JP2019099824A - Polysaccharide derivative - Google Patents

Abstract

To provide a polysaccharide derivative which enables the cleaning properties thereof for clothes and the like to be improved and provides a composition such as a detergent composition with which the polysaccharide derivative is blended, the composition being excellent in handleability.SOLUTION: The polysaccharide derivative having a cationic group, and a hydrocarbon group (R) having 2 or more carbon atoms is provided in which the hydrocarbon group (R) is bound directly or via a connection group (excluding a cationic group) to a group obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkylated polysaccharide, and the hydroxyalkylated polysaccharide has a weight average molecular weight of 10,000 to 190,000.SELECTED DRAWING: None

Description

  The present invention relates to polysaccharide derivatives.

Polysaccharide derivatives are used in formulation components such as detergent compositions, and their applications are diverse.
For example, in Patent Document 1, as an agent useful as a laundry finish, some or all of the hydrogen atoms of hydroxyl groups of polysaccharides or derivatives thereof are the following groups (A), (B) and (C) Polysaccharide derivatives substituted with are described.
(A) a linear or branched alkyl group having a carbon number of 10 to 43, which may be substituted with a hydroxyl group, and may have an oxycarbonyl group (-COO- or -OCO-) or an ether bond inserted; Alkenyl group or acyl group (B) carboxymethyl group or salt thereof (C) specific cationic group

It is an object of the present invention to provide an aqueous hair cleansing agent which is excellent in the slipperiness of hair during washing and rinsing, and which can impart moist feeling to dried hair, even in damaged hair. As the aqueous hair cleansing agent which contains the following components (A), (B) and (C) and water and has a pH of 2 or more and 6 or less at 25 ° C. when diluted to 20 times by mass with water It is done.
(A) Anionic surfactant (B) A main chain derived from anhydroglucose, and the degree of substitution of a cationized oxyalkylene group per unit of the anhydroglucose is 0.01 or more and 1.0 or less, and a glycerol group Cationic group-containing cellulose ether having a substitution degree of 0.5 or more and 5.0 or less, and a substitution degree of a group containing a hydrocarbon group having 3 or more and 18 or less carbon atoms of 0 or more and 0.2 or less C) Monoalkyl glyceryl ether or mono alkenyl glyceryl ether having an alkyl group or alkenyl group having 4 to 12 carbon atoms

  Patent Document 3 discloses that the concentration of the long-acting polymer to the solvent of the solution of the long-acting polymer and the water-miscible polar solvent is about 0, which comprises a) the long-acting polymer and b) the water-miscible polar solvent. .1 wt.% To about 20 wt.% And the molecular weight (Mw) of the long-lasting polymer as determined by size exclusion chromatography is in the range of greater than about 50 kilodaltons to about 800 kilodaltons or less, Persistence effect on keratin surface selected from the group consisting of synthetic polymers comprising a polysaccharide and a cationic monomer, wherein the degree of cation substitution of the persistent polymer is greater than about 0.001 units, Disclosed are personal care composition additives for providing

JP 2000-178303 A JP, 2015-168666, A Japanese Patent Application Publication No. 2013-529644

As a washing component for clothing, it suppresses strong adhesion of sebum dirt, improves the washability of sebum dirt at the time of washing, and has a good flowability of the washing agent containing the washing component and a washing component excellent in handleability. It is done.
However, conventional agents have not been able to exhibit sufficient performance.
The present invention relates to a polysaccharide derivative which can improve the detergency of sebum dirt at the time of cleansing and is excellent in the handleability of a composition such as a detergent composition containing it.

The present inventors have found that a specific polysaccharide derivative solves the above-mentioned problems.
That is, the present invention relates to the following <1> and <2>.
<1> A polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms, wherein the hydrocarbon group (R) is directly or excluding a linking group (a cationic group A polysaccharide derivative, wherein the hydroxyalkylated polysaccharide has a weight average molecular weight of 10,000 or more and 190,000 or less, which is bonded to a group in which a hydrogen atom is removed from a hydroxyl group of a hydroxyalkylated polysaccharide via
<2> A hydrocarbon group (R) having 2 or more carbon atoms is introduced into a hydroxyalkylated polysaccharide having a weight average molecular weight of 10,000 to 190,000 and then reacted with a cationizing agent, as described in <1>. Method of producing a polysaccharide derivative of

ADVANTAGE OF THE INVENTION According to this invention, while being able to improve the washability of the sebum dirt at the time of washing | cleaning, the polysaccharide derivative which is excellent in the handleability of compositions, such as a detergent composition which mix | blended it, is provided.
In the following description, "washing performance" means the ability to suppress strong adhesion of sebum stains at the time of use, such as at the time of dressing, etc., and improve the performance of removing sebum stains at the time of washing. The term "characteristic" means the flowability of a composition containing the polysaccharide derivative, for example, a detergent, etc. When the flowability of the preparation is good, the handleability of the composition is improved.

[Polysaccharide derivative]
The polysaccharide derivative of the present invention is a polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms (hereinafter, also simply referred to as "hydrocarbon group (R)"), The hydrocarbon group (R) is bonded directly or through a linking group (excluding a cationic group) to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide, and the hydroxyalkylated polysaccharide has a weight The average molecular weight is 10,000 or more and 190,000 or less.
By treating a detergent composition or the like containing the polysaccharide derivative of the present invention on a fabric such as a garment, adhesion of sebum dirt is suppressed and good formulation fluidity is obtained. I found it. Although the detailed mechanism of action is unknown, a part is presumed as follows.
The polysaccharide derivative of the present invention has a cationic group, and when it is treated in the presence of an anionic surfactant or electrostatic interaction with a hydrophobic fiber, for example, a negative charge possessed by a polyester fiber, The polysaccharide derivative is adsorbed on the surface of the fabric by electrostatic interaction with the anionic surfactant adsorbed on the surface of the fabric. Furthermore, the polysaccharide derivative of the present invention has a hydrocarbon group (R) having 2 or more carbon atoms and adheres to the surface of the fabric by hydrophobic interaction, particularly when the fabric is hydrophobic. As described above, by having the cationic group and the hydrocarbon group (R), the adsorptivity to the fabric is improved.
On the other hand, by adsorbing the polysaccharide derivative of the present invention to the surface of the fabric, it is considered that the oil repellency is improved while hydrophilizing the surface of the fabric formed of hydrophobic fibers. As a result, it is presumed that firm adhesion of sebum dirt is suppressed.
Furthermore, when the hydroxyalkylated polysaccharide has a specific weight-average molecular weight, good formulation fluidity is obtained when the polysaccharide derivative is incorporated into the composition while maintaining the above-mentioned washing performance. This is because the number of hydroxyl groups or cationic groups contained in one molecule of the polysaccharide derivative of the present invention is less than a specific number, so that the interaction between the hydroxyl groups or cationic groups and the functional groups of the surfactant is reduced. It is presumed that the sex is increased.
The polysaccharide derivative of the present invention is particularly effective for fabrics formed of hydrophobic fibers, but is not limited thereto.

<Hydroxyalkylated polysaccharide>
The polysaccharide derivative of the present invention has a cationic group and a hydrocarbon group (R) bonded to a hydroxyalkylated polysaccharide having a weight average molecular weight of 10,000 or more and 190,000 or less.
The hydroxyalkylated polysaccharides used in the present invention include polysaccharides such as cellulose, guar gum and starch, or polysaccharides in which a substituent such as a methyl group is introduced into these, and hydroxyalkyl such as a hydroxyethyl group and a hydroxypropyl group. Those having a group are mentioned. The term "hydroxyalkylation" means monohydroxyalkylation.
Examples of hydroxyalkylated polysaccharides include hydroxyethyl cellulose, hydroxyethyl guar gum, hydroxyethyl 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 can be mentioned.
The polysaccharide is preferably cellulose or guar gum, more preferably cellulose.
Also, the hydroxyalkylated polysaccharide is preferably hydroxyethyl cellulose, hydroxypropyl cellulose, more preferably hydroxyethyl cellulose.

(Hydroxyalkyl group)
In the present invention, in the hydroxyalkylated polysaccharide, a hydroxyalkyl group is introduced to the polysaccharide. The hydroxyalkyl group is preferably a hydroxyethyl group or a hydroxypropyl group. The hydroxyalkylated polysaccharide preferably has at least one selected from a hydroxyethyl group and a hydroxypropyl group, more preferably only a hydroxyethyl group or a hydroxypropyl group, and still more preferably only a hydroxyethyl group. . That is, the hydroxyalkylated polysaccharide may have both a hydroxyethyl group and a hydroxypropyl group, preferably only one of them, and more preferably only a hydroxyethyl group.
The degree of substitution of the hydroxyalkyl group is preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1 or more, and still more preferably 1.5 or more from the viewpoint of solubility in water. Further, from the viewpoint of cleaning performance, it is preferably 10 or less, more preferably 8 or less, still more preferably 5 or less, still more preferably 3 or less, still more preferably 2.5 or less.
The degree of substitution of a hydroxyalkyl group is, for example, the degree of substitution of any group when it has only a hydroxyethyl group or a hydroxypropyl group. On the other hand, when it has both a hydroxyethyl group and a hydroxypropyl group, it is the sum of the degree of substitution of the hydroxyethyl group and the degree of substitution of the hydroxypropyl group.
In the present invention, the degree of substitution of group X is the molar average degree of substitution (MS) of group X, and the average number of substitution moles of X group per mole of constituent monosaccharide units constituting the main chain of the polysaccharide derivative or polysaccharide Means For example, in the case where the hydroxyalkylated polysaccharide is hydroxyethyl cellulose, the "degree of substitution of hydroxyethyl group" means the average number of moles of (bound) hydroxyethyl groups introduced per 1 mol of anhydroglucose unit. means.

