JPH11106401A - New polysaccharide derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polysaccharide derivative as a thickener, showing excellent thickening effect at a high ionic strength and particularly suitable for construction materials, and to provide a method for producing the same. SOLUTION: This polysaccharide derivative has a hydroxyl group in the polysaccharide or its derivative, whose hydrogen atoms are partially or totally substituted by the following groups A, B and C: (A) a 10-43C straight-chain or branched alkyl, alkenyl or acyl, whose hydroxide group may be substituted, and oxycarbonyl group or ether bond may be inserted therein, (B) a 1-5C sulfoalkyl group or its salt, whose hydroxide group may be substituted, and (C) a group shown by formula I (D<1> is a 1-6C straight-chain or branched alkylene, whose hydroxide group may be substituted; R<1> , R<2> and R<3> are each a 1-3C straight-chain or branched alkyl, whose hydroxide group may be substituted, where they may be the same or different; and X<-> is a hydroxy ion, halide ion or organic ion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polysaccharide derivative,
In detail, a novel polysaccharide derivative that is excellent in water solubility, shows high viscosity under high ionic strength, has little change in viscosity due to coexistence of powder such as metal oxides and aggregates and temperature change, and shows good fluidity And its manufacturing method.

[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. Is introduced hydrophobic non-ionic cellulose derivative,
It is disclosed that a relatively high viscosity can be obtained 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, these alkyl-substituted cellulose derivatives, although showing an excellent viscosity increase compared to the above-mentioned cellulose ethers, have poor water solubility,
There are problems such as a long time required for uniform dissolution and poor viscosity stability over time.

[0005]

As described above, all of these cellulose ethers and alkyl-substituted cellulose derivatives have properties required as ideal thickeners used for building materials and the like, that is, they dissolve easily. It has excellent thickening effect when mixed with building materials, has high dispersion stabilizing ability, does not impair the fluidity of building materials, etc., coexists with metal salts, surfactants and other additives, However, it did not fully satisfy all of the requirements such as that the change in pH had little effect on the viscosity and that it was excellent in microbial resistance.

Accordingly, an object of the present invention is to provide a thickener which sufficiently satisfies the above-mentioned properties and can be suitably used particularly for building materials.

[0007]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a hydrogen atom of a hydroxyl group of a polysaccharide can be replaced with a specific hydrophobic substituent, a substituent containing a sulfonic acid group, and a hydrogen atom. A novel polysaccharide derivative obtained by substitution with a cationic substituent is excellent in water solubility, shows a high viscosity when mixed with building materials, and has little effect on viscosity such as pH and temperature, and is excellent. The present inventors have found that they show a dispersion stabilizing effect and show good fluidity when used in building materials, and have completed the present invention.

That is, in the present invention, the following groups (A), (B) and (C) (A) hydroxyl groups are substituted for some or all of the hydrogen atoms of the hydroxyl groups of the polysaccharide or derivatives thereof. Or an oxycarbonyl group (—COO— or —OCO—) or a linear or branched alkyl group, alkenyl group or acyl group having 10 to 43 carbon atoms to which an ether bond may be inserted [substituent ( The hydrogen atom of the hydroxyl group of A) may be further substituted with a substituent (A), (B) or (C).] (B) A hydroxyl group which may be substituted with 1 to 1 carbon atoms
5 or a salt thereof [The hydrogen atom of the hydroxyl group of the substituent (B) may be further substituted with a substituent (A), (B) or (C)]. A group represented by (1) [The hydrogen atom of the hydroxyl group of the substituent (C) may be further substituted with a substituent (A), (B) or (C)]

[0009]

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[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, and R ¹ , R ² and R ³ are the same or different and each represents a hydroxyl group; Represents a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted, and X ^- represents a hydroxy ion, a halogen ion or an organic acid ion. And a novel polysaccharide derivative.

The present invention also relates to a polysaccharide or a derivative thereof comprising (a) a glycidyl ether having 10 to 40 carbon atoms having a linear or branched alkyl or alkenyl group, an epoxide, a halide and a halohydrin;
(B) vinyl sulfonic acid, halo optionally substituted by hydroxyl group, (b) a hydrophobizing agent selected from esters having from 40 to 40 linear or branched esters having a saturated or unsaturated acyl group, acid halides and carboxylic anhydrides A sulfonating agent selected from C ₁ -C ₅ alkanesulfonic acids and salts thereof, and (c) the following general formula (2)

[0012]

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[Wherein D ² is an epoxidized alkyl group having 3 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group and substituted by a halogen atom. Wherein 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 be substituted by a hydroxyl group, and X ⁻ represents a hydroxy ion, a halogen ion or Shows organic acid ions. And a method for producing a polysaccharide derivative.

[0014]

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.

[0015]

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Wherein R is the same or different and (1):
Hydrogen atom, methyl group, ethyl group, hydroxyethyl group,
(2): hydrophobic substituent (A), (3): sulfoalkyl group (B) which may be substituted by a hydroxyl group, (4): cationic substituent (C)
Wherein Q 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. QO group, R group, a, b
And c may be the same or different within a repeating unit or between repeating units, and the hydroxyl group of the above-mentioned substituents (A), (B) and (C) may be further substituted with another substituent (A),
(B) and (C) may be substituted. ]

In the novel polysaccharide derivative of the present invention, R in the constituent monosaccharide residue represented by the above general formula is a hydrophobic substituent (A) or a sulfoalkyl group (B) which may be substituted by a hydroxyl group. ) And the cationic substituent (C). However, this does not mean that the substituents (A), (B) and (C) must always be present in the same repeating unit, and the substituents (A), (B) ) And (C) may be introduced with the above average degree of substitution. The remaining R is a hydrogen atom, a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group or the like as described above.

