48% N
2.0 g of aOH was added, and cationization was performed at 50 ° C. for 1 hour. 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 400 g of 70% IPA,
After washing twice with 300 g, it was dried under reduced pressure at 70 ° C. for one day and night, and H having an amide group-containing hydrophobic substituent and a cationic substituent was used.
34.2 g of an EC derivative (Compound 3 of the present invention) was obtained. The degree of cationization of the obtained HEC derivative was 0.10.

Synthesis of Comparative Compound (1) An HEC (HEC-QP1) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl group of 1.8 was placed in a reaction vessel.
00MH, manufactured by Union Carbide) 80 g, 80% I
A slurry liquid was prepared by adding 640 g of PA and 5.5 g of 48% NaOH, and the mixture was stirred at 25 ° C. for 30 minutes under a nitrogen atmosphere. To this, 3.5 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make it hydrophobic. After completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was separated by filtration. The reaction product was treated once with 500 g of IPA at 50 ° C.
Then, the mixture was washed twice with acetone and dried at 70 ° C. under reduced pressure for one day to obtain 72.8 g of a hydrophobized HEC derivative.

(2) 20.0 g of the hydrophobized HEC derivative obtained in (1), 200 g of 70% IPA and
A slurry liquid was prepared by charging 1.37 g of 8% NaOH and stirred at 25 ° C. for 30 minutes in a nitrogen atmosphere. To the reaction solution, 16.4 g of sodium 3-chloro-2-hydroxypropanesulfonate and 7.0 g of 48% NaOH were added, and 50
Sulfonation was performed at 5 ° C. for 5 hours. After the completion of the reaction, the reaction solution was neutralized with hydrochloric acid, and the product was separated by filtration. 70% I product
After washing three times with 340 g of PA and then twice with 120 g of IPA, the resultant was dried under reduced pressure at 70 ° C. for one day and night, and the HEC derivative substituted with a 3-stearyloxy-2-hydroxypropyl group and a 3-sulfo-2-hydroxypropyl group ( (Comparative compound) 18.3 g was obtained. The degree of substitution of the 3-stearyloxy-2-hydroxypropyl group in the obtained HEC derivative was 0.0042, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.21.

Test Example 1.4 g each of Compounds 1 to 3 of the present invention or Comparative Compound
Was dissolved in 200 ml of ion-exchanged water (hereinafter referred to as water) with stirring, and the viscosity of a 0.7% aqueous solution after standing at 25 ° C. for one day and night was measured. Further, 1.4 g of each of the present compounds 1 to 3 or the comparative compound was added to 200 ml of Emar 20CM (manufactured by Kao Corporation) at 15.5% by weight and Aminone L-02.
[Manufactured by Kao Corporation] Dissolve with stirring in an aqueous surfactant solution containing 4.3% by weight (hereinafter referred to as an aqueous surfactant solution).
The viscosity of the aqueous 0.7% surfactant solution after standing at ℃ for 24 hours was measured. The viscosity was measured using a Brookfield viscometer (12
rpm, 25 ° C.). Table 1 shows the results.

[0056]

[Table 1]

As is clear from Table 1, the comparative compound shows a sharp decrease in viscosity in the aqueous surfactant solution, whereas the compound of the present invention maintains a high viscosity at a low concentration even in the aqueous surfactant solution. It is possible.

[0058]

Industrial Applicability The polysaccharide derivative of the present invention can exhibit high viscosity in a small amount even in the presence of a surfactant, and therefore can be suitably used as a thickener for washing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C090 AA02 BA08 BA30 BA92 BB12 BB36 BB53 BB55 BB62 BB63 BB65 BB72 BB92 BD08 CA36 DA21 4H003 BA12 EB41 EB46 FA30

Claims (5)

[Claims] 1. A polysaccharide derivative in which part or all of the hydrogen atoms of the hydroxyl group of the polysaccharide or a derivative thereof are substituted with an A group and a B group. Group A: Amide group-containing hydrophobic group Group B: Ionic group 2. A group represented by the general formula (1): -E ¹ -CONH-R (1) wherein E ¹ may have a hydroxyl group or an oxo group, or oxycarbonyl It represents a linear or branched alkylene group having 1 to 20 carbon atoms to which a group or an ether bond may be inserted. R represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms which may be substituted by a hydroxyl group. ]
The polysaccharide derivative according to claim 1. 3. The polysaccharide derivative according to claim 1, wherein the group B is at least one group selected from a group consisting of B ¹ , B ² and B ³ . B ¹ group: 1 carbon atom which may be substituted by a hydroxyl group
To 5 sulfoalkyl groups or salts thereof B ² group: 1 carbon atom which may be substituted by a hydroxyl group
5 of carboxyalkyl oxyalkyl group or a salt thereof B ³ groups: group ## STR1 ## represented by the following general formula (2) [In the formula, D ¹ represents a linear or branched alkylene group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group. R ¹ , R ² and R ³ are the same or different and each represent a linear or branched alkyl group having 1 to 3 carbon atoms which may have a hydroxyl group. X ^- represents an anion. ] 4. A thickener comprising the polysaccharide derivative according to claim 1. 5. A polysaccharide or a derivative thereof, (a) an agent,
A method for producing a polyderivative, comprising reacting at least one agent selected from agents (b), (c) and (d). (A) Agent: General formula (3) E ² —CONH—R (3) wherein E ² represents an oxycarbonyl group or an epoxyalkyl group having 3 to 20 carbon atoms into which an ether bond may be inserted. Or 1 carbon atom having a halogen atom which may be substituted by a hydroxyl group or an oxo group
Represents a straight-chain or branched-chain alkyl group having up to 20 carbon atoms, or a carboxylic acid derivative having 1 to 20 carbon atoms. R represents a linear or branched alkyl or alkenyl group having 4 to 30 carbon atoms which may be substituted by a hydroxyl group. (B) agent: a sulfonating agent selected from vinylsulfonic acid, haloalkanesulfonic acids having 1 to 5 carbon atoms which may be substituted with a hydroxyl group, and salts thereof (c) agent: A carboxylating agent selected from halogenated carboxylic acids having 2 to 6 carbon atoms which may be substituted by a hydroxyl group and salts thereof (d) Agent: the following general formula (4): [Wherein, D ² represents an epoxidized alkyl group having 3 to 6 carbon atoms, or a linear or branched halogenated alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group. R ¹ , R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group. X ^- represents an anion. ]
Cationizing agent represented by