The hydroxyalkylated polysaccharide of the present invention may have a glycerol group as a substituent, but the introduction of the glycerol group tends to lower the cleaning performance. Therefore, from the viewpoint of obtaining high detergency, the degree of substitution of the glycerol group is preferably less than 0.5, more preferably less than 0.1, still more preferably 0, ie, no glycerol group.
The hydroxyalkylated polysaccharide having a glycerol group is obtained by acting a glycerolating agent on the polysaccharide, and as the glycerolating agent, glycidol; 3-chloro-1,2-propanediol, 3-bromo-1,2 3-halo-1,2-propanediol such as propanediol; glycerin; glycerin carbonate. Among these, glycidol is preferred from the viewpoint of no by-production of salt and reactivity.

(Weight average molecular weight)
In the present invention, the weight average molecular weight of the hydroxyalkylated polysaccharide is at least 10,000, preferably at least 30,000, more preferably at least 50,000, still more preferably at least 70,000, still more preferably from the viewpoint of improving the washing performance. It is 100,000 or more, more preferably 130,000 or more.
In addition, from the viewpoint of formulation fluidity, it is 190,000 or less, preferably 180,000 or less, more preferably 170,000 or less, further preferably 160,000 or less.
The weight average molecular weight of the hydroxyalkylated polysaccharide is measured by the method described in the examples.

<Cationic group>
In the polysaccharide derivative of the present invention, a cationic group is bonded to a group obtained by removing a hydrogen atom from the hydroxyl group of the above-described hydroxyalkylated polysaccharide. The phrase "bonded to a group obtained by removing a hydrogen atom from the hydroxyl group of a hydroxyalkylated polysaccharide" is limited to an embodiment in which a hydrogen atom is removed from the hydroxyl group of a hydroxyalkyl group bonded to a polysaccharide. It is not a thing. That is, when the polysaccharide is a cellulose, it may be bonded to a group obtained by removing a hydrogen atom from a hydroxyl group (hydroxyl group to which a hydroxyalkyl group is not bonded) possessed by glucose forming a cellulose skeleton. It is not a thing. Here, the cationic group means a quaternary ammonium salt or a tertiary amine which can be converted to a quaternary ammonium salt by adding a proton and a quaternary ammonium salt (quaternary ammonium cation) thereof.
The degree of substitution (MS _C ) of the cationic group is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, still more preferably 0.02, from the viewpoint of improving the cleaning performance. The above, more preferably 0.05 or more, and still more preferably 0.07 or more.
In addition, the degree of substitution (MS _C ) of the cationic group is preferably 1 or less, more preferably 0.5 or less, and more preferably 1 or less, more preferably 0.5 or less, from the viewpoint of formulation fluidity, particularly formulation fluidity when using an anionic surfactant. Preferably it is 0.4 or less, still more preferably 0.35 or less, still more preferably 0.3 or less, still more preferably 0.25 or less, still more preferably 0.2 or less, still more preferably 0.15 It is below.
The degree of substitution of the cationic group is preferably 0.001 or more and 1 or less, more preferably from the viewpoint of improving the cleaning performance, and from the viewpoint of formulation fluidity, particularly formulation fluidity when using an anionic surfactant. 0.001 or more and 0.5 or less, more preferably 0.001 or more and 0.4 or less, still more preferably 0.001 or more and 0.35 or less, still more preferably 0.001 or more and 0.3 or less, still more preferably Is from 0.005 to 0.3, more preferably from 0.01 to 0.25, still more preferably from 0.02 to 0.2, still more preferably from 0.05 to 0.2, more preferably More preferably, it is 0.07 or more and 0.15 or less.
The introduction amount of the cationic group is measured by the method described in the examples.

  The cationic group preferably contains a quaternary ammonium cation, and the cationic group introduced into the hydroxyalkylated polysaccharide is generally represented by the following formula (2-1) or formula (2-2): Is preferred.

(In Formula (2-1) and Formula (2-2), R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ⁻ represents an anion, and t is 0 or more 3 represents an integer of 3 or less, and * represents a bonding position to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide.)

R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, and is preferably a linear or branched hydrocarbon group.
In a preferred embodiment, R ^{21 to} R ²³ each independently represent a linear or branched hydrocarbon group having 1 to 3 carbon atoms. As a linear or branched hydrocarbon group having 1 to 3 carbon atoms, a methyl group, an ethyl group, an n-propyl group and an isopropyl group are exemplified. Among these, preferably a methyl group or an ethyl group, more preferably all of R ²¹ to R ²³ is a methyl group or an ethyl group, and more preferably all R ²¹ to R ²³ is a methyl group.
Moreover, as another preferable aspect, at least one of R ^{21 to} R ²³ represents a hydrocarbon group having 4 to 24 carbon atoms. Of R ²¹ to R ^23, 1 single but a hydrocarbon group having 4 to 24 carbon atoms, but the remaining two preferably a hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group having 4 to 24 carbon atoms preferably has 6 or more carbon atoms, more preferably 8 or more carbon atoms, and still more preferably 10 or more carbon atoms, from the viewpoint of cleaning performance, and preferably 22 or less carbon atoms, more preferably It is 18 or less, more preferably 16 or less, and still more preferably 14 or less.
Among them, R ²¹ to R ²³ is preferably exhibit a straight-chain or branched hydrocarbon group having 1 to 3 carbon atoms.

In Formula (2-1) and Formula (2-2), t represents an integer of 0 or more and 3 or less, preferably 1 or more and 3 or less, more preferably 1 or 2, and further preferably 1.
X < ^- > shows an anion and is a counter ion of quaternary ammonium cation. Specifically, alkyl sulfate ion having 1 to 3 carbon atoms, sulfate ion, phosphate ion, carboxylate ion having 1 to 3 carbon atoms (formate ion, acetate ion, propionate ion), and halide ion It is illustrated.
Among these, from the viewpoint of easiness of production and availability of raw materials, X ⁻ is preferably at least one selected from alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, and halide ions, Preferably it is a halide ion. The halide ion includes fluoride ion, chloride ion, bromide ion and iodide ion, but from the viewpoint of water solubility and chemical stability of the polysaccharide derivative to be obtained, preferably chloride ion and bromide ion And more preferably a chloride ion.
X ⁻ may be one kind alone, or two or more kinds.

Groups represented by the formulas (2-1) and (2-2) are groups obtained by removing a hydrogen atom from the hydroxyl group of a hydroxyalkylated polysaccharide through the linking group of R ^{21 to} R ²³ which are hydrocarbon groups. It can be said that the linking group of the hydrocarbon group does not contain a cationic group. When at least one of R ^{21 to} R ²³ is a hydrocarbon group having 2 or more carbon atoms (R), a polysaccharide derivative to which a group represented by Formula (2-1) and Formula (2-2) is bonded is a cation Since a hydrocarbon group having 2 or more carbon atoms (R) is bonded via a linking group containing a sexic group, it is regarded as a cationic group.

<Hydrocarbon group (R)>
In the polysaccharide derivative of the present invention, a hydrocarbon group (R) is introduced into a hydroxyalkylated polysaccharide.
The degree of substitution (MS _R ) of the hydrocarbon group (R) in the polysaccharide derivative of the present invention is preferably 0.001 or more, more preferably 0.003 or more, still more preferably 0.005, from the viewpoint of improving the washing performance. As mentioned above, more preferably 0.008 or more, still more preferably 0.01 or more, and still more preferably 0.015 or more. In addition, the degree of substitution (MS _R ) of the hydrocarbon group (R) in the polysaccharide derivative of the present invention is preferably 1 or less, more preferably 0.5 or less, still more preferably 0.3 from the viewpoint of formulation fluidity. Or less, still more preferably 0.1 or less, still more preferably 0.08 or less, still more preferably 0.06 or less, still more preferably 0.05 or less, still more preferably 0.04 or less, still more preferably Is less than 0.03.

In the present invention, the hydrocarbon group (R) is preferably an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is an unsaturated aliphatic hydrocarbon group even if it is a saturated aliphatic hydrocarbon group, Although it is preferable, it is more preferably a saturated aliphatic hydrocarbon group, still more preferably a linear or branched alkyl group, still more preferably a linear alkyl group.
The carbon number of the hydrocarbon group (R) is 2 or more, preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 10 or more, from the viewpoint of improving the cleaning performance. In addition, from the viewpoint of improving the cleaning performance, it is preferably 22 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 15 or less, still more preferably 14 or less.
In the degree of substitution (MS _R ) of the hydrocarbon group (R) having 2 or more carbon atoms, the degree of substitution (MS _9R ) of the hydrocarbon group (R) having 9 or more carbon atoms is preferably from the viewpoint of improving the cleaning performance. It may be 0.25 or more and 1 or less, more preferably 0.5 or more and 1 or less, and further preferably 0.9 or more and 1 or less.