The hydrophobic substituent (A) has 10 to 10 carbon atoms.
As the alkyl group and alkenyl group of 43, a decyl group, an undecyl group, a dodecyl group,
Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henycosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octakosyl, nonacosyl , Triacontyl group, hentriacontyl group, dotriacontyl group, tritriacontyl group, tetratriacontyl group, pentatriacontyl group, hexatriacontyl group, heptatriacontyl group, octatriacontyl group, nonatriacontyl And a tetraalkyl group such as methylundecyl group, methylheptadecyl group, ethylhexadecyl group, methyloctadecyl group, propylpentadecyl group, 2-hexyldecyl group, and 2-octyl group. Dodecyl, 2-heptylundecyl group, 2-decyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecyloctadecyl group, 2-tetradecylbehenyl group and the like are alkenyl groups such as decenyl group, undecenyl group and dodecenyl Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group, henicocenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacocenyl group, hexacocenyl group, octacocenyl group, octacocenyl group, octacocenyl group Examples include a nonacocenyl group, a triacontenyl group, an oleyl group, a linoleyl group, and a linolenyl group. Among them, those having 12 to 36 carbon atoms, particularly 16 to 24 carbon atoms
Are preferred, and from the viewpoint of stability, an alkyl group, particularly a straight-chain alkyl group, is preferred. Examples of the hydrophobic substituent (A) include, in addition to the alkyl group and the alkenyl group, a 2-hydroxyalkyl group, a 1-hydroxymethylalkyl group, a 2-hydroxyalkenyl group, and a 1-hydroxymethylalkenyl group in which a hydroxyl group is 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, such as a group Groups such as 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. Alkyl group, alkenyl group, alkoxypropyl Group, alkenyloxy propyl group, and an acyl group are preferred, in particular, from the stable surface or manufacturing, 2-hydroxyalkyl group,
Alkoxyhydroxypropyl groups are preferred.

These hydrophobic substituents (A) include not only hydrogen atoms of hydroxyl groups directly bonded to polysaccharide molecules, but also hydrogen atoms of hydroxyl groups of hydroxyethyl groups and hydroxypropyl groups bonded to polysaccharide molecules. Alternatively, it may be substituted with a hydrogen atom of a hydroxyl group of another substituent (A), (B) or (C). The degree of substitution by these hydrophobic substituents (A) is 0.00 per constituent monosaccharide residue.
It can be adjusted appropriately within the range of 01 to 1.0, but is preferably in the range of 0.002 to 0.5 per constituent monosaccharide residue.

Examples of the sulfoalkyl group (B) which may be substituted with 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. These substituents (B) are
All or some of them are alkali metals such as Na and K, C
a, a salt with an alkaline earth metal such as Mg, an organic cation group such as an amine, or an ammonium ion. These substituents (B) are not only hydrogen atoms of hydroxyl groups directly bonded to polysaccharide molecules, but also hydrogen atoms of hydroxyl groups of hydroxyethyl groups or hydroxypropyl groups bonded to polysaccharide molecules or other substituents. It may be substituted with a hydrogen atom of a hydroxyl group contained in (A), (B) or (C). The degree of substitution by these substituents (B) can be appropriately adjusted within the range of 0.01 to 1.5 per constituent monosaccharide residue,
A range of 1 to 1.0, particularly 0.02 to 0.5 is preferred.

The hydroxyl group represented by D ¹ in the cationic substituent (C) has 1 to 1 carbon atoms which may be substituted.
6 linear or branched alkylene groups include methylene, ethylene, propylene, trimethylene, 1-methyltrimethylene, tetramethylene, pentamethylene,
Methyltetramethylene, 1,1-dimethyltrimethylene, hexamethylene, 2-hydroxytrimethylene,
-Hydroxytetramethylene, 3-hydroxytrimethylene, 1-hydroxymethylethylene and the like, among which those having 2 or 3 carbon atoms, specifically, ethylene, propylene, trimethylene, 2-hydroxytrimethylene,
1-hydroxymethylethylene and the like are preferred.

R ¹ and R in the cationic substituent (C)
Examples of the linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted on the hydroxyl group represented by ² and R ³ include a methyl group, an ethyl group, a propyl group, and a 2-hydroxyethyl group. Among them, a methyl group and an ethyl group are preferred.

[0023] X in the cationic substituent (C) ^- represented by a chloride ion as a halogen ion, a bromine ion, an iodine ion. Examples of the organic acid ion, CH ₃
COO ⁻ , CH ₃ CH ₂ COO ⁻ , CH ₃ (CH ₂ ) ₂ CO
O- ^{and the} like. X ⁻ is preferably a hydroxy ion, a chlorine ion or a bromine ion.

These cationic substituents (C) include not only a hydrogen atom of a hydroxyl group directly bonded to a polysaccharide molecule, but also a hydrogen atom of a hydroxyethyl group or a hydroxypropyl group bonded to a polysaccharide molecule, or another hydrogen atom. Substituent (A),
It may be substituted with the hydrogen atom of the hydroxyl group of (B) or (C). The degree of substitution by these cationic substituents (C) ranges from 0.0001 to 0.
5, but it is preferably in the range of 0.01 to 0.15 per constituent monosaccharide residue.

The novel polysaccharide derivative of the present invention includes, for example, a polysaccharide or a derivative thereof, which comprises (a) a glycidyl ether, epoxide, halide and halohydrin having a linear or branched alkyl or alkenyl group having 10 to 40 carbon atoms; A hydrophobizing agent selected from esters, acid halides and carboxylic anhydrides having a linear or branched saturated or unsaturated acyl group having 10 to 40 carbon atoms, (b) vinyl sulfonic acid, wherein the hydroxyl group is substituted Good halo C ₁ -C ₅
A sulfonating agent selected from alkanesulfonic acids and salts thereof, and (c) the following general formula (2)

[0026]

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Wherein D ² is an epoxidized alkyl group having 3 to 6 carbon atoms, or a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted by a hydroxyl group and substituted by a halogen atom. Wherein 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 be substituted by a hydroxyl group, and X ⁻ represents a hydroxy ion, a halogen ion or Shows organic acid ions. And a cationizing agent represented by the formula:

The novel polysaccharide derivative of the present invention can be obtained by partially hydrophobizing a hydrogen atom of a hydroxyl group of a polysaccharide or a derivative thereof (introducing a hydrophobic substituent (A)), sulfonating the compound (substituent having a sulfonic acid group). (B)) and cationization (introduction of the cationic substituent (C)). The hydrophobizing, sulfonating, and cationizing reactions may be performed in any order, and two or all three reactions may be performed simultaneously. Preferably, the reaction is carried out.

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 methyl, ethyl, hydroxyethyl, hydroxypropyl, and the like. 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 and the like. 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, with a degree of substitution per constituent monosaccharide residue of 0.1-10.
0, particularly preferably 0.5 to 5.0. The weight average molecular weight of these polysaccharides or derivatives thereof is 10,000 to 1,000.
The range is preferably from 100,000 to 5,000,000, and particularly preferably from 300,000 to 2,000,000.

The hydrophobization reaction, the sulfonation reaction, and the cationization reaction are separately described below.

<Hydrophobic Reaction> The hydrophobic reaction of a polysaccharide or a derivative thereof is carried out by dissolving or dispersing the polysaccharide or a derivative thereof in an appropriate solvent, and (a) a linear or branched alkyl group having 10 to 40 carbon atoms. Or glycidyl ethers having an alkenyl group, epoxides, halides and halohydrins, and hydrophobizing agents selected from esters having 10 to 40 carbon atoms having a linear or branched saturated or unsaturated acyl group, acid halides and carboxylic anhydrides The reaction is carried out by reacting

Among the above hydrophobizing agents, glycidyl ether, epoxide, halide and acyl 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 used is
Although it can be appropriately adjusted depending on the desired amount of the hydrophobic substituent to be introduced into the polysaccharide or its derivative, it is usually from 0.0001 to 0.0001 per monosaccharide residue constituting the polysaccharide or its derivative.
A range of 10 equivalents, particularly 0.0005 to 1 equivalent is preferred.

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
1 to 1000 times the amount of the hydrophobizing agent used, especially 1
A molar amount of from 00 to 500 gives good results and is preferred.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. For the purpose of swelling the polysaccharide or its derivative to increase the reactivity with the hydrophobizing agent, 1
The reaction may be carried out using a mixed solvent to which water is added in an amount of 50 to 50% by weight, more preferably 2 to 30% by weight.

The reaction temperature is 0 to 200 ° 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. 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 or a cationization reaction, it can be used as it is without neutralization, and if necessary, can be separated by filtration or the like. It can also be used after washing with hot water, aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted hydrophobizing agents or salts produced as a result of neutralization or the like. If a sulfonation reaction or a cationization reaction has already been performed before the hydrophobization reaction, neutralization, separation by filtration, etc., washing and the like as necessary, drying, and drying of the present invention New polysaccharide derivatives can be obtained.

<Sulfonation Reaction> The sulfonation reaction of the polysaccharide or its derivative is carried out by dissolving or dispersing the polysaccharide or its derivative in a suitable 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 includes 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 to be used can be appropriately adjusted depending on the desired amount of the sulfonic acid group introduced into the polysaccharide or its derivative, but is usually 0.01 to 10 equivalents per constituent monosaccharide residue of the polysaccharide or its derivative. , Especially 0.0
A range of 3 to 1 equivalent is preferred.

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 to be used is preferably 1.0 to 3.0 mol times, particularly 1.05 to 1.5 mol times with respect to the sulfonating agent to be used, to give good results, and 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 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. The reaction may be carried out.

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. 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 sulfonated polysaccharide thus obtained is subsequently used in a hydrophobization reaction or a cationization reaction, it can be used as it is without neutralization, and if necessary, can be separated by filtration or the like. It can also be used after washing with hot water, aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted sulfonating agents or salts produced as a result of neutralization or the like. In the case where a hydrophobizing reaction or a cationizing reaction has already been performed before the sulfonation reaction, neutralization, separation by filtration, etc., washing and the like as necessary, drying, and drying of the present invention New polysaccharide derivatives can be obtained.

<Cationization Reaction> 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 it with a cationizing agent.

Among the groups represented by D ² in the general formula (2), the epoxidized alkyl group having 3 to 6 carbon atoms includes 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5 -An epoxypentyl group, a 5,6-epoxyhexyl group, etc., which may be substituted with a hydroxyl group and substituted with a halogen atom as a linear or branched alkyl group having 1 to 6 carbon atoms which is 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 a 2,3-epoxypropyl group, a 2-chloroethyl group, a 3-chloropropyl group, and a 2-hydroxy- group.
And a 3-chloropropyl group. These cationizing agents (2) can be used alone or in combination of two or more. The amount of the cationizing agent (2) can be appropriately adjusted depending on the desired amount of the cationic substituent (C) to be introduced into the polysaccharide or its derivative.
Usually, per constituent monosaccharide residue of a polysaccharide or a derivative thereof,
A range of 0.0001 to 10 equivalents, particularly 0.00015 to 5 equivalents is preferred.