In the present invention, the hydrocarbon group (R) is bonded directly or via a linking group (excluding a cationic group) to a group obtained by removing a hydrogen atom from the hydroxyl group of the hydroxyalkylated polysaccharide.
That is, it is preferable that hydrocarbon group (R) is couple | bonded with the group remove | excluding the hydrogen atom from the hydroxyl group of the hydroxyalkylated polysaccharide via the coupling group Z shown by following formula (1).

(In the formula (1), Z represents a single bond or a linking group, R represents a hydrocarbon group having a carbon number of 2 or more, and * represents a bonding position to a group obtained by removing a hydrogen atom from a hydroxyl group of hydroxyalkylated polysaccharide Note that Z contains no cationic group.)

In formula (1), Z represents a single bond or a linking group. The linking group is preferably an alkylene group having a functional group, more preferably a hydrocarbon group having an oxygen atom, and as the functional group, an ester group, an ether group, an amide group, a carbonyl group, a urea group, a hydroxyl group etc. And some of the methylene groups of the alkylene group may be substituted with an ether bond, an amide bond, carbonyl carbon (-C (= O)-), or some of the hydrogen atoms of the alkylene group are It may be substituted by a hydroxyl group, an alkyl group, a hydroxyalkyl group, that is, a group other than a cationic group. In addition, a coupling group excludes a cationic group and a coupling group does not contain a cationic group.
Z preferably represents a single bond or a divalent hydrocarbon group having an oxygen atom. The divalent hydrocarbon group having an oxygen atom preferably contains an ester group and / or an ether group, more preferably an ether group.
When Z is a divalent hydrocarbon group having an oxygen atom (hereinafter, also referred to as a hydrocarbon group (Z)), the hydrocarbon group (Z) is a group derived from an epoxy group or a group derived from an oxyglycidyl group It is preferable to include a group derived from an oxyglycidyl group from the viewpoint of the cleaning performance. When Z is a hydrocarbon group which may have an oxygen atom, the carbon number of the hydrocarbon group is preferably 1 or more and 6 or less, and more preferably 1 or more and 3 or less.

In formula (1), R represents a hydrocarbon group having 2 or more carbon atoms, preferably an aliphatic hydrocarbon group, and the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, It may be a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group, still more preferably a linear or branched alkyl group, still more preferably a linear alkyl group.
The number of carbon atoms of R is 2 or more, preferably 4 or more, more preferably 6 or more, further preferably 8 or more, still more preferably 10 or more, from the viewpoint of improving the cleaning performance, and preferably 22 or less. More preferably, it is 18 or less, more preferably 16 or less, still more preferably 15 or less, still more preferably 14 or less.
R is defined to maximize the carbon number of the hydrocarbon group. Accordingly, Z bonded to R in the formula (1) is, for example, an oxygen atom, carbonate carbon, nitrogen atom, a carbon atom to which a hydroxyl group is bonded, or a carbon atom to which a hydroxyalkyl group is bonded.
The group represented by the formula (1) is more preferably a group represented by any of the following formulas (1-1-1) to (1-4).

(In the formulas (1-1-1) to (1-4), R ¹¹ and R ¹² each independently represent an alkylene group having 2 to 4 carbon atoms, and R represents a hydrocarbon group having 2 or more carbon atoms. In the following, * indicates the bonding position of the hydroxyalkylated polysaccharide with a hydrogen atom removed from the hydroxyl group, n1 indicates the average addition mole number of -R ¹¹ O-, and n2 indicates the average addition of -R ¹² -O- Indicates the number of moles, n1 and n2 are 0 or more and 30 or less.)

R is synonymous with R in Formula (1) in Formula (1-1-1)-Formula (1-4), and its preferable aspect is also the same. Z in Formula (1) is a group obtained by removing R from Formula (1-1-1) to Formula (1-4).
In formulas (1-1-1) to (1-4), R ¹¹ and R ¹² each independently represent an alkylene group having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, that is, an ethylene group Or a propylene group. When a plurality of R ¹¹ and R ¹² exist, they may be the same or different. n1 and n2 are 0 or more and 30 or less, preferably 0 or more and 20 or less, more preferably 0 or more and 10 or less, and further preferably 0 or more and 5 or less, and may be 0.

Formula (1-1-1) and Formula (1-1-2) are groups derived from glycidyl ((poly) alkyleneoxy) hydrocarbyl ether, and Z in Formula (1) is an oxyglycidyl group or ) A group derived from an alkylene oxyglycidyl group. The group represented by the formula (1-1-1) or the formula (1-1-2) is a glycidyl compound ((hereinafter, also referred to as “hydrophobizing agent”) of a hydrocarbon group (R) as glycidyl ( It is obtained by using poly) alkyleneoxy) hydrocarbyl ethers, preferably glycidyl ((poly) alkyleneoxy) alkyl ethers, more preferably glycidyl alkyl ethers.
Moreover, Formula (1-2-1) and Formula (1-2-2) are groups from which Z in Formula (1) originates in an epoxy group. The groups represented by Formula (1-2-1) and Formula (1-2-2) can be obtained by using a terminal epoxidized hydrocarbon, preferably a terminal epoxidized alkane, as a hydrophobizing agent.
Furthermore, Formula (1-3) is a case where hydrocarbon group (R) is directly couple | bonded with the group remove | excluding the hydrogen atom from the hydroxyl group of the hydroxyalkylated polysaccharide. The group represented by Formula (1-3) is obtained by using a halogenated hydrocarbon as a hydrophobizing agent.
Formula (1-4) contains a group in which Z is derived from a carboxy group or the like. Groups represented by the formula (1-4), as a hydrophobic _{^{agent, R- (O-R 12)}} n2 -C (= O) -OH, R- (O-R 12) n2 -C (= O ) -A (a is a halogen _{atom), R- (O-R 12} ) n2 -C (= O) -O-C (= O) -. (R 12 -O) using the n2 -R etc. It is obtained by
Among these, there is no by-production of a salt at the time of synthesis of the polysaccharide derivative, and from the viewpoint of washing performance, formula (1-1-1), formula (1-1-2), formula (1-2-1) Or it is preferable that it is group represented by Formula (1-2-2), More preferably, it is group represented by Formula (1-1-1) or Formula (1-1-2).

In the present invention, the ratio (MS _R / MS _C ) of the substitution degree (MS _R ) of the hydrocarbon group (R) of the polysaccharide derivative to the substitution degree (MS _C ) of the cationic group is preferably from the viewpoint of cleaning performance 0.001 or more, more preferably 0.005 or more, still more preferably 0.01 or more, still more preferably 0.05 or more, and from the same viewpoint, preferably 1 or less, more preferably 0.8 The following is more preferably 0.6 or less, still more preferably 0.5 or less, and still more preferably 0.3 or less.

  Further, in the present invention, the hydrocarbon group (R) and the cationic group are, from the viewpoint of washing performance, a polysaccharide derivative which is bonded to an oxygen atom of different hydroxyl groups which the hydroxyalkylated polysaccharide has. In other words, it is not a polysaccharide derivative having a hydrocarbon group (R) and a cationic group on one side chain. That is, the hydrocarbon group (R) and the cationic group are attached on different side chains of the polysaccharide derivative. Therefore, a cationic group is included at a location other than the linking group of the hydrocarbon group (R). In addition, as long as the present invention is not impaired, a polysaccharide derivative in which a hydrocarbon group (R) and a cationic group are bonded to an oxygen atom of the same hydroxyl group possessed by the hydroxyalkylated polysaccharide may be included.

In the present invention, the polysaccharide derivative may have an anionic group, but the ratio of the substitution degree (MS _A ) of the anionic group to the substitution degree (MS _C ) of the cationic group in the polysaccharide derivative (MS _A / MS _C ) is preferably 3 or less, more preferably 2 or less, still more preferably 1.7 or less, still more preferably 1.5 or less, still more preferably 1 or less, more preferably from the viewpoint of cleaning performance It is 0.5 or less, more preferably 0.1 or less, may be 0 or more, and still more preferably 0.
In addition, the degree of substitution (MS _A ) of the anionic group in the polysaccharide derivative is preferably 0.3 or less, more preferably 0.1 or less, still more preferably 0.03 or less, still more preferably 0, from the viewpoint of washing performance. It may be less than .01, more preferably 0.001 or less, 0 or more, and it is more preferred that it be 0.
When the polysaccharide derivative has an anionic group, examples of the anionic group include a sulfuric acid ester group, a sulfonic acid group, and a carboxymethyl group.

The carboxymethylation reaction (reaction of introducing a carboxymethyl group) is carried out by reacting a hydroxyalkylated polysaccharide with monohalogenated acetic acid and / or a metal salt thereof in the presence of a basic compound.
Specific examples of monohalogenated acetic acid and monohalogenated acetic acid metal salt include monochloroacetic acid, sodium monochloroacetate, potassium monochloroacetate, sodium monobromoacetate, potassium monobromoacetate and the like. These monohalogenated acetic acids and their metal salts can be used alone or in combination of two or more.