This reaction is preferably carried out in the presence of an alkali, if necessary. Such alkali is not particularly limited, and examples thereof include hydroxides, carbonates and bicarbonates of alkali metals or alkaline earth metals. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are 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 cationizing agent (2) to be used, and good results are obtained.

Examples of the solvent include lower alcohols such as isopropyl alcohol and tert-butyl alcohol. Further, for the purpose of increasing the reactivity between the polysaccharide or its derivative and the cationizing agent (2), 0.1 to 100% by weight, more preferably 1 to 5% by weight, based on the lower alcohol.
The reaction may be performed using a mixed solvent to which 0% by weight of water is added.

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. 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 cationized polysaccharide thus obtained is subsequently used in a hydrophobization reaction or a sulfonation reaction, it can be used as it is without neutralization, and if necessary, can be separated by filtration or the like. It can also be used after washing with hot water, aqueous isopropyl alcohol, aqueous acetone solvent or the like to remove unreacted sulfonating agents or salts produced as a result of neutralization or the like. In the case where a hydrophobizing reaction or a sulfonating reaction has already been performed before the cationization reaction, neutralization, separation by filtration, etc., washing and the like as necessary, drying, and drying of the present invention New polysaccharide derivatives can be obtained.

The polysaccharide derivative of the present invention can be suitably used as a thickener, a dispersion stabilizer and the like in various fields such as building materials.

[0050]

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 by the substitution of the substituent (A)
Has no oxo group at the 1-position (forms an ether), the Zeisel method (DG Anderson, Anal. Ch.
em., 43, 894 (1971)).
When the sample had an oxo group at the position (in the case of forming an ester), the sample was hydrolyzed with an acid and neutralized, then esterified with diazomethane, and quantified by gas chromatography. The degree of substitution of the sulfoalkyl group (B) was determined by a colloid titration method. That is, a thickener solution having a known concentration is prepared, and an N / 200 methyl glycol chitosan solution (Wako Pure Chemicals, for colloid titration) of known weight is added thereto with stirring, and a toluidine blue indicator solution (Wako Pure Chemicals, Colloid) is added. Several drops were added). This was back-titrated with an N / 400 polyvinyl potassium sulfate solution (Wako Pure Chemical, colloid titration), and the degree of substitution was calculated from the titer. The degree of substitution of the cationic substituent (C) was determined by a colloid titration method. That is, a thickener solution having a known concentration is prepared, and under stirring,
A known weight of N / 400 polyvinyl potassium sulfate solution (Wako Pure Chemicals, for colloid titration) was added, and several drops of a toluidine blue indicator solution (Wako Pure Chemicals, for colloid titration) were added. This was back-dropped with an N / 400 methyl glycol chitosan solution (Wako Pure Chemical Industries, Ltd., for colloid titration), and the degree of substitution was calculated from the drop constant.

The reaction is carried out in the order of sulfonation and cationization, and when the degree of substitution of the sulfoalkyl group is smaller than the degree of substitution of the cationic substituent, a part is taken out after the sulfonation reaction and washed. Is purified and dried, the degree of substitution of the sulfoalkyl group is calculated by the above method, and after the cationization reaction is completed (part is taken out when the hydrophobicization reaction is further performed).
After washing and other purification and drying, titration is performed according to the method for determining the degree of substitution of the cationic substituent, and the degree of substitution of the cationic substituent is calculated from the titration constant and the degree of substitution of the sulfoalkyl group obtained earlier. did. When the degree of substitution of the sulfoalkyl group was larger than the degree of substitution of the cationic substituent, the degree of substitution of the sulfoalkyl group was determined by the above method. Further, if hydrophobizing reaction is performed, a part is taken out.) Purification and drying are performed, titration is performed in accordance with the method for determining the degree of sulfoalkyl group substitution, and cationicity is determined from the titration constant and the previously obtained degree of sulfoalkyl group substitution. The substitution degree of the substituent was calculated. In addition, the reaction is performed in the order of cationization and sulfonation, and when the degree of substitution of the sulfoalkyl group is smaller than the degree of substitution of the cationic substituent, a part is taken out after the cationization reaction, and purified and dried. The degree of substitution of the cationic substituent is calculated by the above method, and after the sulfonation reaction is completed (part is taken out when the hydrophobic reaction is further performed), purification and drying are performed, and then the substitution of the cationic substituent is performed. The degree of substitution was determined according to the method for determining the degree, and the degree of substitution of the sulfoalkyl group was calculated from the titration constant and the degree of substitution of the cationic substituent obtained above. When the degree of substitution of the sulfoalkyl group was larger than the degree of substitution of the cationic substituent, the degree of substitution of the cationic substituent was determined by the above method. If a hydrophobizing reaction is to be carried out, a portion is taken out), purified and dried, titrated according to the method for determining the degree of substitution of the sulfoalkyl group, and the titration constant and the degree of substitution of the previously obtained cationic substituent are determined. , The degree of substitution of the sulfoalkyl group was calculated.

In the following examples, “degree of substitution” indicates the average number of substituents per constituent monosaccharide residue.

Example 1 (1) Hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-
QP15000H, manufactured by Union Carbide) 80 g,
A slurry liquid was prepared by mixing 640 g of 80% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 2.5 g of stearyl glycidyl ether was added to this solution,
The reaction was carried out at 8 ° C. for 8 hours to effect hydrophobicization. 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 is treated with 500 g of 80% isopropyl alcohol 2
This was washed twice with 500 g of isopropyl alcohol twice, and dried at 70 ° C. under reduced pressure for one day to obtain 74.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) 35.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 350 g of 70% isopropyl alcohol and 2.4 g of 48% aqueous sodium hydroxide solution were mixed to prepare a slurry, which was then subjected to a nitrogen stream. Stirred at room temperature for 30 minutes. 70 mg of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 20 mg of a 48% aqueous sodium hydroxide solution were added to the reaction solution.
And cationization was performed at 50 ° C. for 1 hour. Further 3-
42.6 g of sodium chloro-2-hydroxypropanesulfonate and 18.0 of 48% aqueous sodium hydroxide solution
g was added and sulfonation 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% isopropyl alcohol and twice with 300 g of isopropyl alcohol, and then washed under reduced pressure at 70%.
Dried at ℃ for 24 hours, stearyl glyceryl ether group,
38.3 g of a hydroxyethyl cellulose derivative (the present compound 1) substituted with a 2-hydroxy-3-trimethylammoniumpropyl group and a 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0
The degree of substitution of 031 and 2-hydroxy-3-trimethylammonium propyl groups was 0.001, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.301.

Example 2 (1) Hydroxyethyl cellulose (HEC) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8
-QP100M, manufactured by Union Carbide) 80g, 8
A slurry was prepared by mixing 640 g of 0% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 0.84 g of stearyl glycidyl ether was added to this solution,
The reaction was carried out at 8 ° C. for 8 hours to effect hydrophobicization. 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 is treated with 500 g of 80% isopropyl alcohol 2
This was washed twice with 500 g of isopropyl alcohol twice and dried under reduced pressure at 70 ° C. for one day to obtain 72.8 g of a hydrophobized hydroxyethylcellulose derivative.

(2) 20.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 200 g of 70% isopropyl alcohol, and 1.37 g of 48% aqueous sodium hydroxide solution were mixed to prepare a slurry liquid, and the mixture was stirred under a nitrogen stream. Stirred at room temperature for 30 minutes. 48 mg of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 48% aqueous sodium hydroxide solution 14 were added to the reaction solution.
mg was added and cationization was performed at 50 ° C. for 1 hour. 3 more
4.1 g of sodium chloro-2-hydroxypropanesulfonate and 1.73 of 48% aqueous sodium hydroxide solution
g was added and sulfonation was performed at 50 ° C. for 3 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% isopropyl alcohol and twice with 300 g of isopropyl alcohol, and then washed under reduced pressure at 70%.
Dried at ℃ for 24 hours, stearyl glyceryl ether group,
Thus, 19.4 g of a hydroxyethyl cellulose derivative (the present compound 2) substituted with a 2-hydroxy-3-trimethylammonium propyl group and a 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.0
The degree of substitution of 010, 2-hydroxy-3-trimethylammoniumpropyl group was 0.002, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.078.

Example 3 (1) Hydroxyethyl cellulose (HEC) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8
-QP100M, manufactured by Union Carbide) 80g, 8
A slurry was prepared by mixing 640 g of 0% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 1.7 g of stearyl glycidyl ether was added to this solution,
For 8 hours for hydrophobization. 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 is treated with 500 g of 80% isopropyl alcohol 2
This was washed twice with 500 g of isopropyl alcohol twice and dried under reduced pressure at 70 ° C. for one day to obtain 73.4 g of a hydrophobized hydroxyethylcellulose derivative.

(2) A slurry liquid was prepared by mixing 20.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 200 g of 70% isopropyl alcohol and 1.4 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred under a nitrogen stream. Stirred at room temperature for 30 minutes. 48 mg of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 14 mg of a 48% aqueous sodium hydroxide solution were added to the reaction solution.
And cationization was performed at 50 ° C. for 1 hour. Further 3-
4.7 g of sodium chloro-2-hydroxypropanesulfonate and 1.96 g of a 48% aqueous sodium hydroxide solution
And sulfonated at 50 ° C. for 3 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% isopropyl alcohol and twice with 300 g of isopropyl alcohol, and then reduced under reduced pressure to 70 ° C.
And dried for one day and night with stearyl glyceryl ether group, 2
19.0 g of a hydroxyethyl cellulose derivative (Compound 3 of the present invention) substituted with -hydroxy-3-trimethylammoniumpropyl group and 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the stearyl glyceryl ether group in the obtained hydroxyethyl cellulose derivative was 0.0
The degree of substitution of 019, 2-hydroxy-3-trimethylammonium propyl group was 0.002, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.105.

Example 4 (1) Hydroxyethyl cellulose (HEC) having a weight average molecular weight of about 1.5 million and a degree of hydroxyethyl group substitution of 1.8
-QP100H, manufactured by Union Carbide) 80g, 8
A slurry was prepared by mixing 640 g of 0% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 2.5 g of stearyl glycidyl ether was added to this solution,
For 8 hours for hydrophobization. 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 is treated with 500 g of 80% isopropyl alcohol 2
This was washed twice with 500 g of isopropyl alcohol twice and dried under reduced pressure at 70 ° C. for one day to obtain 76.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) A slurry was prepared by mixing 35.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 350 g of 70% isopropyl alcohol and 2.4 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred under a nitrogen stream. Stirred at room temperature for 30 minutes. 6.0 g of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 48% aqueous sodium hydroxide solution were added to the reaction solution.
74 g was added, and cationization was performed at 50 ° C. for 3 hours. Further, 3.6 g of sodium 3-chloro-2-hydroxypropanesulfonate and 48% aqueous sodium hydroxide solution 1.
51 g was added, and sulfonation 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% isopropyl alcohol,
After washing twice with 300 g of isopropyl alcohol, drying at 70 ° C. under reduced pressure for one day and night, hydroxyethyl cellulose substituted with stearyl glyceryl ether group, 2-hydroxy-3-trimethylammonium propyl group and 3-sulfo-2-hydroxypropyl group. 38.3 g of a derivative (Compound 4 of the present invention) was obtained.