A preferred embodiment of the polysaccharide derivative of the present invention is a polysaccharide derivative having a cationic group and a hydrocarbon group having 4 to 15 carbon atoms (R), and the substitution degree (MS _C ) of the cationic group is 0.001 or more It is a polysaccharide derivative having a degree of substitution of hydrocarbon group (MS _R ) of not more than 0.4 and not less than 0.001 and not more than 0.05, and the above-mentioned hydrocarbon group (R) is directly or The hydroxylated polysaccharide is bonded to a group obtained by removing a hydrogen atom from the hydroxyl group of the hydroxyalkylated polysaccharide by removing the property group, and the hydroxyalkylated polysaccharide has a weight average molecular weight of 10,000 to 190,000.
Moreover, as another preferable embodiment of the polysaccharide derivative of the present invention, a polysaccharide derivative in which a hydrocarbon group (R) is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide by a linking group derived from an ether group. And the hydroxyalkylated polysaccharide has a weight average molecular weight of 10,000 or more and 190,000 or less.

<Use>
The polysaccharide derivative of the present invention can suppress firm adhesion of oily stains such as sebum dirt to the cloth by treating the fabric such as clothes, and can improve the cleaning property of the sebum dirt at the time of washing. Excellent in formulation fluidity.
The polysaccharide derivative of the present invention is preferably added to a laundry detergent composition. By treating clothes in advance before dressing, it is possible to suppress strong adhesion of sebum dirt at the time of use such as at the time of dressing and to improve the cleaning property of the sebum dirt at the time of washing. The laundry detergent composition may contain the polysaccharide derivative of the present invention as a component thereof, or may be added separately.
The polysaccharide derivative of the present invention preferably has a concentration in the aqueous solution of 0.01 mg / L or more, more preferably 0.1 mg / L or more, from the viewpoint of washing performance and formulation fluidity when treating a fabric such as a garment. , More preferably 0.3 mg / L or more, still more preferably 0.5 mg / L or more, and from the viewpoint of economy, preferably 10,000 mg / L or less, more preferably 1,000 mg / L or less More preferably, it is 500 mg / L or less, still more preferably 100 mg / L or less.

[Method for producing polysaccharide derivative]
<Hydroxyalkylated polysaccharide>
The hydroxyalkylated polysaccharide is obtained by reacting a polysaccharide and a hydroxyalkylating agent in the presence of a basic compound.
Hereinafter, although the case where a polysaccharide is a cellulose is demonstrated to an example, this invention is not limited to this. Since cellulose generally has high crystallinity and is low in reactivity, it is preferable to carry out a treatment to reduce its crystallinity and improve its reactivity before the reaction.

As a method for producing hydroxyalkylated cellulose, for example, the following methods (i) to (iii) can be mentioned.
Method (i): An activation method generally called arselation or mercerization, ie, after mixing the raw material cellulose with a large amount of water and a large excess of alkali metal hydroxide to obtain an alkali cellulose, followed by hydroxyalkylation How to react with agents.
Method (ii): Solvents such as cellulose, for example, dimethylsulfoxide containing tetrabutylammonium fluoride, dimethylsulfoxide containing paraformaldehyde, dimethylacetamide containing lithium chloride, etc., “Encyclopedia of Cellulose, Editor: Cellulose Society, Publication place: Asakura Shoten Co., Ltd., Macromol. Chem. Phys. 201, 627-631 (2000) etc. The method of making a raw material cellulose dissolve using the solvent which can melt | dissolve the cellulose described in etc., and making a raw material cellulose and a hydroxyalkylating agent react after that.
Method (iii): As in the methods (i) and (ii), a powdery or cotton-like raw material cellulose and a hydroxyalkylating agent are used without using a special solvent capable of dissolving an excess of alkali or cellulose. To react in the presence of alkali.
Hereinafter, a hydroxyalkylating agent, a cationizing agent, a hydrophobizing agent, an activation method, and the like used as a raw material for producing the polysaccharide derivative of the present invention will be described.

(Hydroxyalkylating agent)
Specific examples of the hydroxyalkylating agent used for producing the polysaccharide derivative of the present invention include epoxyalkanes, alkyl glycidyl ethers, alkyl halohydrin ethers and the like. Among these, at least one selected from epoxy alkanes and alkyl glycidyl ethers is preferable, and epoxy alkanes are more preferable, from the viewpoint that no salt is formed during the reaction.
Among the above, as the hydroxyalkylating agent, one or more selected from ethylene oxide and propylene oxide is preferable, and ethylene oxide is more preferable.
The amount of the hydroxyalkylating agent used is not limited, and may be appropriately adjusted according to the desired degree of substitution.

Hydroxyalkylated polysaccharides are commercially available, and hydroxyalkylated polysaccharides obtained from the market may be used.
Specifically, as hydroxyethyl cellulose, Natrosol series (Ashland) is illustrated. In addition, hydroxyethyl cellulose and hydroxypropyl cellulose are also available from Shin-Etsu Chemical Co., Ltd., Dow Chemical Co., Nippon Soda Co., Ltd., Sumitomo Seika Co., Ltd., Sansei Co., Ltd., Daicel Finechem Co., Ltd., Tokyo Chemical Industry Co., Ltd., etc. It is available.

(Cationizing agent)
As a cationizing agent used for manufacture of the polysaccharide derivative of this invention, the compound etc. which are represented by following formula (3) or Formula (4) are mentioned.

In formulas (3) and (4), R ^{21 to} R ²³ and preferred embodiments thereof are the same as R ^{21 to} R ^{23 in} formulas (2-1) and (2-2). t and preferred embodiments thereof are the same as n in the above formulas (2-1) and (2-2). X ^- and its preferred embodiments, X in the formula (2-1) and (2-2) ^- are the same as. A represents a halogen atom, preferably a chlorine atom. R ^{21 to} R ²³ may be identical to or different from one another.

Specific examples of the compound represented by the formula (3) or (4) include glycidyl trimethyl ammonium, glycidyl triethyl ammonium, glycidyl tripropyl ammonium, glycidyl dimethyl lauryl ammonium, glycidyl diethyl lauryl ammonium, and glycidyl ethyl methyl lauryl ammonium. Chloride, bromide or iodide, 3-chloro-2-hydroxypropyltrimethylammonium, 3-chloro-2-hydroxypropyltriethylammonium, 3-chloro-2-hydroxypropyltripropylammonium, 3-chloro-2-hydroxyl Propyldimethyl lauryl ammonium, 3-chloro-2-hydroxypropyl diethyl lauryl ammonium, or 3-chloro-2-hydroxypropyl ether Each chloride of methyl methyl lauryl ammonium, 3-bromo-2-hydroxypropyltrimethylammonium, 3-bromo-2-hydroxypropyltriethylammonium, 3-bromo-2-hydroxypropyltripropylammonium, 3-bromo-2-hydroxy Bromide of propyldimethyl lauryl ammonium, 3-bromo-2-hydroxypropyl diethyl lauryl ammonium or 3-bromo-2-hydroxypropyl ethyl methyl lauryl ammonium, 3-iodo-2-hydroxypropyl trimethyl ammonium, 3-iodo- 2-hydroxypropyltriethylammonium, 3-iodo-2-hydroxypropyltripropylammonium, 3-iodo-2-hydroxypropyldimethyl laure Ammonium, 3-iodo-2-hydroxypropyl-diethyl lauryl ammonium, or 3-iodo-2-hydroxypropyl each ethyl iodide methyl lauryl ammonium.
Among these, glycidyl trimethyl ammonium or chloride or bromide of glycidyl triethyl ammonium from the viewpoint of availability of raw materials and chemical stability; 3-chloro-2-hydroxypropyl trimethyl ammonium or 3-chloro-2- Chloride of hydroxypropyl triethylammonium; One or more selected from bromide of 3-bromo-2-hydroxypropyltrimethylammonium or 3-bromo-2-hydroxypropyltriethylammonium is preferable, and glycidyl trimethyl ammonium chloride and 3-chloro-2 are preferable. -One or more types selected from -hydroxypropyl trimethyl ammonium chloride are more preferable, and glycidyl trimethyl ammonium chloride is more preferable.
These cationizing agents can be used alone or in combination of two or more.

The amount of cationizing agent to be used may be appropriately selected in consideration of the desired degree of substitution of the cationic group (MS _C ) and the reaction yield, but the water solubility of the polysaccharide derivative and the effect of the present invention can be obtained From the viewpoint, per mole of constituent monosaccharide unit of hydroxyalkylated polysaccharide, preferably 0.01 mole or more, more preferably 0.03 mole or more, further preferably 0.05 mole or more, still more preferably 0.1 The amount is preferably 30 mol or less, more preferably 25 mol or less, still more preferably 10 mol or less, still more preferably 1 mol or less, and still more preferably from the viewpoints of the above and the production cost of the polysaccharide derivative. It is 0.5 mol or less.
The method of adding the cationizing agent may be batch, intermittent or continuous.

<Introducer for Hydrocarbon Group (R) (Hydrophobicizing Agent)>
As the introducing agent (hydrophobizing agent) of the hydrocarbon group (R) used for the production of the polysaccharide derivative of the present invention, any agent capable of introducing the group represented by the formula (1) may be used.
As an introducer which can introduce group represented by said Formula (1-1-1) and Formula (1-1-2), the compound represented by following formula (5) or (6) is mentioned.

In formulas (5) and (6), R and a preferred embodiment thereof are the same as R in formula (1) above. A represents a halogen atom, preferably a chlorine atom. R ¹¹ and preferred embodiments thereof are the same as ^{R 11} and its preferred embodiments of the formula (1-1-1) and (1-1-2). Moreover, n1 and its preferable aspect are the same as that of n1 of the said Formula (1-1-1) and (1-1-2), and its preferable aspect.
Specific examples of the compound represented by the formula (5) include ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl Glycidyl ethers having alkyl groups such as ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, octadecyl glycidyl ether; butenyl Glycidyl ether, pentenyl glycidyl ether, hexenyl glycidyl ether, Butenyl glycidyl ether, octenyl glycidyl ether, nonenyl glycidyl ether, decenyl glycidyl ether, undecenyl glycidyl ether, dodecenyl glycidyl ether, tridecenyl glycidyl ether, tetradecenyl glycidyl ether, pentadece And glycidyl ethers having an alkenyl group such as nyl glycidyl ether, hexadecenyl glycidyl ether, heptadecenyl glycidyl ether, octadecenyl glycidyl ether and the like. Among these, alkyl glycidyl ethers having a hydrocarbon group and having 5 to 25 carbon atoms, such as lauryl glycidyl ether and cetyl glycidyl ether, are preferable.
Specific examples of the compound represented by the formula (6) include 3-halo-2-hydroxy-propyl alkyl ether such as 3-chloro-2-hydroxypropyl-dodecyl ether, and the like.
Among these, it is represented by the above-mentioned formula (5) from the viewpoints of no salt by-production when the hydrophobization agent and the hydroxyalkylated polysaccharide are reacted, the availability of the hydrophobization agent and the chemical stability. Compounds are preferred.
These can be used alone or in combination of two or more.

  As an introducer which can introduce | transduce group represented by said Formula (1-2-1) and Formula (1-2-2), the compound etc. which are represented by following formula (7) or (8) are mentioned. .

In the formulas (7) and (8), R and a preferred embodiment thereof are the same as R in the formula (1). A represents a halogen atom, preferably a chlorine atom.
Specific examples of the compound represented by the formula (7) include hydrocarbon groups such as 1,2-epoxyhexane, 1,2-epoxy-heptane, 1,2-epoxytetradecane, and 1,2-epoxyoctadecane. There may be mentioned 1,2-epoxyalkanes having 4 to 24 carbon atoms. As a specific example of the compound represented by said Formula (8), C4-C24 1-halo- 2-hydroxy alkane etc. which have hydrocarbon groups, such as 1-chloro- 2-hydroxy tetradecane, etc. are mentioned. Be
Among these, it is represented by the above-mentioned formula (7) from the viewpoints of no salt by-production when the hydrophobization agent and the hydroxyalkylated polysaccharide are reacted, the availability of the hydrophobization agent and the chemical stability. Compounds are preferred.
These can be used alone or in combination of two or more.

  As an introducer which can introduce | transduce the structural unit represented by said Formula (1-3), the compound etc. which are represented by following formula (9) are mentioned.

In the formula (9), R and a preferred embodiment thereof are the same as R in the formula (1). A represents a halogen atom, preferably a chlorine atom.
Specific examples of the compound represented by the formula (9) include halogenated alkanes having the desired carbon number.

  As an introducer which can introduce | transduce the structural unit represented by said Formula (1-4), the compound etc. which are represented by following formula (10)-(12) are mentioned.

In the formulas (10) to (12), R and a preferred embodiment thereof are the same as R in the formula (1). A represents a halogen atom, preferably a chlorine atom.
In formulas (10) to (12), R ¹² and n 2 and preferred embodiments thereof are the same as R ¹² and n 2 in formula (1-4).
Specific examples of the compounds represented by the formulas (10) to (12) include fatty acids having the desired carbon number, fatty acid halides and fatty acid anhydrides.

The amount of the hydrophobizing agent to be used may be appropriately selected in consideration of the degree of substitution (MS _R ) of the desired hydrocarbon group (R) and the reaction yield, but the water solubility of the polysaccharide derivative and From the viewpoint of obtaining effects, the amount is preferably 0.01 mol or more, more preferably 0.03 mol or more, per 1 mol of constituent monosaccharide units of the hydroxyalkylated polysaccharide, and the above viewpoint and the viewpoint of the production cost of the polysaccharide derivative It is preferably 5 mol or less, more preferably 3 mol or less, still more preferably 1 mol or less, still more preferably 0.5 mol or less, still more preferably 0.2 mol or less.
The method of adding the hydrophobizing agent may be batchwise, intermittent or continuous.

<Method of producing polysaccharide derivative>
The method for producing a polysaccharide derivative of the present invention comprises reacting a hydroxyalkylated polysaccharide with the cationizing agent described above and an introducing agent (hydrophobizing agent) for a hydrocarbon group (R) to form a cationic group and a hydrocarbon group (R Is preferred to be introduced.
The method for producing a polysaccharide derivative of the present invention is characterized in that the hydroxyalkylated polysaccharide having a weight average molecular weight of 10,000 or more and 190,000 or less has 2 or more carbon atoms from the viewpoint of ease of production and transparency of the resulting polysaccharide derivative. It is more preferable to react with the above-mentioned cationizing agent after introducing a hydrocarbon group (R). That is, after the hydrophobizing agent described above is reacted with a hydroxyalkylated polysaccharide having a weight average molecular weight of 10,000 or more and 190,000 or less to introduce a hydrocarbon group (R), it is reacted with the above cationizing agent to form a cation. It is more preferable to introduce a sex group.
More preferably, the method for producing a polysaccharide derivative of the present invention is a hydroxyalkyl having a weight average molecular weight of 10,000 or more and 190,000 or less in the presence of an alkali compound from the viewpoint of easiness of production and transparency of the resulting polysaccharide derivative. After the hydrophobized polysaccharide is reacted with the above-mentioned hydrophobizing agent to introduce a hydrocarbon group (R) having 2 or more carbon atoms, it is a production method in which it is reacted with a cationizing agent without having a washing step.
All these reactions are preferably carried out in the presence of an alkali compound. Examples of the alkali compound used in the reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, trimethylamine and triethylamine And tertiary amine compounds, and the like. Among these, from the viewpoint of the reaction rate of the introduction reaction, alkali metal hydroxides or alkaline earth metal hydroxides are preferable, alkali metal hydroxides are more preferable, and sodium hydroxide and potassium hydroxide are still more preferable. These alkali compounds can be used alone or in combination of two or more.
There is no particular limitation on the method of adding the alkali compound, and batch addition or split addition may be used. The alkali compound may be added in the solid state or may be added as an aqueous solution.

The amount of the alkali compound used in each of the introduction reaction of the hydrocarbon group (R) and the introduction reaction of the cationic group is the reaction selection of the hydrophobizing agent or the cationizing agent when the alkali compound is a monovalent basic compound. From the viewpoint of the property, per 1 mol of constituent monosaccharide units of hydroxyalkylated polysaccharide (when hydroxyalkylated polysaccharide is hydroxyalkylated cellulose, per 1 mol of anhydroglucose unit (AGU) of raw material cellulose) Is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and from the same viewpoint, preferably 10 mol or less, more preferably 5 mol or less Preferably, it is 3 mol or less, more preferably 2 mol or less, still more preferably 1.0 mol or less, still more preferably 0.8 Le below, still more preferably 0.5 mol or less.
The preferable amount of the alkali compound used when the introduction reaction of the cationic group and the introduction reaction of the hydrocarbon group (R) are simultaneously performed is also used in the introduction reaction of the cationic group and the introduction reaction of the hydrocarbon (R), respectively. It is the same as the amount of the alkali compound to be
When the alkali compound used in the introduction reaction of a hydroxyalkyl group, the introduction reaction of a cationic group, or the introduction reaction of a hydrocarbon group (R) is a polyvalent base such as an alkaline earth metal hydroxide, the alkali compound used The preferred range of the amount of is the range obtained by dividing the range of the preferred amount of the alkali compound in each of the above reactions by the multivalent base number. For example, when the alkali compound to be used is calcium hydroxide (divalent base), the amount of calcium hydroxide used in the cationization reaction or the reaction of introducing a hydrocarbon group (R) is hydroxy from the viewpoint of reaction selectivity. The amount is preferably 0.005 mol or more, more preferably 0.025 mol or more, still more preferably 0.05 mol or more, per 1 mol of constituent monosaccharide units of the alkylated polysaccharide, and from the same viewpoint, preferably 5 Or less, more preferably 2.5 or less, still more preferably 1.5 or less, still more preferably 1 or less, still more preferably 0.5 or less, still more preferably 0.4 or less, more preferably More preferably, it is 0.25 mol or less.
That is, the alkali compound is added to 1 mol of anhydroglucose unit (AGU) of raw material cellulose when 1 mol of constituent monosaccharide units of hydroxyalkylated polysaccharide is used (hydroxyalkylated polysaccharide is hydroxyalkylated cellulose) ), Preferably 0.01 molar equivalent or more, more preferably 0.05 molar equivalent or more, still more preferably 0.1 molar equivalent or more, preferably 10 molar equivalents or less, more preferably 5 molar equivalents or less, More preferably, it is 3 molar equivalents or less, more preferably 2 molar equivalents or less, still more preferably 1 molar equivalent or less, still more preferably 0.8 molar equivalents or less, still more preferably 0.5 molar equivalents or less.
The molar equivalent of the alkali compound is the same as the number of moles when the alkali compound is a monovalent base compound such as sodium hydroxide, and when the alkali compound is a divalent base compound such as calcium hydroxide, It is a value obtained by multiplying the number of moles by the valence.
The molar equivalent ratio of the alkali compound to the cationizing agent (alkali compound / cationizing agent) is preferably 0.1 or more, more preferably 0.5 or more from the viewpoint of reactivity, and the transparency of the polysaccharide derivative to be obtained is From the viewpoint of improving the properties, it is preferably 2 or less, more preferably 1.8 or less. In addition, when a cationizing agent is polyvalent, it calculates similarly.