The degree of substitution of the stearyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.0
The degree of substitution of 031 and 2-hydroxy-3-trimethylammonium propyl groups was 0.045, and the degree of substitution of 3-sulfo-2-hydroxypropyl group was 0.040.

Example 5 (1) Hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a hydroxyethyl group substitution degree of 1.8 (HEC-
QP15000H, manufactured by Union Carbide) 80 g,
A slurry liquid was prepared by mixing 640 g of 80% isopropyl alcohol and 5.5 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. 2.5 g of stearyl glycidyl ether was added to this solution,
The reaction was carried out at 8 ° C. for 8 hours to effect hydrophobicization. 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 is treated with 500 g of 80% isopropyl alcohol 2
This was washed twice with 500 g of isopropyl alcohol twice and dried under reduced pressure at 70 ° C. for one day to obtain 75.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) 35.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 350 g of 70% isopropyl alcohol and 2.4 g of 48% aqueous sodium hydroxide solution were mixed to prepare a slurry, and the slurry was prepared under a nitrogen stream. Stirred at room temperature for 30 minutes. 10.5 g of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 3.0 g of a 48% aqueous sodium hydroxide solution were added to the reaction solution, and cationization was performed at 50 ° C. for 1 hour.
Further, 17.2 g of sodium 3-chloro-2-hydroxypropanesulfonate and 7.2 g of a 48% aqueous sodium hydroxide solution were added, and sulfonation 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 is mixed with 400 g of 70% isopropyl alcohol 3
After washing twice with 300 g of isopropyl alcohol twice, the mixture was dried at 70 ° C. under reduced pressure for one day and night, and substituted with stearyl glyceryl ether group, 2-hydroxy-3-trimethylammonium propyl group and 3-sulfo-2-hydroxypropyl group. 37.3 g of a hydroxyethyl cellulose derivative (the present compound 5) was obtained.

The degree of substitution of the stearyl glyceryl ether group of the obtained hydroxyethyl cellulose derivative was 0.0
The substitution degree of 030 and 2-hydroxy-3-trimethylammonium propyl groups was 0.13, and the substitution degree of 3-sulfo-2-hydroxypropyl group was 0.16.

Example 6 (1) Hydroxyethylcellulose (HEC) having a weight average molecular weight of about 1.5 million and a degree of hydroxyethyl group substitution of 1.8
−QP100MH, manufactured by Union Carbide) 80 g,
A slurry liquid was prepared by mixing 640 g of 80% isopropyl alcohol and 5.5 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 solution, 4.82 g of dodecyl glycidyl ether (purity 83
%) And reacted at 80 ° C. for 8 hours to effect hydrophobicization. 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 washed twice with 500 g of 80% isopropyl alcohol,
g, and dried under reduced pressure at 70 ° C. for one day to obtain 76.3 g of a hydrophobized hydroxyethylcellulose derivative.

(2) A slurry was prepared by mixing 35.0 g of the hydrophobized hydroxyethyl cellulose derivative obtained in (1), 350 g of 70% isopropyl alcohol and 2.4 g of a 48% aqueous sodium hydroxide solution, and the mixture was stirred under a nitrogen stream. Stirred at room temperature for 30 minutes. 140 mg of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 40% of 48% aqueous sodium hydroxide solution were added to the reaction solution.
mg was added and cationization was performed at 50 ° C. for 1 hour. 3 more
11. 28.3 g of sodium chloro-2-hydroxypropanesulfonate and 48% aqueous sodium hydroxide solution.
0 g was added, and sulfonation was performed at 50 ° C. for 3 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% isopropyl alcohol and twice with 300 g of isopropyl alcohol.
Dried at 0 ° C. for one day and night to obtain dodecyl glyceryl ether group,
38.3 g of a hydroxyethyl cellulose derivative (the present compound 6) substituted with a 2-hydroxy-3-trimethylammoniumpropyl group and a 3-sulfo-2-hydroxypropyl group was obtained.

The degree of substitution of the dodecylglyceryl ether group in the obtained hydroxyethylcellulose derivative was 0.01
The degree of substitution of the 32,2-hydroxy-3-trimethylammoniumpropyl group was 0.002, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.223.

Example 7 (1) Hydroxyethyl cellulose having a weight average molecular weight of about 800,000 and a degree of hydroxyethyl group substitution of 1.8 (HEC-
QP1500H, manufactured by Union Carbide) 50.0
g, 80% isopropyl alcohol 400 g and 48%
A slurry solution was prepared by mixing 3.4 g of an aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. Octyl bromide (40.6 g) was added to the solution, and the mixture was reacted at 80 ° C. for 8 hours to make the solution 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 washed twice with 500 g of 80% isopropyl alcohol,
It was washed twice with 500 g of isopropyl alcohol and dried at 70 ° C. under reduced pressure for one day to obtain 61.6 g of a hydrophobized hydroxyethylcellulose derivative.