In the present invention, hydroxyalkyl cellulose can be obtained by reacting powdered cellulose or cotton-like cellulose with the above-described hydroxyalkylating agent to carry out a reaction for introducing hydroxyalkyl group.
Hereinafter, the “polysaccharide derivative” is a generic term for the hydroxyalkyl group introduction reaction (hydroxyalkylation reaction), the cationic group introduction reaction (cationization reaction), and the hydrocarbon group (R) introduction reaction (hydrophobization reaction). It is also called "reaction during production".
In each reaction at the time of polysaccharide derivative production, the form at the time of addition of the hydroxyalkylating agent, cationizing agent and hydrophobizing agent is not particularly limited. When the hydroxyalkylating agent, the cationizing agent and the hydrophobizing agent are in the liquid state, they may be used as they are, or in a form diluted with a hydroxyalkylating agent or a good solvent for the cationizing agent such as water or nonaqueous solvent. You may use.
As the non-aqueous solvent used for dilution, secondary or tertiary C 3 -C 4 lower alcohols such as isopropanol and tert-butanol which are generally used; C 3 such as acetone, methyl ethyl ketone and methyl isobutyl ketone Ketones of 6 or less; ethers such as tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; aprotic polar solvents such as dimethyl sulfoxide and the like.
Each reaction at the time of polysaccharide derivative production is carried out by dissolving the raw material cellulose using a solvent capable of dissolving cellulose at the time of reaction in the above method (ii), but also in methods (i) and (iii) From the viewpoint of the reaction yield of the hydroxyalkylating agent, the cationizing agent and the introducing agent of the hydrocarbon group, the reaction can also be carried out in the presence of a non-aqueous solvent. As the non-aqueous solvent, the same non-aqueous solvent as described above can be used.
Although there may be a washing step between the introduction reaction (hydrophobization reaction) of the hydrocarbon group (R) and the introduction reaction (cationization reaction) of the cationic group, from the viewpoint of the easiness of production, the washing It is preferred not to have a step. By setting the molar ratio of the alkali compound to the cationizing agent (alkali compound / cationizing agent) within the above range, it is not necessary to remove the excess alkali compound by the washing step after the hydrophobization reaction, It can be cationized. In the washing step, the reaction intermediate having a hydrocarbon group (R) introduced therein is washed with a solvent such as hot water, isopropyl alcohol, acetone or the like to introduce an agent for introducing an unreacted hydrocarbon group (R) or It is the process of removing an alkali compound as a salt by neutralization etc. After the washing step, after filtration and drying, the alkali compound can be added again to cause a cationization reaction.

The apparatus used for each reaction at the time of the production of the polysaccharide derivative is a so-called flask, a SUS reaction tank, a mixer such as a Lidige mixer capable of stirring, a mixture of powder, high viscosity substance, resin, etc. A mixer such as a kneader can be mentioned.
The temperature at the time of reaction of each reaction at the time of polysaccharide derivative production is preferably 0 ° C. or more, more preferably 20 ° C. or more, still more preferably 30 ° C. or more from the viewpoint of the reaction rate. Moreover, it is preferably 200 ° C. or less, more preferably 100 ° C. or less, from the viewpoint of suppressing the decomposition of the hydroxyalkylating agent, the cationizing agent, or the introducing agent of the hydrocarbon group.
The reaction temperature for introducing a hydrocarbon group (in the hydrophobization reaction) is preferably 55 ° C. or more, more preferably 60 ° C. or more from the viewpoint of reactivity, and preferably 200 ° C. or less from the viewpoint of suppression of decomposition. Preferably it is 100 degrees C or less.
The reaction temperature to be reacted with the cationizing agent is preferably 20 ° C. or more, more preferably 30 ° C. or more, still more preferably 40 ° C. or more from the viewpoint of reactivity, and preferably from the viewpoint of transparency of the obtained polysaccharide derivative. Is less than 55.degree. C., more preferably 53.degree. C. or less, still more preferably 51.degree. C. or less.
In addition, it is preferable to carry out each reaction at the time of polysaccharide derivative production in an inert gas atmosphere such as nitrogen, as needed, from the viewpoint of suppressing coloring and the molecular weight decrease of the main chain derived from the monosaccharide unit.

After completion of the reaction, the alkali compound can be neutralized using an acid. When the hydroxyalkylation reaction, the cationization reaction, and the introduction reaction of the hydrocarbon group are separately performed, neutralization can be performed between each reaction, but from the viewpoint of suppressing the formation of the neutralization salt, all reactions are performed. Preferably after the end of the As the acid, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid and lactic acid can be used.
The polysaccharide derivative obtained after completion of all reactions at the time of polysaccharide derivative production is fractionated by filtration etc., or washed with hot water, water-containing isopropyl alcohol, water-containing acetone solvent etc. and unreacted hydroxyalkylated, if necessary. It can also be used after removing by-products such as agents, cationizing agents, hydrocarbon group introducing agents, by-products derived from these reactants, and by-products such as neutralization. In addition, as purification methods, general purification methods such as reprecipitation purification, centrifugation, dialysis and the like can be used.

The measurement methods used in the examples and comparative examples are as follows.
[Measurement of substitution degree (molar average substitution degree (MS))]
Pretreatment After dissolving 1 g of powdered polysaccharide derivative (cellulose derivative) in 100 g of water, the aqueous solution was placed in a dialysis membrane (Spectrapore, molecular weight cut off 1,000) and dialyzed for 2 days. The obtained aqueous solution was lyophilized using a lyophilizer (eyela, FDU1100) to obtain a purified polysaccharide derivative (purified cellulose derivative).

<Calculation of cationic group mass by Kjeldahl method>
200 mg of the purified polysaccharide derivative was precisely weighed, 10 mL of sulfuric acid and 1 tablet of Kjeldahl tablet (Merck) were added, and thermal decomposition was performed in a Kjeldahl decomposition apparatus (BUCHI, K-432). After completion of the decomposition, 30 mL of ion-exchanged water was added to the sample, and the mass of the cationic group was calculated by determining the nitrogen content (% by mass) of the sample using an automatic Kjeldahl distillation apparatus (BUCHI, K-370).

<Calculation of alkyl group mass by the Zeisel method>
Hereinafter, the method of calculating the mass of the alkyl group will be described by taking the case of Example 1 (using lauryl glycidyl ether as a hydrocarbon group introducing agent) as an example. Even when other introducers are used, measurement can be performed by appropriately selecting a sample for calibration curve (iodoalkane, introducer of hydrocarbon group, etc.).
200 mg of the purified polysaccharide derivative and 220 mg of adipic acid are precisely weighed into 10 mL vials (Mighty vial No. 3), 3 mL of an internal standard solution (tetradecane / o-xylene = 1/25 (v / v)) and 3 mL of hydroiodic acid In addition, it was sealed up. Also, a sample for calibration curve was prepared by adding 2, 4 or 9 mg of 1-iodododecane instead of the cellulose derivative. Each sample was heated under conditions of 160 ° C. for 2 hours using a block heater (PIERCE, Reacti-ThermIII Heating / Stirring module) while being stirred by a stirrer chip. After the sample was allowed to cool, the upper layer (o-xylene layer) was recovered, and the amount of 1-iodododecane was analyzed by gas chromatography (Shimadzu Corporation, GC-2010 plus).

GC analysis conditions Column: Agilent HP-1 (length: 30 m, liquid phase film thickness: 0.25 μL, inner diameter: 32 mm)
Split ratio: 20
Column temperature: 100 ° C (2 min) → 10 ° C / min → 300 ° C (15 min)
Injector temperature: 300 ° C
Detector: FID
Detector temperature: 330 ° C
Amount of implantation: 2 μL
The mass of the alkyl group in the sample was determined from the detected amount of 1-iodododecane obtained by GC.

<Measurement of hydroxyalkyl group mass>
By quantifying the alkyl iodide derived from a hydroxyalkyl group, it carried out like the measurement of the above-mentioned alkyl group mass.

<Calculation of degree of substitution (molar average degree of substitution) of cationic group and alkyl group>
Degree of substitution of the cationic group (MS _C ) by calculating the mass of the hydroxyalkylated polysaccharide backbone from the mass of the cationic group and the alkyl group described above and the total sample mass, and converting each to the substance mass (mol) The degree of substitution (MS _R ) of the alkyl group was calculated.

<Calculation of anionic group mass by atomic absorption spectrometry>
0.1 g of the cellulose derivative obtained in Examples 11 and 12 is collected in a decomposition vessel, 4 mL of sulfuric acid (for precision analysis, Wako Pure Chemical Industries Ltd.) and nitric acid (for atomic absorption analysis, Kanto Chemical Co., Ltd.), Hydrogen oxide (for atomic absorption analysis, Wako Pure Chemical Industries, Ltd.) is added as appropriate to perform wet decomposition, and the solution made up to 100 mL with ultrapure water is used as a sample measurement solution, and this solution is diluted 25 times to obtain a sample It was used as a measurement solution (the sulfuric acid content was adjusted to the same degree as the calibration curve).
Preparation of calibration curve solution: Preparation of a calibration curve solution of 0.1 to 20 mg / L using a standard solution for atomic absorption analysis (Na: 1000 mg / L, standard solution for atomic absorption analysis 1000 mg / L, Kanto Chemical Co., Ltd.) did. Sulfuric acid was added to each solution so that the sulfuric acid concentration was 4%.
The prepared sample was subjected to measurement of Na content with an ICP emission spectrometer under the following conditions.
(Analysis conditions)
・ Analyzer: Thermo Fisher Scientific, iCAP 6500 Duo
・ Measurement wavelength: Na 589.52 nm
・ RF power: 950 W
· Coolant gas flow rate: 12 L / min
・ Nebulizer flow rate: 0.70 L / min
Auxiliary gas: 0.5 L / min
Pump flow rate: 50 r. p. m
The mass of the anionic group was calculated by determining the Na content (mass%) of the sample.

<Calculation of degree of substitution (molar average degree of substitution) of anionic group, cationic group, alkyl group, and hydroxyalkyl group>
By calculating the mass of the HEC skeleton from the mass of the anionic group described above, the mass of the cationic group and the alkyl group described above, and the total sample mass, the degree of substitution of the anionic group is obtained MS _A ), substitution degree of cationic group (MS _C ), and substitution degree of alkyl group (MS _R ) were calculated. The degree of substitution was calculated similarly for the hydroxyalkyl group.

<Calculation of mass of hydrophobic group (bonded species: ammonium group) by Kjeldahl method>
200 mg of the cellulose derivative obtained in Comparative Example 4 was precisely weighed, 10 mL of sulfuric acid and 1 Kjeldahl tablet (Merck) were added, and thermal decomposition was performed in a Kjeldahl decomposition apparatus (BUCHI, K-432). After completion of the decomposition, 30 mL of ion exchanged water was added to the sample, and the nitrogen content (% by mass) of the sample was determined using an automatic Kjeldahl distillation apparatus (BUCHI, K-370). The mass of the hydrophobic group (binding species: ammonium group) was calculated by subtracting the mass of the GMAC-derived cationic group.

<Calculation of degree of substitution (molar average degree of substitution) of alkyl group (binding species: ammonium group), cationic group, and hydroxyalkyl group>
Calculating the mass of the HEC skeleton from the mass of the above-mentioned alkyl group (binding species: ammonium group), the mass of the above-mentioned cationic group and the total sample mass, and converting each to the substance mass (mol) species: degree of substitution of ammonium groups) _{(MS R-C),} was calculated degree of substitution of cationic groups (MS _C). The degree of substitution was calculated similarly for the hydroxyalkyl group.

[Measurement of weight average molecular weight]
The weight average molecular weight of the hydroxyalkylated polysaccharide (hydroxyethyl cellulose, HEC) was calculated based on polyethylene glycol by GPC (gel permeation chromatography).
The measurement conditions are as follows.
・ Column: TSKgel α-M
Eluent: 50 mmol / L LiBr, 1% CH ₃ COOH, ethanol / water = 3/7
Temperature: 40 ° C
・ Flow rate: 0.6 mL / min

Example 1
(1) Synthesis of polysaccharide derivative (cellulose derivative) 90 g of hydroxyethyl cellulose (hereinafter referred to as HEC) (Ashland, Natrosol 250 JR, weight average molecular weight: 150,000, hydroxyethyl MS value: 2.5) was placed in a 1 L separa flask Nitrogen flow was done. 77.2 g of ion exchange water and 414.5 g of isopropyl alcohol (hereinafter referred to as IPA) were added, and 200 r.p. p. m. After stirring for 5 minutes, 10.9 g of 48% aqueous sodium hydroxide solution was added, and the mixture was further stirred for 15 minutes. Next, 3.9 g of lauryl glycidyl ether (Yokkaichi Synthetics Co., Ltd., LA-EP) was added, and the alkylation reaction was performed at 80 ° C. for 13 hours. Furthermore, 14.5 g of glycidyl trimethyl ammonium chloride (hereinafter, also referred to as "GMAC", Sakamoto Yakuhin Kogyo Co., Ltd., SY-GTA 80) was added, and a cationization reaction was performed at 50 ° C for 1.5 hours. Thereafter, 10.9 g of a 90% aqueous acetic acid solution was added, and the reaction was neutralized by stirring for 30 minutes.
The obtained suspension was equally transferred to two 500 mL centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Hitachi Koki Co., Ltd., CR21G III). The supernatant was removed by decantation, and the same amount of 85% IPA aqueous solution as the removed supernatant was added and redispersed. The operation of centrifugation and redispersion was repeated again, and the precipitate was removed after the third centrifugation. The resulting precipitate is dried under reduced pressure at 80 ° C. for 12 hours using a vacuum dryer (Advantec, VR-420) and disintegrated using an Extreme mill (Warling, MX-1200XTM) to obtain powdered polysaccharide. A derivative (cellulose derivative) was obtained.

(2-1) Preparation of chemical fiber for washing evaluation: In a 100 mL screw tube, 40 mL of a treatment liquid having the following composition and 5 sheets of a polyester cloth (6 cm × 6 cm, polyester fiber, manufactured by Dyeing Materials, Inc.) were loaded. Using a shaker (Yamato Scientific Co., Ltd., model number: SA300), 300 r. p. m. The sample solution was subjected to horizontal reciprocating shaking under the conditions of 5 minutes to treat the polyester cloth with the treating solution. After the treatment, the polyester cloth was dewatered for 1 minute with a two-tank washing machine (manufactured by Hitachi, Ltd., PS-H45L). Next, 40 mL of ion exchange water for washing and the obtained polyester cloth were put into a 100 mL screw tube, and 300 r. p. m. The polyester cloth was rinsed under conditions of 3 minutes. After rinsing, it was dewatered for 1 minute in a 2-bath washing machine and allowed to dry naturally for 24 hours.

<Composition of Processing Solution>
(A) Cellulose derivative: 0 or 30 mg / kg
(B) Surfactant (polyoxyethylene (3) sodium lauryl ether sulfate (trade name: Emar 20C) / polyoxyethylene (10) lauryl ether (trade name: Emulgen 110 L) = 1/1 (w / l) active ingredient w)): 80 mg / kg

(2-2) Preparation of Contaminated Fabric 0.1 mL of a model sebum artificially contaminated solution prepared by mixing 0.02% of Sudan III with oleic acid, uniformly applied to the polyester fabric (36 cm ² ) prepared in (2-1) above. The solution was applied and dried at 40 ° C. for 1 hour using a constant temperature drier (EYELA, incubator FMS).

(3) Washing test By ion-exchanged water so that surfactant (polyoxyethylene (3) lauryl ether sodium sulfate / polyoxyethylene (10) lauryl ether = 1/1 (w / w)) would be 150 mg / kg. Diluted and prepared the washing solution. In a 1 L stainless beaker for a washing test, 600 mL of the washing solution and 5 sheets of the polyester cloth obtained in the above (2-2) were charged. Using a tergotometer (MS- 8212, manufactured by Ueshima Seisakusho Co., Ltd.), 85 r. p. m. The polyester cloth was washed at 20 ° C. for 10 minutes. The obtained polyester cloth was rinsed with a large amount of water, dewatered with a two-tank washing machine, and naturally dried for 24 hours.

[Evaluation of cleaning rate, cleaning rate improvement performance]
The reflectance at 460 nm of polyester fabric before contamination and polyester fabric before and after washing is measured by a colorimetric color difference meter (SE-2000, manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the cleaning ratio (%) is calculated by the following equation. I asked.
Cleaning ratio (%) = 100 × [(reflectance after cleaning−reflectance before cleaning) / (reflectance of base fabric−reflectance before cleaning)]
Moreover, the cleaning rate improvement performance (%) was calculated | required by following Formula from the difference with the cleaning rate of the blank which set (A) component to 0 mg / kg by said (2-1).
Washing rate improvement performance (%) = [washing rate (%) of 30 mg / kg of component (A)-washing rate (%) of 0 mg / kg of component (A)]

[Evaluation of formulation fluidity]
20 mL of surfactant (polyoxyethylene (10) lauryl ether (trade name "Emulgen 110L", manufactured by Kao Corporation)) as an active ingredient, 10 mL of an aqueous solution (5 mL) containing 3 wt% of the polysaccharide derivative It was prepared in (marked) and stirred (20 ° C.) with a stirrer for 24 hours and allowed to dissolve.
The obtained solution was turned upside down with the screw tube, and the fluidity was evaluated visually.
The time for almost all of the solution (90% or more) to move from the top to the bottom was measured.
The time for almost all the solution (90% or more) to move from the top to the bottom is preferably within 5 seconds, more preferably within 3 seconds.

Examples 2 to 10 and Comparative Examples 1 to 3
The polysaccharide derivatives shown in Table 1 were synthesized using the same method as Example 1. Further, in the same manner as in Example 1, the cleaning performance and the flowability of the preparation were evaluated.

Example 11
10 g of the powdered cellulose derivative synthesized in Example 1 was placed in a 1 L separa flask, and a nitrogen flow was performed. Add 43.3 g of IPA and 4.8 g of ion exchanged water, and add 100 r. p. m. After stirring for 5 minutes, 5.4 g of a 48% aqueous solution of sodium hydroxide was added, and the mixture was further stirred for 15 minutes. Next, 0.8 g of sodium monochloroacetate (Wako Pure Chemical Industries, Ltd.) was added, and the carboxymethylation reaction was performed at 70 ° C. for 2.5 hours. Thereafter, 3.5 g of acetic acid was added, and the reaction was neutralized by stirring for 30 minutes.
The obtained suspension was equally transferred to two 50 mL centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Hitachi Koki Co., Ltd., CR21G III). The supernatant was removed by decantation, and the same amount of 85% IPA aqueous solution as the removed supernatant was added and redispersed. The operation of centrifugation and redispersion was repeated again, and the precipitate was removed after the third centrifugation. The obtained precipitate is dried under reduced pressure overnight at 80 ° C. using a vacuum dryer (Advantec, VR-420), and pulverized using an Extreme mill (Waring, MX-1200XTM) to obtain powdered cellulose. The derivative was obtained.
The washing performance and the formulation fluidity were evaluated in the same manner as in Example 1 using the obtained cellulose derivative.

Example 12
The cellulose derivative shown in Table 1 was synthesized using the same method as in Example 11.
Further, in the same manner as in Example 1, the cleaning performance and the recontamination prevention property were evaluated.

Comparative example 4
70 g of HEC was placed in a 1 L separa flask and a nitrogen flow was performed. Add 56.8 g of ion exchanged water and 314.4 g of IPA, add 200 r. p. m. After stirring for 5 minutes, 8.2 g of 48% aqueous sodium hydroxide solution was added, and the mixture was further stirred for 15 minutes. Next, 10.4 g of GMAC was added, and a cationization reaction was performed at 50 ° C. for 1.5 hours. Further, 34.3 g of 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride (Yokkaichi Synthetic Co., Ltd., CDDA) was added, and the reaction was performed at 50 ° C. for 1.5 hours. Thereafter, 8.2 g of 90% aqueous acetic acid solution was added, and the reaction was neutralized by stirring for 30 minutes.
The obtained suspension was equally transferred to two 500 mL centrifuge tubes, and centrifuged using a high-speed cooling centrifuge (Hitachi Koki Co., Ltd., CR21G III). The supernatant was removed by decantation, and the same amount of 85% IPA aqueous solution as the removed supernatant was added and redispersed. The operation of centrifugation and redispersion was repeated again, and the precipitate was removed after the third centrifugation. The obtained precipitate is dried under reduced pressure overnight at 80 ° C. using a vacuum dryer (Advantec, VR-420), and pulverized using an Extreme mill (Waring, MX-1200XTM) to obtain powdered cellulose. The derivative was obtained.
The washing performance and the formulation fluidity were evaluated in the same manner as in Example 1 using the obtained cellulose derivative.

The polysaccharide raw materials used in Table 1 are as follows.
-HEC, molecular weight 150,000: Hydroxyethylcellulose manufactured by Ashland, Natrosol 250JR (trade name), weight average molecular weight = 150,000, degree of substitution of hydroxyethyl group = 2.5
-HEC, molecular weight 90,000: Hydroxyethylcellulose manufactured by Ashland, Natrosol 250 LR (trade name), weight average molecular weight 90,000, degree of substitution of hydroxyethyl group = 2.5
-HEC, molecular weight 300,000: Hydroxyethylcellulose manufactured by Ashland, Natrosol 250 GR (trade name), weight average molecular weight = 300,000, degree of substitution of hydroxyethyl group = 2.5
-HEC, molecular weight 1,000,000: Hydroxyethylcellulose manufactured by Ashland, Natrosol 250 HR (trade name), weight average molecular weight = 1,000,000, degree of substitution of hydroxyethyl group = 2.5

The hydrophobizing agents used in Table 1 are as follows.
-Glycidyl, C4: butyl glycidyl ether, manufactured by Yokkaichi Synthetic Co., Ltd., DY-BP (trade name)
・ Glycidyl, C12: lauryl glycidyl ether, manufactured by Yokkaichi Synthetic Co., Ltd., Epogorose LA (D) (trade name)
Epoxy, C4: 1,2-epoxy hexane, manufactured by Wako Pure Chemical Industries, Ltd. Epoxy, C12: 1,2-epoxy tetradecane, manufactured by Wako Pure Chemical Industries, Ltd. Epoxy, C14: 1,2-epoxy hexadecane, Wako Pure Chemical Industries Ltd. ・ Glycidyl ammonium, C12: 3-chloro-2-hydroxypropyl dodecyl dimethyl ammonium chloride, Yokkaichi synthesis Co., Ltd., CDDA (trade name)

  As is clear from Table 1, the treatment of the polysaccharide derivative of the present invention suppressed adhesion of sebum dirt and improved the cleaning performance, and it became clear that the polysaccharide derivative of the present invention is excellent in formulation fluidity. .

  The polysaccharide derivative of the present invention can improve the washing performance, and the polysaccharide derivative of the present invention exhibits excellent formulation fluidity. The polysaccharide derivative of the present invention is extremely excellent in the improvement of the cleaning performance to the fabric treated with these compositions by being added to the component of the cleaning composition for clothes or to the cleaning composition. It can give an effect. Furthermore, good formulation flowability with these compositions is obtained.

Claims (10)

It is a polysaccharide derivative having a cationic group and a hydrocarbon group (R) having 2 or more carbon atoms,
The hydrocarbon group (R) is bonded directly or through a linking group (excluding a cationic group) to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide,
The hydroxyalkylated polysaccharide has a weight average molecular weight of 10,000 or more and 190,000 or less.
Polysaccharide derivatives. Degree of substitution of cationic groups (MS _C) is 0.001 to 1., polysaccharide derivative according to claim 1. The polysaccharide derivative according to claim 1 or 2, wherein the degree of substitution (MS _R ) of the hydrocarbon group (R) is 0.001 or more and 1 or less. The hydrocarbon group (R) is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group of a hydroxyalkylated polysaccharide by a group represented by any one of formulas (1-1-1) to (1-4) The polysaccharide derivative according to any one of Items 1 to 3.

(In the formulas (1-1-1) to (1-4), R ¹¹ and R ¹² each independently represent an alkylene group having 2 to 4 carbon atoms, and R represents a hydrocarbon group having 2 or more carbon atoms. In the following, * indicates the bonding position of the hydroxyalkylated polysaccharide with a hydrogen atom removed from the hydroxyl group, n1 indicates the average addition mole number of -R ¹¹ O-, and n2 indicates the average addition of -R ¹² -O- Indicates the number of moles, n1 and n2 are 0 or more and 30 or less.)   The polysaccharide derivative according to any one of claims 1 to 4, wherein the carbon number of the hydrocarbon group (R) is 4 or more and 22 or less.   The polysaccharide derivative according to any one of claims 1 to 5, wherein the polysaccharide is cellulose or guar gum. The polysaccharide derivative according to any one of claims 1 to 6, wherein the cationic group is represented by formula (2-1) or formula (2-2).

(In Formula (2-1) and Formula (2-2), R ^{21 to} R ²³ each independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ⁻ represents an anion, and t is 0 to 3) The following integer is shown, and * shows the bonding position with the group except the hydrogen atom from the hydroxyl group of the hydroxyalkylated polysaccharide.) The ratio of the substitution degree of the hydrocarbon group _(R) (MS R) and the degree of substitution of cationic groups _{(MS C) (MS R /} MS C) is 0.001 to 1., of claims 1 to 7 The polysaccharide derivative according to any one. Degree of substitution of anionic groups (MS _A) and the degree of substitution of the cationic groups ratio _{(MS C) (MS A /} MA C) is 3 or less, polysaccharide derivative according to claim 1 .   10. The hydrocarbon group (R) having 2 or more carbon atoms is introduced into a hydroxyalkylated polysaccharide having a weight average molecular weight of 10,000 or more and 190,000 or less, and then reacted with a cationizing agent. The manufacturing method of the polysaccharide derivative as described in-.