(2) A slurry was prepared by mixing 35.0 g of the hydrophobized hydroxyethylcellulose derivative obtained in (1), 350 g of 70% isopropyl alcohol and 2.3 g of a 48% aqueous sodium hydroxide solution to prepare a slurry. Stirred at room temperature for 30 minutes. 0.305 g of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 90 mg of a 48% aqueous sodium hydroxide solution were added to the reaction solution, and cationization was performed at 50 ° C. for 1 hour. Further, 28.3 g of sodium 3-chloro-2-hydroxypropanesulfonate and 48% aqueous sodium hydroxide solution 1
2.0 g was added, and sulfonation was performed at 50 ° C. for 3 hours.
After completion of the reaction, the reaction solution was neutralized with acetic acid, and the product was separated by filtration.
The product is diluted with 600 g of 70% isopropyl alcohol 3
After washing twice with 400 g of isopropyl alcohol twice, the mixture was dried under reduced pressure at 70 ° C. for one day and night to obtain an octyl ether group, 2-
Hydroxyethyl cellulose derivatives substituted with a hydroxy-3-trimethylammonium propyl group and a 3-sulfo-2-hydroxypropyl group (Compound 7 of the present invention)
24.8 g were obtained.

The degree of substitution of the octyl ether group of the obtained hydroxyethylcellulose derivative was 0.296, the degree of substitution of the 2-hydroxy-3-trimethylammonium propyl group was 0.005, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.005. The degree was 0.21.

Example 8 (1) Weight average molecular weight: about 400,000, degree of substitution of methyl group
60 g of methyl cellulose (Metrouse SM-800, manufactured by Shin-Etsu Chemical Co., Ltd.), 600 g of 90% tert-butyl alcohol, and 5.7 of a 48% aqueous sodium hydroxide solution.
g was mixed to prepare a slurry liquid, and the mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this solution, 3.8 g of stearyl glycidyl ether was added, and the mixture was reacted at 80 ° C. for 8 hours to make the solution 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 washed three times with 500 g of isopropyl alcohol, dried under reduced pressure at 70 ° C. for one day, and hydrophobized methylcellulose derivative.
6 g were obtained.

(2) 35.0 g of the hydrophobized methylcellulose derivative obtained in (1), 350 g of 80% tert-butyl alcohol and a 48% aqueous solution of sodium hydroxide.
A slurry liquid was prepared by mixing 33 g, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. 60% (3-chloro-2) was added to the reaction solution.
5.6 g of -hydroxypropyl) trimethylammonium chloride and 1.6 g of a 48% aqueous sodium hydroxide solution
Was added and cationization was performed at 50 ° C. for 3 hours. 25 more
% Sodium vinyl sulfonate 72.8 g and tert
220 g of -butyl alcohol was added, and sulfonation was performed at 50 ° C for 3 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 300 g of 70% isopropyl alcohol, 300 g of isopropyl alcohol
And dried under reduced pressure at 70 ° C. for one day and night, and methylcellulose derivative (Compound 8 of the present invention) substituted with stearyl glyceryl ether group, 2-hydroxy-3-trimethylammonium propyl group and sulfoethyl group 3
3.6 g were obtained.

The degree of substitution of the stearyl glyceryl ether group of the obtained methyl cellulose derivative was 0.00277,
The degree of substitution of the 2-hydroxy-3-trimethylammonium propyl group was 0.029, and the degree of substitution of the sulfoethyl group was 0.19.

Example 9 (1) Hydroxyethylcellulose (HEC) having a weight average molecular weight of about 1.5 million and a degree of substitution of hydroxyethyl groups of 1.8
-QP100MH, manufactured by Union Carbide) 50 g,
A slurry liquid was prepared by mixing 500 g of 70% isopropyl alcohol and 3.45 g of a 48% aqueous sodium hydroxide solution, and stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this solution, 7.48 g of 60% (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 2.16 g of a 48% aqueous sodium hydroxide solution were added, and the mixture was reacted at 50 ° C. for 3 hours to perform cationization. After the completion of the cationization reaction, the reaction solution was filtered, and the reaction product was separated by filtration. The reaction product was washed three times with 300 g of 70% isopropyl alcohol and twice with 200 g of isopropyl alcohol.
It was dried at 0 ° C. for one day to obtain 47.6 g of a cationized hydroxyethyl cellulose derivative.

(2) 30.0 g of the cationized hydroxyethyl cellulose derivative obtained in (1), pyridine 70
g and ion-exchanged water 5 g were mixed to prepare a slurry liquid, and the mixture was stirred at room temperature for 30 minutes under a nitrogen stream. This solution is
After cooling to 0 ° C or lower, dodecanoic acid chloride 1
3.6 g was added dropwise, the solution was further heated, and hydrophobized at 90 ° C. for 5 hours. After completion of the reaction, the reaction solution was added to 500 g of 80% isopropyl alcohol, and the resulting solid was separated by filtration.
Wash three times with 400 g of 80% isopropyl alcohol and twice with 300 g of isopropyl alcohol,
For 1 day to obtain 28.5 g of a cationized and hydrophobized hydroxyethyl cellulose derivative.

(3) The cationized and hydrophobized hydroxyethyl cellulose derivative obtained in (2) 20.0
g, 70% isopropyl alcohol 200 g and 48%
A slurry solution was prepared by mixing 1.4 g of an aqueous sodium hydroxide solution, and the mixture was stirred at room temperature under a nitrogen stream for 20 minutes. The reaction mixture was charged with 7.8 g of sodium 3-chloro-2-hydroxypropanesulfonate and a 48% aqueous sodium hydroxide solution.
3 g was added, and sulfonation was performed at 50 ° C. for 3 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 70% isopropyl alcohol 600 and twice with 400 g of isopropyl alcohol, and then dried under reduced pressure at 70%.
Dried at room temperature for one day and night, and a hydroxyethyl cellulose derivative (compound 9 of the present invention) substituted with a dodecyl ester group, a 2-hydroxy-3-trimethylammoniumpropyl group and a 3-sulfo-2-hydroxypropyl group (19.0).
g was obtained.

The degree of substitution of the dodecyl ester group of the obtained hydroxyethyl cellulose derivative was 0.051, the degree of substitution of the 2-hydroxy-3-trimethylammonium propyl group was 0.049, and the degree of substitution of the 3-sulfo-2-hydroxypropyl group was 0.059. The degree was 0.172.

Comparative Example 1 Hydroxyethyl cellulose (HEC-QP) having a weight average molecular weight of about 1.5 million and a degree of hydroxyethyl group substitution of 1.8 was used.
Comparative Compound 1 was used as it was (100 MH, manufactured by Union Carbide).

Test Example 1 Thickening Test 20 g of the compound of the present invention and 1.0 g of each of the comparative compounds were added.
After dissolving in 0 ml of ion-exchanged water with stirring and leaving it at room temperature for 24 hours, the viscosity of each aqueous solution was measured. Further, 1.0 g of the compound of the present invention and 1.0 g of the comparative compound were dissolved in 200 ml of a 3.0% by weight aqueous sodium chloride solution with stirring, and left at room temperature for 24 hours.
The viscosity of each aqueous solution was measured. The viscosity was measured using a Brookfield viscometer (12 rpm, 25 ° C.).
Table 1 shows the results.

[0084]

[Table 1]

The novel polysaccharide derivative of the present invention not only gives an aqueous solution having high transparency, but also has an excellent thickening property under a high ionic strength, as is clear from Table 1.

Example 10 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 0.14g

[0087]

Industrial Applicability The novel polysaccharide derivative of the present invention is excellent in an aqueous solution, shows an excellent thickening effect by adding a small amount under a high ionic strength, and has little change in viscosity due to coexistence of powder and temperature.
Has an excellent dispersion stabilizing effect. 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 dispersant, and the like for building materials, cosmetics, toiletries, and the like.

Claims (5)

[Claims] 1. A part or all of hydrogen atoms of a hydroxyl group of a polysaccharide or a derivative thereof may be substituted with the following groups (A), (B) and (C): (A) a hydroxyl group; In addition, an oxycarbonyl group (—COO— or —OCO—) or a linear or branched alkyl group, alkenyl group, or acyl group having 10 to 43 carbon atoms which may have an inserted ether bond [the substituent (A) The hydrogen atom of the hydroxyl group may be further substituted with a substituent (A), (B) or (C).] (B) A hydroxyl group which may be substituted with 1 to 1 carbon atoms
5 or a salt thereof [The hydrogen atom of the hydroxyl group of the substituent (B) may be further substituted with a substituent (A), (B) or (C)]. A group represented by (1) [The hydrogen atom of the hydroxyl group of the substituent (C) may be further substituted with a substituent (A), (B) or (C)] [In the formula, D ¹ represents a linear or branched alkylene 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 represent a linear or branched alkyl group having 1 to 3 carbon atoms which may be substituted by a hydroxyl group, and X ⁻ represents a hydroxy ion, a halogen ion or an organic acid ion Is shown. ] The novel polysaccharide derivative characterized by being substituted by: 2. The average degree of substitution per constituent monosaccharide residue by the substituent (A) is 0.0001 to 1.0, and the average degree of substitution per constituent monosaccharide residue by the substituent (B) is 0. .0
The novel polysaccharide derivative according to Claim 1, wherein the average degree of substitution per constituent monosaccharide residue by the substituent (C) is from 0.0001 to 0.5. 3. A linear or branched alkyl group, alkenyl group or acyl group having 12 to 36 carbon atoms which may be substituted with a hydroxyl group for the substituent (A) and into which an ether bond may be inserted. Wherein the substituent (B) is a 2-sulfoethyl group, a 3-sulfopropyl group, a 3-sulfo-2-hydroxypropyl group, and a 2-sulfo-1- (hydroxymethyl) group. One or more selected from ethyl groups, and D ¹ of the substituent (C) has 2 to 2 carbon atoms which may be substituted by a hydroxyl group.
The novel polysaccharide derivative according to claim ¹ , which is a linear alkylene group of 4, wherein R ¹ , R ² and R ³ are the same or different and are linear alkyl groups having 1 to 3 carbon atoms. 4. 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 novel polysaccharide derivative according to any one of claims 1 to 3, which is selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylmethylguar gum, and hydroxypropylmethylstarch. 5. A polysaccharide or a derivative thereof, comprising: (a) a glycidyl ether, epoxide, halide or halohydrin having a linear or branched alkyl group or alkenyl group having 10 to 40 carbon atoms, and a straight chain having 10 to 40 carbon atoms. Esters having a chain or branched saturated or unsaturated acyl group, hydrophobizing agents selected from acid halides and carboxylic anhydrides,
(B) vinyl sulfonic acid, a halo C ₁ -C ₅ alkane sulfonic acid optionally substituted with a hydroxyl group and a sulfonating agent selected from salts thereof, and (c) a sulfonating agent represented by the following general formula (2): [Wherein, D ² is an epoxidized alkyl group having 3 to 6 carbon atoms,
Or a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group and substituted with a halogen atom, wherein R ¹ , R ² and R ³ are the same or different and are substituted by a hydroxyl group; Represents an optionally substituted linear or branched alkyl group having 1 to 3 carbon atoms, and X ^- represents a hydroxy ion, a halogen ion or an organic acid ion. And a cationizing agent represented by the formula: