WO2024122361A1 - Poly(alkylene oxide)-containing compound - Google Patents

Abstract

The present invention provides a poly(alkylene oxide)-containing compound having satisfactory biodegradability and having satisfactory storage stability in detergent compositions, a production method therefor, and a detergent composition containing the compound. The present invention relates to a poly(alkylene oxide)-containing compound comprising a cation group, a linking group, and a structural unit derived from a poly(alkylene oxide), characterized in that the linking group has been combined with the structural unit derived from a poly(alkylene oxide) and the cation group has at least one amide bond.

Description

Polyalkylene oxide-containing compounds

The present invention relates to a polyalkylene oxide-containing compound that is biodegradable and has excellent storage stability in a detergent composition, a method for producing the compound, and a detergent composition containing the compound.

Conventionally, polymers in which polyalkyleneimine has a main chain and ethylene oxide or the like is added to the nitrogen atom in the polyalkyleneimine have been known as polyalkyleneimine polyalkyleneoxide. This polymer is known to act as a polymer builder, and is used as a component of liquid detergents because it has the property of dissolving in liquid detergents. When polyalkyleneimine polyalkyleneoxide is contained in a detergent together with an activator, it prevents re-contamination due to dirt removed by washing, and exerts high cleaning power.

Various studies have been conducted on polyalkyleneimine polyalkyleneoxide. For example, Patent Document 1 discloses a copolymer having a structure in which maleic anhydride is added to the terminal group of the polyalkyleneoxide of a polyalkyleneimine alkyleneoxide copolymer having an alkyleneimine monomer unit with polyalkyleneoxide.

Patent Document 2 discloses a polyalkyleneamine alkyleneoxide copolymer containing an alkyleneamine structural unit having a polyalkyleneoxide chain, in which a part or all of the terminal groups of the polyalkyleneoxide chain of the polyalkyleneamine alkyleneoxide copolymer have been subjected to an addition reaction with lauryl glycidyl ether. Patent Document 3 discloses a polymer having a structure constituting the polymer, the structure of which includes at least one amine having at least two amino groups, at least one acrylate selected from predetermined acrylates, and at least one monoacrylate, each in a predetermined ratio.

JP 2010-168185 A JP 2012-149185 A International Publication No. 2022/128684

By the way, the inventors have found through their investigations that the anti-redeposition ability can be improved by using in a detergent composition a polymer in which the alkylene oxide end group of a polyalkylene oxide copolymer containing an alkyleneamine structural unit having a polyalkylene oxide chain is modified.

However, the polymers in which the alkylene oxide end groups of the polyalkyleneamine alkylene oxide copolymers containing alkyleneamine structural units having polyalkylene oxide chains, as described in Patent Documents 1 to 3, have been modified, have room for improvement in terms of biodegradability and storage stability in detergent compositions.

The present invention has been made in consideration of the above-mentioned problems, and aims to provide a polyalkylene oxide-containing compound having good biodegradability and good storage stability in a detergent composition, a method for producing the compound, and a detergent composition containing the compound.

The present inventors have investigated polyalkylene oxide-containing compounds that have good anti-soil redeposition ability and good storage stability in detergent compositions, and have found that a polyalkylene oxide-containing compound having a cationic group, a structural unit derived from polyalkylene oxide, and a linking group bonded to the structural unit derived from polyalkylene oxide, and further having a structure in which the cationic group has at least one amide bond, is a polymer that has excellent anti-soil redeposition ability and also has good storage stability in detergent compositions, thereby arriving at the present invention.

That is, the present invention is as follows.
[1] A polyalkylene oxide-containing compound having a cationic group, a linking group, and a structural unit derived from a polyalkylene oxide,
the linking group is bonded to a structural unit derived from a polyalkylene oxide,
A polyalkylene oxide-containing compound, wherein the cationic group has at least one amide bond.

[2] The polyalkylene oxide-containing compound according to [1], wherein the linking group is one or more groups selected from an ester group, a thioester group, an amide group, a thioamide group, an acetal group, a hemiacetal group, and a hemiketal group.

[3] A substituent represented by the following general formula (1),

In the general formula (1), R ¹ is the same or different and represents a hydrocarbon group having 2 to 6 carbon atoms. X is one or more selected from a -C(=α ¹ )-β ¹ - group, a >C=α ¹ group, a -α ¹ -CR ² R ³ -β ¹ - group, and a -CR ⁴ (OH)-α ¹ - group, and α ¹ and β ¹ are the same or different and represent a hetero atom or a group in which a hydrogen atom is bonded to a hetero atom. R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 10 carbon atoms. s is an integer from 1 to 300. Y is a direct bond, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a substituent represented by the following general formula (2). Z is a direct bond, -(CH ₂ ) _n -(S) _m -(CH ₂ ) _p represents an -O- group, a -(CH ₂ ) _n -α ² - group, or a substituent represented by the following general formula (3). α ² represents a heteroatom or a group in which a hydrogen atom is bonded to a heteroatom. m is 0 or 1, and n is an integer from 1 to 10. p is an integer from 1 to 10. T represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.

(In general formula (2), q is an integer of 1 to 300. R ⁵ and R ⁶ are the same or different and each represents a hydrocarbon group having 2 to 6 carbon atoms.)

(In general formula (3), n is an integer from 1 to 10.)
and a cationic group having two or more nitrogen atoms,
The polyalkylene oxide-containing compound according to [1] or [2], characterized in that the substituent represented by the general formula (1) is bonded to at least one nitrogen atom contained in the cationic group.

[4] The polyalkylene oxide-containing compound according to [3], wherein the heteroatoms α ¹ and β ¹ of X in the substituent represented by the general formula (1) are oxygen atoms or nitrogen atoms.

[5] The polyalkylene oxide-containing compound according to [3] or [4], characterized in that Y in the substituent group according to the general formula (1) is a hydrocarbon group having 2 to 4 carbon atoms.

[6] The polyalkylene oxide-containing compound according to any one of [3] to [5], characterized in that the amount of NH groups contained in the polyalkylene oxide-containing compound is 80 mol% or less based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

[7] A method for producing a polyalkylene oxide-containing compound according to any one of [1] to [6], comprising the steps of:
The production method includes a first step of subjecting an α,β-unsaturated carbonyl compound having a polyalkylene oxide chain to a cationic amino group by Michael addition;
and a second step of reacting an NH group in the structure of the cationic group portion of the product obtained in the first step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

[8] A method for producing a polyalkylene oxide-containing compound according to any one of [1] to [6], comprising the steps of:
The production method includes a first step of subjecting one or more compounds selected from a cyclic lactone compound and a cyclic lactam compound to a ring-opening addition reaction with an amino group, which is a cationic group;
A method for producing a polyalkylene oxide-containing compound, comprising: a second step of introducing a polyalkylene oxide chain into the active hydrogen generated in the first step; and a third step of reacting an NH group in the structure of the cationic group portion of the product obtained in the second step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

[9] A detergent or detergent composition containing a polyalkylene oxide-containing compound according to any one of [1] to [6].

The polyalkylene oxide-containing compound of the present invention has good biodegradability and good storage stability in a detergent composition, and therefore can be suitably used as a component of a detergent composition.
The method for producing a polyalkylene oxide-containing compound of the present invention is a suitable method for producing such a polyalkylene oxide-containing compound.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following preferred embodiments of the present invention are merely exemplary in nature and are not intended to limit the present invention, its applications, or its uses.
Furthermore, a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

Unless otherwise specified in the following explanation, "%" means "% by mass", "parts" means "parts by mass", and the range "A to B" indicates that the range is from A to B. In addition, in the present invention, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic" means "acrylic" or "methacrylic".

1. Polyalkylene Oxide-Containing Compound The polyalkylene oxide-containing compound of the present invention has the following substituents and structural units 1) to 4).
1) a cationic group; 2) a linking group; 3) a structural unit derived from a polyalkylene oxide; and 4) an amide structure bonded to a cationic group.

The cationic group is a group having an amino group, which may be in the form of a primary amine, a secondary amine, a tertiary amine, or a quaternary amine.
In the polyalkylene oxide-containing compound of the present invention, the cationic group may have one amino group or may have two or more amino groups, but it is preferable that the cationic group has two or more amino groups.When the polyalkylene oxide-containing compound has two or more amino groups in its structure, the cationic group may be in the form of a polymer having two or more structural units having amino groups.Specific examples of the cationic group will be described later.

The polyalkylene oxide-containing compound of the present invention is preferably a compound having a structure in which the structural unit derived from polyalkylene oxide and the cationic group (or the structural unit having the cationic group) are not directly bonded, but are linked via the linking group.Furthermore, the polyalkylene oxide-containing compound of the present invention is preferably a compound having a structure in which the nitrogen atom of the amino group of the cationic group is bonded to the linking group.
In the present invention, the structural unit derived from polyalkylene oxide means a structural unit in which a plurality of structures represented by -R-O- (R represents an alkylene group) are bonded together.

The linking group in the present invention is preferably at least one selected from an ester group, an amide group, a thioester group, a thioamide group, a hemiacetal group, a hemiketal group, and an acetal group.
When the linking group is one or more selected from ester group, amide group, thioester group, thioamide group, hemiacetal group, hemiketal group, and acetal group, there is no particular limitation on the linking group, but it is preferably one or more selected from ester group, amide group, thioester group, thioamide group, and acetal group, and more preferably one or more selected from ester group and amide group. When the linking group is one of these groups, it is preferable because it can improve the storage stability and decomposition after use of the polyalkylene oxide-containing compound. In addition, it is preferable because the mud particle dispersion ability and redeposition prevention ability of the polyalkylene oxide-containing compound of the present invention tend to be improved.
In recent years, detergent compositions are required to have excellent cleaning ability and also to be easily decomposed in nature from the viewpoint of environmental friendliness. For this reason, the linking group is preferably a hydrolyzable group or a functional group that is decomposed by an extracellular enzyme, and among the above linking groups, an ester group or an amide group is particularly preferred.
Biodegradable means that it can be metabolized and broken down by bacteria, fungi, and other living organisms.

The polyalkylene oxide-containing compound of the present invention preferably has a substituent represented by the following general formula (1): The substituent represented by the following general formula (1) is a substituent containing a structural moiety derived from a polyalkylene oxide represented by (-R ¹ -O-) _s and a linking group represented by -Y-X-Z-.
The polyalkylene oxide-containing compound of the present invention preferably has a structure in which a substituent represented by the following general formula (1) is bonded to a cationic group.

In the general formula (1), R ¹ is the same or different and represents a hydrocarbon group having 2 to 6 carbon atoms. X is one or more selected from a -C(=α ¹ )-β ¹ - group, a >C=α ¹ group, a -α ¹ -CR ² R ³ -β ¹ - group, and a -CR ⁴ (OH)-α ¹ - group, and α ¹ and β ¹ are the same or different and represent a hetero atom or a group in which a hydrogen atom is bonded to a hetero atom. R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 10 carbon atoms. s is an integer from 1 to 300. Y is a direct bond, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a substituent represented by the following general formula (2). Z is a direct bond, -(CH ₂ ) _n -(S) _m -(CH ₂ ) _p represents an -O- group, a -(CH ₂ ) _n -α ² - group, or a substituent represented by the following general formula (3). α ² represents a heteroatom or a group in which a hydrogen atom is bonded to a heteroatom. m is 0 or 1, and n is an integer from 1 to 10. p is an integer from 1 to 10. T represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.

(In general formula (2), q is an integer of 1 to 300. R ⁵ and R ⁶ are the same or different and each represents a hydrocarbon group having 2 to 6 carbon atoms.)

(In general formula (3), n is an integer from 1 to 10.)

In the general formula (1), X is preferably at least one selected from a -C(=α ¹ )-β ¹ - group, a >C=α ¹ group, a -α ¹ -CR ² R ³ -β ¹ - group, and a -CR ⁴ (OH)-α ¹ - group.
X is preferably an ester group, a thioester group, an amide group, a thioamide group, an acetal group, or a hemiacetal group, and more preferably an ester group, an amide group, or an acetal group.
Furthermore, when α ¹ and β ¹ are heteroatoms, the type of the heteroatom is not particularly limited, but is preferably at least one type selected from an oxygen atom and a sulfur atom.
When α ¹ and β ¹ are groups in which a hydrogen atom is bonded to a heteroatom, they are preferably NH groups.
By using these preferable substituents and atoms, the storage stability and decomposition property of the polyalkylene oxide compound are improved.

R ¹ in the general formula (1) is not particularly limited as long as it is a hydrocarbon group having 2 to 6 carbon atoms, but is preferably a hydrocarbon group having 2 to 4 carbon atoms. The s number of R ¹ in the general formula (1) may be hydrocarbon groups having the same number of carbon atoms, or may be a combination of hydrocarbon groups having different numbers of carbon atoms, but the carbon number of R ¹ is preferably 2 to 4, as described above.
For this reason, the —R ¹ —O— group in the general formula (1) is preferably at least one type selected from an oxyethylene group, an oxypropylene group, and an oxybutylene group.
These preferred substituents and atoms improve the water solubility of the polyalkylene oxide compound, and the polyalkylene oxide compound of the present invention can have superior mud dispersibility and compatibility with liquid detergents.

In the general formula (1), s is not particularly limited as long as it is an integer of 1 to 300. It is preferably 1 to 200, more preferably 2 to 100, and further preferably 3 to 50.
When s in the general formula (1) is within such a range, the mud dispersibility and anti-soil redeposition performance of the polyalkylene oxide compound are further improved.

When s R ^1s present in the general formula (1) are a combination of hydrocarbon groups having different numbers of carbon atoms, the general formula (1) preferably has a structure represented by the following general formula (1′):

(In general formula (1'), R ^1a and R ^1b each represent a hydrocarbon group having 2 to 6 carbon atoms, each having a different carbon number. s1 and s2 each represent the same or different integers, and s1+s2 is an integer of 2 to 300. X, Y, Z, and T are the same as X, Y, Z, and T in general formula (1), respectively.)

In the above general formula (1'), R ^1a is preferably a hydrocarbon group having 3 to 6 carbon atoms, and more preferably a hydrocarbon group having 3 to 4 carbon atoms.
R ^1b is preferably a hydrocarbon group having 2 to 4 carbon atoms, more preferably a hydrocarbon group having 2 to 3 carbon atoms, and even more preferably a hydrocarbon group having 2 carbon atoms.
s1 is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
s2 is preferably 1 to 200, more preferably 5 to 100, and further preferably 10 to 50.

Furthermore, when R ^1b in the general formula (1') is a hydrocarbon group having 2 carbon atoms, the content of -R 1b -O- groups is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more, when the total amount of -R ^1a -O- groups and -R ^1b -O- groups in the general formula (1 ^' ) is taken as 100 mol %.
When R ^1b is a hydrocarbon group having 2 carbon atoms, if the content of -R ^1b -O- groups in the general formula (1') is within the above-mentioned range, the hydrophilicity of the polyalkylene oxide chain is improved, and therefore, the dispersibility of mud particles and the mud redeposition prevention performance of the polyalkylene oxide-containing compound produced using that compound as a raw material are improved, which is preferable.

R ² , R ³ , and R ⁴ in the general formula (1) are not particularly limited as long as they are the same or different and are a hydrogen atom or an organic group having 1 to 10 carbon atoms. They are preferably a hydrogen atom or an organic group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or a methyl group.

Y in the general formula (1) is a direct bond, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a group represented by the general formula (2). When Y in the general formula (1) is a hydrocarbon group having 1 to 10 carbon atoms, it is preferably a hydrocarbon group having 2 to 6 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms. Furthermore, the hydrocarbon group is preferably an alkylene group.

In the general formula (2), q is an integer of 1 to 300, and the preferred range is the same as that of s in the general formula (1).
R ⁵ and R ⁶ in formula (2) are the same or different and each is a hydrocarbon group having 2 to 6 carbon atoms, and preferred hydrocarbon groups are the same as R ¹ in formula (1).

The polyalkylene oxide-containing compound of the present invention is preferably one that is decomposed at the linking group portion. In this case, it is preferable that the decomposition portion of the linking group that bonds the cationic group and the structural unit derived from the polyalkylene oxide is not directly bonded to the cationic group, but is bonded to a position somewhat distant from the cationic group, as explained as the preferred structure in the above general formula (1), from the viewpoint of ensuring the decomposition property of the polyalkylene oxide compound.

Z in the general formula (1) is not particularly limited as long as it is a direct bond, a -(CH ₂ ) _n -(S) _m -(CH ₂ ) _p -O- group, a -(CH ₂ ) _n -α ² - group, or the following general formula (3).
^α2 is a heteroatom. n and p each represent an integer of 1 to 10, and m is 0 or 1.
When ^α2 is a heteroatom, it is not particularly limited, but is preferably an oxygen atom or a sulfur atom.
When ^α2 is a group in which a hydrogen atom is bonded to a heteroatom, it is preferably an NH group.
There are no particular limitations on n and p so long as they are integers of 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
There is no particular limitation on m so long as it is 0 or 1.
When Z in the general formula (1) has such a preferred structure, synthesis for introducing a linking group into the polyalkylene oxide becomes easy.

In the general formula (1), T may be the same or different and is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and the structure may be appropriately selected in order to adjust the hydrophilicity or hydrophobicity. As the organic group, a hydrocarbon group is preferable. More preferable are a linear or branched alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
Also preferred are organic groups having a structure in which any one of a carboxyl group, a phosphoric acid group, and a sulfonic acid group is bonded to the above-mentioned hydrocarbon group.

In the polyalkylene oxide-containing compound of the present invention, the cationic group has at least one amide bond.
As described above, the cationic group in the present invention has an amino group. If the cationic group has a primary amino group ( _NH2 group) or a secondary amino group (NH group), and if the structure of the polyalkylene oxide-containing compound contains an ester structure, ester amide exchange or hydrolysis occurs at the primary or secondary amino group portion with the ester structure in the detergent composition, which causes a decrease in the storage stability of the polymer.
In response to this, such ester-amide exchange and hydrolysis can be suppressed by amidating the NH group in the cationic group with an acid compound or the like, thereby imparting excellent storage stability to the polyalkylene oxide-containing compound of the present invention in a detergent composition.

When the cationic group has at least one amide bond, the amide bond may be formed by bonding a linking group to a primary or secondary amino group (NH group) in the cationic group, or may be formed by reacting the primary or secondary amino group in the cationic group with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.
The amide bond in the cationic group of the polyalkylene oxide-containing compound of the present invention may be formed by any of these methods, but a preferred embodiment of the polyalkylene oxide-containing compound of the present invention is one in which a linking group is bonded to the primary and secondary amino groups in the cationic group, and then the remaining primary and secondary amino groups are reacted with one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds to reduce the number of primary and secondary amino groups.
Therefore, the polyalkylene oxide-containing compound of the present invention preferably has a structure containing an amide bond in the cationic group formed by a reaction between a primary amino group ( _NH2 group) or a secondary amino group (NH group) and one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.
Furthermore, the acid anhydride is preferably an acid anhydride derived from a compound having two or more carboxyl groups, such as a dicarboxylic acid. By performing an addition reaction with an NH group using an acid anhydride derived from a compound having two or more carboxyl groups, the terminal of the amide structure becomes a carboxylic acid (or a salt thereof), thereby improving storage stability through intramolecular neutralization and enabling the expression of a chelating ability to improve cleaning performance.

The structure including an amide bond formed by a reaction of a primary amino group ( _NH2 group) or a secondary amino group (NH group) in the cationic group with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound is a structure represented by the following general formula (4-1) or (4-2).

(In general formulas (4-1) and (4-2), R ⁷ represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a -R ⁹ -COOX group. R ⁹ represents a divalent hydrocarbon group having 1 to 16 carbon atoms, and X represents a hydrogen atom, a halogen atom, or a metal atom. R ⁸ represents a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms.)
The hydrocarbon groups of ^R7 and ^R9 may be saturated or unsaturated. They may also have a chain structure, a cyclic structure, or a combination of a chain structure and a cyclic structure. If they have a cyclic structure, they may be an alicyclic structure or an aromatic ring.
Examples of the metal atom of X include metal atoms of Group 1 of the periodic table, such as lithium, sodium, and potassium; and metal atoms of Group 2 of the periodic table, such as magnesium, calcium, and strontium.

The amount of NH groups contained in the polyalkylene oxide-containing compound of the present invention is not particularly limited, but is preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less, based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.
As mentioned above, the NH group in the cationic group of the polyalkylene oxide-containing compound of the present invention is reduced by amidation with an acid compound or the like. Also, the NH group is reduced by bonding with a linking group at the amino group part contained in the cationic group. From the viewpoint of making the polyalkylene oxide-containing compound more excellent in mud dispersibility and redeposition prevention performance, it is preferable that the amount of polyalkylene oxide group introduced into the polyalkylene oxide compound is large, and it is preferable that the amount of NH group is small. Also, as mentioned above, from the viewpoint of making the polyalkylene oxide-containing compound of the present invention have excellent storage stability in a detergent composition, it is preferable that the amount of NH group is small.

As described above, the cationic group of the polyalkylene oxide-containing compound of the present invention can also be expressed as a structural unit having an amino group. The cationic group can be formed by reacting a precursor that is a raw material of the structural unit having an amino group with a compound that is a raw material of a linking group or a structural unit portion derived from a polyalkylene oxide, and further reacting it with a compound such as an acid anhydride for forming an amide bond in the cationic group as necessary.
Specific examples of the structural units include those derived from compounds such as polyethylene polyamines (PEA) such as diethylene triamine, triethylene tetramine, and tetraethylene pentamine, tetrabutylene pentamine, polyethylene imine (PEI), and polyamidoamine.

The precursor that serves as the raw material for the structural unit having an amino group can be represented by the following general formula (5).

(In general formula (5), R ¹⁰ may be the same or different and represent a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. P may be the same or different and represent a hydrogen atom or a structural unit having another amino group due to branching. a, b and c may be the same or different and represent an integer of 0 or 1 or more, and at least one of a, b and c is an integer of 1 to 100. Note that at least two or more -N-R ¹⁰ - units are present in the structural unit having an amino group.)
When a precursor represented by the above general formula (5) is used, the group formed by removing the hydrogen atom bonded to the nitrogen atom from the precursor becomes the cationic group possessed by the polyalkylene oxide compound of the present invention.
In addition, with respect to the precursor serving as a raw material for the structural unit having an amino group, examples of the structural formula of the amino group constituting the precursor in the case of the general formula (5) include H ₂ N—R ¹⁰ —, —NH—R ¹⁰ —, and —N(—)—R ¹⁰ —.

When P in the general formula (5) is a structural unit having another amino group, the structural unit having another amino group is preferably represented by the following general formula (6), and is preferably bonded to the structure represented by general formula (5) via an R ^10′ group.

(In the general formula (6), a', b', c', P', and ^R10' are the same as a, b, c, P, and ^R10 in the general formula (5), respectively.)

In the precursors serving as raw materials for structural units having an amino group represented by the above general formulas (5) and (6), the alkylene group in R ¹⁰ may be one type or two or more types, but is preferably one type, and is preferably an ethylene group. Note that when R ¹⁰ is a branched alkylene group having 3 to 6 carbon atoms, a 1,2-propylene group is preferred.
In the above general formulas (5) and (6), a, b, and c may be the same or different and may be an integer of 0 or 1 or more, but each is preferably an integer of 0 to 100. Furthermore, a+b+c may be a number of 1 or more, but a+b+c being 1 to 4, 1 to 3, or 1 or 2 is a preferred embodiment of the precursor that serves as a raw material for the structural unit having an amino group. A number of a+b+c being 5 or more is also a preferred embodiment of the precursor that serves as a raw material for the structural unit having an amino group.

Examples of the polyalkylene oxide-containing compound of the present invention (having a substituent represented by the above general formula (1)) include compounds having a structure in which a linking group is bonded to the nitrogen atom of an amino group of a (poly)alkyleneamine having at least one unit selected from the group consisting of an amino group unit containing a primary amine nitrogen atom, an amino group unit containing a secondary amine nitrogen atom, and an amino group unit containing a tertiary amine nitrogen atom, and a structural unit derived from a polyalkylene oxide is bonded to the other side of the linking group, and further at least one cationic group has an amide bond.
The amino group unit containing a primary amine nitrogen atom is represented, for example, by the following formula:
( _H2 -N- ^R10 )-
^R10 is the same as in formula (5).
In some cases, it also contains a structural unit represented by the following formula:
_-NH2
The amino group unit containing a secondary amine nitrogen atom is represented, for example, by the following general formula (7).

The amino group unit containing the tertiary amine nitrogen atom is represented, for example, by the following general formula (8):

(P and ^R10 in general formulas (7) and (8) are the same as those in general formula (5).)

In the structural unit having an amino group, the form of the amino group unit is not particularly limited, and for example, an amino group unit containing a primary amine nitrogen atom, an amino group unit containing a secondary amine nitrogen atom, and an amino group unit containing a tertiary amine nitrogen atom may be randomly present. The nitrogen atom constituting the amino group may be quaternized or oxidized.

An example of a precursor that serves as a raw material for the structural unit having a cationic group of the present invention represented by the general formula (5) is an amine compound represented by the following general formula (9).

(In general formula (9), R ¹¹ may be the same or different and represent a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. In addition, r represents an integer of 0 to 10.)
Specific examples of the cationic group of the polyalkylene oxide compound of the present invention will be described in detail below, taking as an example a case where the precursor serving as a raw material for the structural unit having a cationic group is an amine compound having two primary amines; however, the precursor serving as a raw material for the structural unit having a cationic group of the present invention is not limited to an amine compound having two primary amines.

The cationic group (structural unit having an amino group) of the present invention can be represented by the following general formula (10) in addition to those having an amino group unit represented by the general formulas (7) and (8).

(In general formula (10), R ¹¹ may be the same or different and represent a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms.)

The diamine compound serves as a precursor of the structural unit of the general formula (10).
When a (meth)acrylic acid compound is subjected to a Michael addition reaction with a diamine compound, which is a precursor of the general formula (10), a compound represented by the following general formula (11) is produced. When this product is further reacted with a diamine compound and an ester-amide exchange reaction occurs, a polyamine compound represented by the following general formula (12) is produced.

(R ¹¹ in general formula (11) and general formula (12) is the same as in general formula (9) and general formula (10). R ¹² may be the same or different and represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ¹³ represents a hydrogen atom or a methyl group.)

In the general formula (11), R ¹² may be the same or different and is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be appropriately selected in order to adjust the hydrophilicity or hydrophobicity. The organic group is preferably a hydrocarbon group.

The polyalkylene oxide-containing compound of the present invention can be obtained by addition reacting a glycidyl ether compound having a polyalkylene oxide structure with the polyamine compound represented by the general formula (12). In this case, the amino group portion introduced by the reaction of a diamine compound with the compound represented by the general formula (11) can be regarded as a cationic group, and the cationic group can be regarded as having an amide bond.
The polyalkylene oxide-containing compound of the present invention can also be obtained by subjecting a polyamine compound represented by the general formula (12) to a Michael addition reaction with a (meth)acrylic acid compound having a polyalkylene oxide structure.
Furthermore, the polyalkylene oxide-containing compound of the present invention can also be obtained by addition polymerization of an alkylene oxide to the compound of the general formula (12).

The polyalkylene oxide-containing compound of the present invention can undergo a decomposition reaction by one or more decomposition methods selected from alkaline hydrolysis, enzymatic decomposition, and activated sludge, thereby reducing the molecular weight.
When the polyalkylene oxide-containing compound of the present invention is subjected to a decomposition test using one or more decomposition methods selected from alkaline hydrolysis, enzymatic decomposition, and activated sludge, the number average molecular weight after the decomposition test is preferably 0.5 or less, more preferably 0.4 or less, and even more preferably 0.2 or less, relative to the number average molecular weight before the decomposition test.
It is preferable that the number average molecular weight after the decomposition test is smaller than the number average molecular weight before the decomposition test, because when the polyalkylene oxide-containing compound of the present invention is used, for example, as a detergent or detergent composition, the burden on the environment caused by the compound discharged after washing is reduced.

The weight average molecular weight of the polyalkylene oxide-containing compound of the present invention is preferably 1,000 to 1,000,000, more preferably 3,000 to 500,000, and even more preferably 5,000 to 200,000.
It is preferable that the weight average molecular weight of the polyalkylene oxide-containing compound of the present invention is within the above-mentioned range, since the compound has excellent anti-soil redeposition ability while reducing the environmental load due to the decomposition reaction.
The weight average molecular weight of the polyalkylene oxide-containing compound can be measured by GPC under the following measurement conditions.
<Gel Permeation Chromatography (GPC) Measurement Conditions>
Apparatus: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector column: TSKgel α-M, α-2500 manufactured by Tosoh Corporation
Column temperature: 40°C
Flow rate: 0.8 mL / min
Injection volume: 100 μL
Calibration curve: Polyethylene glycol manufactured by GL Sciences, Mw = 194, 410, 615, 1020, 1450, 3860, 8160, 16100, 21160, 49930, 67600, 96100, 205500, 542500, 942000, the order of the calibration curve is third order.
GPC software: EcoSEC-WS manufactured by Tosoh Corporation
Eluent: 0.5 M acetic acid + 0.2 M Na nitrate / acetonitrile = 50/50 (v/v)

2. Composition of polyalkylene oxide-containing compound The polyalkylene oxide-containing compound of the present invention can be produced by a production method including a step of reacting one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds with the NH group contained in the cationic group, as described below.When a polyalkylene oxide-containing compound is produced by such a production method, a composition containing a polyalkylene oxide-containing compound and one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds may be produced.Such a composition containing a polyalkylene oxide-containing compound and one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds is also one of the present inventions.
The content of one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the total amount of the polyalkylene oxide-containing compound composition.

3. Production method of polyalkylene oxide-containing compound The production method (I) of the polyalkylene oxide-containing compound of the present invention includes a production method including a step of condensing a polyalkylene oxide compound having a carboxyl group with a hydrogen atom of an amino group of a (poly)alkyleneamine, or esterifying a polyalkylene oxide compound having a carboxylic acid halide group (hereinafter, this step is also referred to as the first step).

The (poly)alkyleneamine used in the manufacturing method (I) is a compound having the structural formula represented by the above-mentioned general formula (5). The polyalkylene oxide compound having a carboxyl group or the polyalkylene oxide compound having a carboxylic acid halide group used in the manufacturing method (I) can be represented by the following general formula (13).

(In general formula (13), R ¹ and s are the same as those in general formula (1). R ¹⁴ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ¹⁵ represents an organic group having 1 to 6 carbon atoms. R ¹⁴ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, or an aryl group. R ¹⁵ is preferably an alkyl group having 1 to 6 carbon atoms. Q represents OH, Cl, Br, or I.)

Among the compounds represented by formula (13), a compound represented by the following formula (13') in which R ¹⁵ is an organic group having a carbonyl group at the terminal is preferred.

(In general formula (13'), R ¹ , s, R ¹⁴ and Q are the same as those in general formula (13). ^{R 15'} represents an organic group having 1 to 5 carbon atoms.)

The organic group of R ¹⁴ in the general formula (13) and R ^15' in the general formula (13') is preferably a saturated or unsaturated hydrocarbon group.

Specific examples of the polyalkylene oxide compound having a carboxyl group include an esterification reaction product of an alkoxypolyalkylene glycol with a dicarboxylic anhydride such as succinic anhydride or maleic anhydride; a reaction product of an alkoxypolyalkylene glycol with a carboxylic acid halide; and a compound in which the terminal hydroxyl group of an alkoxypolyalkylene glycol is oxidized and carboxylated with an oxidizing agent.
Specific examples of the polyalkylene oxide compound having a carboxylic acid halide group include compounds having a structure in which the carboxyl group of the specific examples of the polyalkylene oxide compound having a carboxyl group is replaced with a carboxylic acid halide group.
The carboxylic acid halide includes fluorides, chlorides, bromides, and iodides of carboxylic acids.

The temperature at which the (poly)alkyleneamine represented by the general formula (5) is reacted with the polyalkylene oxide compound having a carboxyl group or a carboxylic acid halide group represented by the general formula (13) is preferably 50 to 200° C., and more preferably 100 to 200° C.
The reaction time is preferably 1 to 20 hours, and more preferably 1 to 10 hours.
When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively, improving reactivity and reducing the amount of unreacted raw materials, which tends to improve the mud particle dispersion ability and redeposition prevention ability of the polyalkylene oxide-containing compound of the present invention.

The proportion of the polyalkylene oxide compound having a carboxyl group or a carboxylic acid halide group used in the first step of the production method (I) is preferably 10 to 100 mol % relative to the number of moles of NH groups contained in the (poly)alkyleneamine used in the first step. It is more preferably 15 to 90 mol %, and even more preferably 20 to 80 mol %.

The manufacturing method (I) may further include a second step after the first step, in which the NH group in the structure of the cationic group portion of the product obtained in the first step is reacted with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound. This step is a step of further reducing the NH groups in the polyalkylene oxide-containing compound by forming an amide bond in the cationic group portion of the polyalkylene oxide-containing compound.

Examples of the acid anhydride used in the second step of the production method (I) include anhydrides of monocarboxylic acids having 2 to 18 carbon atoms, such as acetic anhydride, propionic anhydride, butyric anhydride, lauric anhydride, stearic anhydride, and benzoic anhydride; anhydrides of dicarboxylic acids having 3 to 18 carbon atoms, such as succinic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, and malonic anhydride; and derivatives of these monocarboxylic anhydrides and dicarboxylic anhydrides to which a substituent such as a hydrocarbon group having 1 to 10 carbon atoms, a sulfonic acid group, a phosphoric acid group, or an amino group is bonded, and one or more of these can be used.
The anhydride of a monocarboxylic acid is preferably one derived from a monocarboxylic acid having 2 to 14 carbon atoms, more preferably one derived from a monocarboxylic acid having 2 to 12 carbon atoms, more preferably one derived from a monocarboxylic acid having 2 to 10 carbon atoms, and even more preferably one derived from a monocarboxylic acid having 2 to 8 carbon atoms.
The dicarboxylic acid anhydride preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 4 to 8 carbon atoms.
The substituents on the derivatives of monocarboxylic anhydrides and dicarboxylic anhydrides preferably have 1 to 8 carbon atoms, and more preferably have 1 to 6 carbon atoms.
Furthermore, the acid anhydride is preferably an acid anhydride derived from a compound having two or more carboxyl groups, such as a dicarboxylic acid. By performing an addition reaction with an NH group using an acid anhydride derived from a compound having two or more carboxyl groups, the terminal of the amide structure becomes a carboxylic acid (or a salt thereof), thereby improving storage stability through intramolecular neutralization and enabling the expression of a chelating ability to improve cleaning performance.

Examples of the acid halide used in the second step of the production method (I) include halides of monocarboxylic acids having 2 to 18 carbon atoms, such as acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, and benzoic acid; halides of dicarboxylic acids having 3 to 18 carbon atoms, such as succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, phthalic acid, itaconic acid, and malonic acid; and derivatives of these monocarboxylic acid halides and dicarboxylic acid halides to which a substituent such as a hydrocarbon group having 1 to 10 carbon atoms, a sulfonic acid group, a phosphoric acid group, or an amino group is bonded. One or more of these may be used.
Halides include fluorides, chlorides, bromides, iodides, and the like.
The monocarboxylic acid preferably has 2 to 18 carbon atoms, and more preferably has 2 to 10 carbon atoms.
The dicarboxylic acid preferably has 4 to 18 carbon atoms, and more preferably has 4 to 10 carbon atoms.
The substituents on the derivatives of monocarboxylic acids and dicarboxylic acids preferably have 1 to 10 carbon atoms, and more preferably have 1 to 8 carbon atoms.

A cyclic ester compound can also be used in the second step of the production method (I). The cyclic ester compound undergoes a ring-opening addition reaction with the NH group in the structure of the cationic group portion to form an amide bond.
Examples of the cyclic ester compound used in the second step of the production method (I) include lactone compounds having 2 to 18 carbon atoms, such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, and γ-nonalactone; condensates of two or more molecules of hydroxycarboxylic acids having 4 to 18 carbon atoms, such as lactide and glycolide, and derivatives in which a substituent such as a hydrocarbon group having 1 to 10 carbon atoms, a sulfonic acid group, a phosphoric acid group, or an amino group is bonded to these lactone compounds or hydroxycarboxylic acid condensates, and one or more of these may be used.
The lactone compound preferably has 2 to 10 carbon atoms, and more preferably has 2 to 6 carbon atoms.

The ratio of the acid anhydride, acid halide, and cyclic ester compound used in the second step of the production method (I) is not particularly limited, but it is preferable that the sum of the number of moles of the polyalkylene oxide compound having a carboxyl group or a carboxylic acid halide group used in the first step and the number of moles of the acid anhydride, acid halide, and cyclic ester compound used in the second step is 10 to 100 mol % relative to the number of moles of NH groups contained in the (poly)alkyleneamine used in the first step. More preferably, it is 15 to 100 mol %, and even more preferably, it is 20 to 100 mol %.

Another example of the method (II) for producing the polyalkylene oxide-containing compound of the present invention is a production method including a step of subjecting one or more compounds selected from a cyclic lactone compound and a cyclic lactam compound to a ring-opening addition reaction with an amino group contained in a cationic group (hereinafter, this step is also referred to as the first step), and then a step of introducing a polyalkylene oxide chain into the active hydrogen generated by the ring-opening addition reaction (hereinafter, this step is also referred to as the second step).
More specifically, an ester bond or an amide bond can be introduced by ring-opening addition reaction of a caprolactone compound or a caprolactam compound to the hydrogen atom of the amino group of a (poly)alkyleneamine. The terminal residue obtained by ring-opening addition reaction of a caprolactone compound or a caprolactam compound is a hydroxyl group or an _NH2 group. The polyalkylene oxide-containing compound of the present invention can be produced by ring-opening addition reaction of an epoxy compound such as ethylene oxide to this hydroxyl group or NH2 _group .

The (poly)alkyleneamine used in the production method (II) is a compound having the structural formula represented by the above-mentioned general formula (5).
The lactone compound used in the production method (II) may be α-lactone (three-membered ring), β-lactone (four-membered ring), γ-lactone (five-membered ring), δ-lactone (six-membered ring), ε-lactone (seven-membered ring), or a derivative thereof. Specific examples include α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone. The lactam compound may be one or more of α-lactam (three-membered ring), β-lactam (four-membered ring), γ-lactam (five-membered ring), δ-lactam (six-membered ring), ε-lactam (seven-membered ring), or a derivative thereof.

In the first step of the above-mentioned manufacturing method (II), a lactone compound and/or a lactam compound is bonded to the hydrogen atom of the amino group of the (poly)alkyleneamine represented by the general formula (5) through a ring-opening addition reaction of the lactone compound and/or the lactam compound to the (poly)alkyleneamine represented by the general formula (5), thereby obtaining a (poly)alkyleneamine-lactone adduct and/or a (poly)alkyleneamine-lactam adduct. An example of the reaction is shown in the following scheme.

(R ¹¹ and r in general formula (14), general formula (15), and general formula (16) are the same as those in general formula (9) above.)

In the first step of the production method (II), the reaction temperature for the ring-opening addition reaction between the (poly)alkyleneamine represented by the general formula (5) and the lactone compound and/or lactam compound is preferably 0 to 100° C., and more preferably 20 to 80° C.
The reaction time is preferably 1 hour or longer.

In the (poly)alkyleneamine-lactone adduct and (poly)alkyleneamine-lactam adduct obtained as the product of the first step of the production method (II), the terminal residues resulting from the addition reaction of the lactone compound and the lactam compound are hydroxyl groups or _NH2 groups. In the second step of the production method (II), the polyalkylene oxide-containing compound of the present invention can be obtained by subjecting this hydroxyl group or _NH2 group to a ring-opening addition reaction with an alkylene oxide such as ethylene oxide or propylene oxide. The reaction conditions for the ring-opening addition reaction of the alkylene oxide are the same as those for a conventional method.

The production method (II) may further include a third step after the second step, in which one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound are reacted with the NH group in the structure of the cationic group portion of the product obtained in the second step. This step is a step of forming an amide bond in the cationic group portion of the polyalkylene oxide-containing compound to further reduce the NH group in the polyalkylene oxide-containing compound.
The acid anhydrides, acid halides and cyclic ester compounds that can be used in this third step are the same as those used in the second step of the above-mentioned production method (I).
The amount of the acid anhydride, acid halide, and cyclic ester compound used in the third step is preferably such that the sum of the number of moles of the cyclic lactone compound or cyclic lactam compound used in the first step and the number of moles of the acid anhydride, acid halide, and cyclic ester compound used in the second step is 10 to 100 mol %, more preferably 15 to 100 mol %, and even more preferably 20 to 100 mol %, relative to the number of moles of NH groups contained in the (poly)alkyleneamine used in the first step.

Another method (III) for producing the polyalkylene oxide-containing compound of the present invention includes a first step of Michael addition of an α,β-unsaturated carbonyl compound having a polyalkylene oxide chain to an amino group, which is a cationic group, and a second step of reacting one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound with the NH group in the structure of the cationic group portion of the product obtained in the first step.

The α,β-unsaturated carbonyl compound having a polyalkylene oxide chain used in the first step of the production method (III) is preferably an (alkoxy)polyalkylene oxide (meth)acrylate or an (alkoxy)polyalkylene glycol (meth)acrylamide, and the compound having an amino group, which is a cationic group, is preferably a polyalkyleneamine.
Therefore, the first step is preferably a step of obtaining a compound in which a polyamine and an alkylene oxide are bonded via an ester bond by subjecting the double bond of an (alkoxy)polyalkylene oxide (meth)acrylate or an (alkoxy)polyalkylene glycol (meth)acrylamide to a Michael addition reaction with an amino group of a polyalkyleneamine.

The (poly)alkyleneamine used in the manufacturing method (III) may be a compound having the structural formula represented by the above-mentioned general formula (5). The (alkoxy)polyalkylene oxide (meth)acrylate compound or (alkoxy)polyalkylene glycol (meth)acrylamide used in the manufacturing method (III) may be represented by the following general formula (17).

(In general formula (17), R ¹ , s, and T are the same as those in general formula (1). R ¹⁶ is the same or different and is a hydrogen atom or a methyl group. G represents O, N, or NH, and d is 1 or 2. When G is N, d is 2, and when G is O or NH, d is 1.)

The above general formula (17) can also be expressed as the following general formula (18):

(In general formula (18), R ¹⁶ , G, T, and d are the same as those in general formula (17). m ¹ and n ¹ each represent an integer of 0 to 300, and m ¹ +n ¹ is the same as s in general formula (1). R ¹⁷ and R ¹⁸ are the same or different and each represent a hydrocarbon group having 2 to 6 carbon atoms.)

In general formula (18), R ¹⁷ is a hydrocarbon group having 2 to 6 carbon atoms, preferably a hydrocarbon group having 2 to 4 carbon atoms, more preferably a hydrocarbon group having 2 to 3 carbon atoms, and even more preferably a hydrocarbon group having 2 carbon atoms.
R ¹⁸ is a hydrocarbon group having 3 to 6 carbon atoms, preferably a hydrocarbon group having 3 to 4 carbon atoms.
^m1 is not particularly limited as long as it is an integer of 0 to 300, and is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3.
When ^m1 is 1 or more, R ¹⁶ is preferably a hydrogen atom.

In the general formula (18), specific examples of the polyalkylene oxide (meth)acrylate compound when ^m1 is 1 or more are (meth)acrylic acid esters in which an alkylene glycol having 3 or more carbon atoms is bonded to the ester bond moiety, such as (alkoxy)polyethylene glycol (poly)propylene glycol (meth)acrylic acid ester and (alkoxy)polyethylene glycol (poly)butylene glycol (meth)acrylic acid ester. Particularly preferred are (alkoxy)polyethylene glycol (poly)propylene glycol acrylic acid ester, (alkoxy)polyethylene glycol (poly)butylene glycol acrylic acid ester, methoxypolyethylene glycol (poly)propylene glycol acrylic acid ester, and methoxypolyethylene glycol (poly)butylene glycol acrylic acid ester.
When ^m1 is 0, (alkoxy)polyethylene glycol methacrylate and methoxypolyethylene glycol methacrylate are preferred.
When the value of ^m1 is within the above-mentioned range, hydrophobicity and steric hindrance can be imparted to the ester bond moiety, which is preferable in that the stability of the ester bond can be improved when stored in a protic solvent such as water, methanol, or ethanol.

In the general formula (18), ⁿ¹ is not particularly limited as long as it is an integer of 0 to 300, and is preferably 1 to 200, more preferably 5 to 100, and further preferably 10 to 50.
It is preferable that the value of ⁿ¹ is within the above-mentioned range, since the dispersibility of mud particles, the mud redeposition prevention performance, and the compounding stability in liquid detergent of the polyalkylene oxide-containing compound produced using the compound as a raw material are improved.

Furthermore, when R ¹⁷ is a hydrocarbon group having 2 carbon atoms, the content of -R ¹⁷ -O- groups is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more, assuming that the total amount of ^{-R 18} -O- groups and -R ¹⁷ -O- groups in general formula (18) is 100 mol %.
When R ¹⁷ is a hydrocarbon group having 2 carbon atoms, it is preferable that the content of -R ¹⁷ -O- groups in the general formula (18) is within the above-mentioned range in order to improve the hydrophilicity of the polyalkylene oxide chain, thereby improving the dispersibility of mud particles and the mud redeposition prevention performance of the polyalkylene oxide-containing compound produced using that compound as a raw material.

In the first step of the manufacturing method (III), the (poly)alkyleneamine represented by the general formula (5) and the (alkoxy)polyalkyleneoxide (meth)acrylate or (alkoxy)polyalkyleneglycol (meth)acrylamide represented by the general formula (17) or (18) are bonded to the hydrogen atom of the amino group of the (poly)alkyleneamine represented by the general formula (5) by a Michael addition reaction to obtain a (poly)alkyleneamine-(alkoxy)polyalkyleneoxide (meth)acrylate adduct or a (poly)alkyleneamine-(alkoxy)polyalkyleneoxide (meth)acrylamide adduct.

In the first step of the production method (III), the reaction temperature for the Michael addition reaction of the (poly)alkyleneamine represented by the general formula (5) and the (alkoxy)polyalkylene oxide (meth)acrylate or (alkoxy)polyalkylene glycol (meth)acrylamide represented by the general formula (17) or (18) is preferably 20 to 100° C., and more preferably 40 to 80° C.
The reaction time of the first step is preferably 1 hour or more, more preferably 5 hours or more, and further preferably 10 hours or more.
When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively and is improved, so that the amount of unreacted raw materials is reduced, which is preferable.

When the manufacturing process of the (alkoxy) polyalkylene oxide (meth) acrylate used in the manufacturing method (III) includes a process of esterification with (meth) acrylic acid and (alkoxy) polyalkylene oxide, (meth) acrylic acid may remain.In this case, the Michael addition of (alkoxy) polyalkylene oxide (meth) acrylate is easier to proceed than that of (meth) acrylic acid, so that the reaction of the (poly) alkylene oxide (meth) amine represented by the general formula (5) and the (alkoxy) polyalkylene oxide (meth) acrylate is carried out at a low temperature, and the (alkoxy) polyalkylene oxide (meth) acrylate can be preferentially added to the (poly) alkylene amine represented by the general formula (5).Furthermore, by increasing the reaction temperature or extending the reaction time, (meth) acrylic acid can also be Michael added to the (poly) alkylene amine represented by the general formula (5).
The same applies to the case where an (alkoxy)polyalkylene glycol (meth)acrylamide is used in place of an (alkoxy)polyalkylene oxide (meth)acrylate.
Furthermore, when the production process of the (alkoxy)polyalkylene oxide (meth)acrylate used in the production method (III) includes an esterification step, esterifying (meth)acrylic acid in an excess amount relative to the (alkoxy)polyalkylene oxide shortens the esterification reaction time, which is preferable in terms of productivity.

In the production method (III), when the (poly)alkyleneamine represented by the general formula (5) is reacted with the (alkoxy)polyalkylene oxide (meth)acrylate or (alkoxy)polyalkylene glycol (meth)acrylamide represented by the general formula (17) or the general formula (18), the reaction may be carried out without a solvent. When the reaction is carried out using a reaction solvent, alcohols such as methanol and ethanol; alkanes such as pentane, hexane, and cyclohexane; ethers such as diethyl ether and tetrahydrofuran; polar solvents such as dimethyl sulfoxide and dimethylformamide; water; and mixed solvents of water and an organic solvent may be used.

The second step of the production method (III) is a step of reacting an NH group in the structure of the cationic group portion of the (poly)alkyleneamine-(alkoxy)polyalkyleneoxide-(meth)acrylate adduct or (poly)alkyleneamine-(alkoxy)polyalkyleneoxide-(meth)acrylamide adduct obtained in the first step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.
This step reduces the number of NH groups in the structure of the (poly)alkyleneamine-(alkoxy)polyalkyleneoxide (meth)acrylate adduct or the (poly)alkyleneamine-(alkoxy)polyalkyleneoxide (meth)acrylamide adduct, thereby making it possible to impart excellent storage stability in the detergent composition.

Specific examples of the acid anhydride, acid halide and cyclic ester compound used in the second step of the production method (III) are the same as those described in the above production method (I).
The amount of the acid anhydride, acid halide, or cyclic ester compound used in the second step is preferably such that the molar number of the acid anhydride, acid halide, or cyclic ester compound used in the second step is 10 to 100 mol %, more preferably 15 to 90 mol %, and even more preferably 20 to 80 mol %, relative to the molar number of NH groups contained in the (poly)alkyleneamine used in the first step.

Also, a production method similar to production method (III) includes a method of obtaining the polyalkylene oxide-containing compound of the present invention by carrying out a first step of Michael addition of an α,β-unsaturated carbonyl compound having a polyalkylene oxide chain to an amino group contained in a cationic group, and a second step of reacting an NH group in the structure of the cationic group portion of the product obtained in the first step with one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds.
Another example of a production method similar to production method (III) is a method for obtaining a polyalkylene oxide-containing compound of the present invention by carrying out a first step of Michael addition of an α,β-unsaturated carbonyl compound to an amino group, which is a cationic group, a second step of introducing a polyalkylene oxide chain into the product obtained in the first step, and a third step of reacting an NH group in the structure of the cationic group portion of the product obtained in the second step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

Another example of the manufacturing method (IV) is a method for obtaining the polyalkylene oxide-containing compound of the present invention by carrying out a first step of introducing an amide bond by Michael addition of the double bond of acrylamide to the amino group of a (poly)alkyleneamine, a second step of carrying out a ring-opening addition reaction of an epoxy compound such as ethylene oxide with the amino group or hydroxyl group, which is the terminal residue obtained by the Michael addition reaction, and a third step of reacting the NH group in the structure of the cationic group portion of the product obtained in the second step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

Another example of the manufacturing method (V) is a method for obtaining the polyalkylene oxide-containing compound of the present invention by carrying out a first step of subjecting the hydrogen atoms of the amino groups of a (poly)alkyleneamine to a ring-opening addition reaction with an epoxy compound such as ethylene oxide, a second step of acetalizing the (poly)alkyleneamine alkoxylate obtained in the first step with an (alkoxy)polyalkylene oxide, an acetalizing agent, and an acid catalyst, and a third step of reacting the NH group in the structure of the cationic group portion of the product obtained in the second step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

Another example of the production method (VI) is a method for obtaining the polyalkylene oxide-containing compound of the present invention by carrying out a first step of Michael addition of the double bond of an alkyl (meth)acrylate to the amino group of a (poly)alkyleneamine, a second step of ester-amide exchange of the ester-containing compound obtained in the first step with an (alkoxy)polyalkylene oxide-containing terminal amine compound, and a third step of reacting the NH group in the structure of the cationic group portion of the product obtained in the second step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound.

Furthermore, the production methods (I) to (VI) may further include, in addition to the above-mentioned steps, a step of reducing the number of unreacted NH groups by subjecting unreacted NH groups, which are not bonded to a linking group contained in the cationic group, to one or more of a Michael addition reaction and an epoxy compound addition reaction.
More specifically, the method may include a step of reducing the number of unreacted NH groups by subjecting an alkyl acrylate such as methyl acrylate to Michael addition and/or an epoxy compound such as ethylene oxide or propylene oxide to unreacted NH groups that are not bonded to a linking group contained in the cationic group.

The above-mentioned production method may further include a step of neutralizing with an acid compound as another method for reducing the number of NH groups. By including this step, the stability of the polyalkylene oxide-containing compound of the present invention is further improved.
More specifically, it is preferable to reduce the number of NH groups by neutralizing unreacted NH groups that are not bonded to a linking group contained in the cationic group with an acid compound such as acetic acid, citric acid, hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid, or other common acid compounds.
The amount of the acid compound added is preferably 50 to 300 mol % based on the NH groups contained in the cationic groups before the addition of the acid compound.

4. Uses of polyalkylene oxide-containing compound The polyalkylene oxide-containing compound of the present invention (also simply referred to as "the compound of the present invention") can be suitably used for detergent builders, detergents, water treatment agents, dispersants, fiber treatment agents, scale inhibitors (scale inhibitors), cement additives, metal ion sequestering agents, thickeners, various binders, etc. Among these, it can be suitably used for detergent builders, detergents, water treatment agents, and dispersants.

The present invention further relates to a detergent builder, a detergent, a detergent composition, a water treatment agent, or a dispersant containing, as an essential component, the polyalkylene oxide-containing compound of the present invention or the polyalkylene oxide-containing compound produced by the production method of the present invention.
The detergent and detergent composition of the present invention may be in a solid or liquid form, and may be for use in dishes or laundry.

The content of the polyalkylene oxide-containing compound of the present invention in the detergent or detergent composition of the present invention is preferably 0.1% by mass to 15% by mass, more preferably 0.3% by mass to 10% by mass, and even more preferably 0.5% by mass to about 5% by mass, based on the total amount of the detergent or cleaning composition.

The detergent and detergent composition of the present invention may contain, in addition to the polyalkylene oxide-containing compound of the present invention, one or more other components such as a solvent, a surfactant, a cleaning auxiliary additive, and an encapsulating agent.
Examples of cleaning auxiliary additives include builders, surfactants or thickeners, mud stain removal/redeposition prevention agents, polymeric stain release agents, polymeric dispersants, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleaching catalysts, brightening agents, dyes, hueing agents, dye transfer inhibitors, chelating agents, foam suppressors, softeners, fragrances, and the like, and these may be used alone or in combination of two or more.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by mass."

Production Example 1
In an autoclave equipped with a thermometer, a pressure gauge, and a stirrer, 504.0 g of methoxypoly(n=25)ethylene glycol and 0.50 g of potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged, and the temperature was raised to 100°C while stirring. After the inside of the autoclave was replaced with nitrogen, the pressure was reduced to 1.2 kPa using a vacuum pump and dehydration was carried out for 1 hour. After completion of dehydration, the inside of the autoclave was adjusted to 0.3 MPa with nitrogen, and 96.4 g of 1,2-butylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually poured in over 120 minutes, and the mixture was further held at 100°C for 40 minutes. The reaction system was then heated to 120°C, and after aging by holding for 150 minutes, the inside of the system was returned to normal pressure. Furthermore, a cold trap and a vacuum pump were connected with the inside of the system at 60°C, and unreacted butylene oxide was distilled off under reduced pressure. The remaining product was collected to obtain methoxypoly(n=25)ethylene glycol-poly(n=2.5)butylene glycol (compound (1)).
A jacketed glass reactor (capacity: 1 liter) equipped with a thermometer, a stirrer, a product water separator, a reflux condenser as a condenser, and a nitrogen inlet tube was charged with 538.93 g of compound (1), 35.48 g of acrylic acid, 19.06 g of paratoluenesulfonic acid monohydrate, 0.14 g of phenothiazine, 0.03 g of 4-hydroxyTEMPO, and 57.44 g of cyclohexane, and the esterification reaction was carried out at a reaction temperature of 115°C. It was confirmed that the esterification rate reached 97% in 60 hours. 8.61 g of 49% aqueous sodium hydroxide solution and 98.50 g of water were added to 655.75 g of the obtained esterification reaction liquid to neutralize the paratoluenesulfonic acid, and the temperature was raised to 105°C, and cyclohexane was distilled off by azeotropy with water. When the internal temperature of the jacketed glass reactor reached 98°C, nitrogen was introduced into the reaction liquid in the reactor, and dissolved cyclohexane was expelled. Then, adjusting water was added to obtain an 80% aqueous solution of the esterified product (compound (2)).

Production Example 2
In an autoclave equipped with a thermometer, a pressure gauge, and a stirrer, 705.4 g of methoxypoly(n=25)ethylene glycol and 0.70 g of potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged, and the temperature was raised to 120° C. while stirring. After the inside of the autoclave was replaced with nitrogen, the pressure was reduced to 1.2 kPa using a vacuum pump and dehydration was performed for 1 hour. After completion of dehydration, the inside of the autoclave was adjusted to 0.3 MPa with nitrogen, 144.7 g of propylene oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dropped over 120 minutes, and the mixture was further maintained at 120° C. for 120 minutes for aging, and the inside of the system was returned to normal pressure. Furthermore, with the inside of the system at 80° C., a cold trap and a vacuum pump were connected, and unreacted propylene oxide was distilled off under reduced pressure. The remaining product was collected to obtain methoxypoly(n=25)ethylene glycol-poly(n=4.0)propylene glycol (compound (3)).
A jacketed glass reactor (capacity: 1 liter) equipped with a thermometer, a stirrer, a product water separator, a reflux condenser as a condenser, and a nitrogen inlet tube was charged with 363.89 g of compound (3), 38.44 g of acrylic acid, 19.07 g of 70% paratoluenesulfonic acid monohydrate, 0.10 g of phenothiazine, 0.02 g of 4-hydroxy TEMPO, and 40.33 g of cyclohexane, and the esterification reaction was carried out at a reaction temperature of 110°C. It was confirmed that the esterification rate (reaction rate of compound (3)) reached 95% in 48 hours. 7.65 g of 48% aqueous sodium hydroxide solution and 7.07 g of water were added to the obtained esterification reaction liquid of 461.86 g to neutralize paratoluenesulfonic acid, and the temperature was raised to 105°C, and cyclohexane was distilled off by azeotropy with water. When the internal temperature of the jacketed glass reactor reached 98°C, nitrogen was introduced into the reaction liquid in the reactor, and dissolved cyclohexane was expelled. Then, adjusting water was added to obtain a 92% aqueous solution of the esterified product (compound (4)).

Production Example 3
In an autoclave equipped with a thermometer, a pressure gauge, and a stirrer, 710.6 g of methoxypoly(n=25)ethylene glycol and 1.14 g of potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were charged, and the temperature was raised to 120° C. while stirring. After the inside of the autoclave was replaced with nitrogen, the pressure was reduced to 1.2 kPa using a vacuum pump and dehydration was carried out for 1 hour. After completion of dehydration, the inside of the autoclave was adjusted to 0.3 MPa with nitrogen, 690.1 g of ethylene oxide was dropped over 240 minutes, and the mixture was further kept at 120° C. for 60 minutes for aging, and the inside of the system was returned to normal pressure. The product was recovered to obtain methoxypoly(n=50)ethylene glycol (compound (5)).
1398.9 g of the obtained methoxypoly(n=50)ethylene glycol (compound (5)) was charged into an autoclave equipped with a thermometer, a pressure gauge, and a stirrer, and the temperature was raised to 120° C. while stirring. After the autoclave system was replaced with nitrogen, the pressure was reduced to 1.2 kPa using a vacuum pump and dehydration was performed for 1 hour. After completion of dehydration, the pressure in the autoclave was adjusted to 0.3 MPa with nitrogen, 109.1 g of propylene oxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dropped over 90 minutes, and the system was further maintained at 120° C. for 120 minutes for aging, and the system was returned to normal pressure. Furthermore, with the system at 80° C., a cold trap and a vacuum pump were connected, and unreacted propylene oxide was distilled off under reduced pressure. The remaining product was collected to obtain methoxypoly(n=50)ethylene glycol-poly(n=3.0)propylene glycol (compound (6)).
A jacketed glass reaction vessel (capacity: 1 liter) equipped with a thermometer, a stirrer, a water separator, a reflux condenser as a condenser, and a nitrogen inlet tube was charged with 671.88 g of compound (6), 60.31 g of acrylic acid, 34.65 g of 70% paratoluenesulfonic acid monohydrate, 0.18 g of phenothiazine, 0.04 g of 4-hydroxyTEMPO, and 72.54 g of cyclohexane, and the esterification reaction was carried out at a reaction temperature of 110°C. It was confirmed that the esterification rate (reaction rate of compound (6)) reached 95% in 67 hours. To the obtained esterification reaction liquid 839.60 g, 13.94 g of 48% aqueous sodium hydroxide solution and 48.62 g of water were added to neutralize the paratoluenesulfonic acid, and the temperature was raised to 105°C, and cyclohexane was distilled off by azeotropy with water. When the internal temperature of the jacketed glass reactor reached 98° C., nitrogen was introduced into the reaction solution in the reactor to expel dissolved cyclohexane, and adjustment water was added to obtain a 94% aqueous solution of the esterified product (compound (7)).

Example 1
<First step>
2.40 g of polyethyleneimine (manufactured by Nippon Shokubai, average molecular weight 600) and 29.59 g of compound (2) were charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the atmosphere inside the reaction vessel was replaced with nitrogen. The temperature was then raised to 40° C. with stirring, and the reaction was continued for 3 hours. After completion of the reaction, it was confirmed by liquid chromatography that the esterification product of compound (2) had been consumed, and a methoxypoly(n=25)ethylene glycol-poly(n=2.5)butylene glycol acrylate adduct of polyethyleneimine (polymer (1)) was obtained.
<Second step>
4.50 g of polymer (1) was charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.30 g of maleic anhydride (manufactured by Nippon Shokubai) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this way, a polymer (polymer (2)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which an NH group contained in a cationic group not bonded to a linking group is converted into an amide bond. The polymer (2) was 66% in the resulting reaction liquid.

Example 2
<First step>
The same procedure as in the first step of Example 1 was carried out to obtain polymer (1).
<Second step>
4.50 g of polymer (1) was charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.40 g of propionic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, first grade) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this way, a polymer (polymer (3)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which the NH group contained in the cationic group to which no linking group is bonded is converted into an amide bond. The polymer (3) was 67% in the obtained reaction solution.

Example 3
<First step>
The same procedure as in the first step of Example 1 was carried out to obtain polymer (1).
<Second step>
4.50 g of polymer (1) was charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.30 g of succinic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, special grade) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this way, a polymer (polymer (4)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which an NH group contained in a cationic group not bonded to a linking group is converted into an amide bond. The polymer (4) was 66% in the obtained reaction solution.

Example 4
<First step>
The same procedure as in the first step of Example 1 was carried out to obtain polymer (1).
<Second step>
4.50 g of polymer (1) was charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.45 g of phthalic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, special grade) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this way, a polymer (polymer (5)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which an NH group contained in a cationic group not bonded to a linking group is converted into an amide bond. The polymer (5) was 67% in the obtained reaction liquid.

Example 5
<First step>
The same procedure as in the first step of Example 1 was carried out to obtain polymer (1).
<Second step>
4.50 g of polymer (1) was charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.31 g of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, first grade) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this way, a polymer (polymer (6)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which the NH group contained in the cationic group to which no linking group is bonded is converted into an amide bond. The polymer (6) was 66% in the obtained reaction solution.

Example 6
<First step>
The same procedure as in the first step of Example 1 was carried out to obtain polymer (1).
<Second step>
A glass reaction vessel equipped with a reflux condenser and a stirrer was charged with 6.00 g of polymer (1), and the temperature was raised to 50° C. while stirring. After the temperature was raised, 0.58 g of ε-caprolactone (Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 5 hours. In this manner, a polymer (polymer (7)), which is a polyalkylene oxide-containing compound of the present invention, was obtained in which an NH group contained in a cationic group not bonded to a linking group was converted into an amide bond. The content of polymer (7) in the obtained reaction liquid was 67%.

Example 7
<First step>
A glass reaction vessel equipped with a reflux condenser and a stirrer was charged with 1.24 g of polyethyleneimine (manufactured by Nippon Shokubai, average molecular weight 600) and 12.73 g of compound (4), and the atmosphere inside the reaction vessel was replaced with nitrogen. The temperature was then raised to 60° C. with stirring, and the reaction was continued for 12 hours. After completion of the reaction, it was confirmed by liquid chromatography that the esterification product of compound (4) had been consumed, and a methoxypoly(n=25)ethylene glycol-poly(n=4.0)propylene glycol acrylate adduct of polyethyleneimine (polymer (8)) was obtained.
<Second step>
5.02 g of polymer (8) was placed in a glass reaction vessel equipped with a reflux condenser and a stirrer, and the temperature was raised to 50° C. with stirring. After heating, 0.30 g of maleic anhydride (manufactured by Nippon Shokubai) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 3 hours. In this manner, a polymer (polymer (9)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which an NH group contained in a cationic group not bonded to a linking group is converted into an amide bond.

Example 8
<First step>
0.70 g of polyethyleneimine (manufactured by Nippon Shokubai, average molecular weight 600), 9.81 g of compound (7) and 1.91 g of pure water were charged into a glass reaction vessel equipped with a reflux condenser and a stirrer, and the atmosphere inside the reaction vessel was replaced with nitrogen. Thereafter, the temperature was raised to 60° C. with stirring, and the reaction was continued for 10 hours. After completion of the reaction, it was confirmed by liquid chromatography that the esterification product of compound (7) had been consumed, and a methoxypoly(n=50)ethylene glycol-poly(n=3.0)propylene glycol acrylate adduct of polyethyleneimine (polymer (10)) was obtained.
<Second step>
A glass reaction vessel equipped with a reflux condenser and a stirrer was charged with 4.99 g of polymer (10), and the temperature was raised to 50° C. with stirring. After the temperature was raised, 0.30 g of maleic anhydride (manufactured by Nippon Shokubai) was added dropwise over 1 hour, and the mixture was stirred at 50° C. for 3 hours. In this manner, a polymer (polymer (11)) was obtained, which is a polyalkylene oxide-containing compound of the present invention, in which an NH group contained in a cationic group not bonded to a linking group is converted into an amide bond.

Comparative Example 1
Polyethyleneimine ethoxylate (product name PN100, manufactured by Nippon Shokubai) was used as a comparative polymer (1).

Comparative Example 2
10.0 g of methanol, 0.028 g of 4-methoxyphenol, and 2.76 g of trimethylpropane ethoxylate triacrylate (Aldrich) were mixed and stirred in a glass reaction vessel equipped with a reflux condenser and a stirrer. 2.24 g of N,N'-bis(3-aminopropyl)ethylenediamine (Tokyo Chemical Industry Co., Ltd.) was slowly dropped into the mixed solution. The mixture was stirred at 60°C for 15 hours to obtain a comparative polymer solution (2). It was confirmed by 1H-NMR that the peak derived from acrylate had disappeared. Next, 8.75 g of the comparative polymer solution (2) and 2.09 g of methoxypolyethylene glycol methacrylate (Shin-Nakamura Chemical Co., Ltd., product name M-230G) were added to a glass reaction vessel equipped with a reflux condenser and a stirrer, and the mixture was stirred at 50°C for 20 hours to obtain a comparative polymer solution (3). The comparative polymer (3) was 46% in the obtained reaction solution.

Polymers (2) to (6), (9), and (11) produced in Examples 1 to 5, and comparative polymers (1) and (3) in Comparative Examples 1 and 2 were subjected to stability tests in water, stability tests in a surfactant blend, and biodegradability tests by the following methods. The results are shown in Table 1.

<Stability test in water>
The polymers obtained in the examples and comparative examples were diluted to 10% with pure water, and then the pH of the aqueous solution was adjusted to 7 using 0.1 M sodium hydroxide, 1 M sodium hydroxide, and 1 M hydrochloric acid (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After adjusting the pH, pure water was further added so that the polymer was 5%, and a 5% polymer aqueous solution of pH 7 was obtained. The polymer aqueous solution was adjusted to 1.0% with the GPC eluent and GPC measurement was performed. The 5% polymer aqueous solution was stored at 60 ° C. for 24 hours, and then GPC measurement was performed again. In the GPC chart, the peaks from 16.0 min to 18.5 min were taken as the polymer peaks (for polymers (9) and (11), the peaks from 16.0 min to 19.0 min) were taken as the reduction rate of the polymer-derived peak area before and after storage at 60 ° C., which was calculated by the following formula as the polymer decomposition rate, and was used as a stability test in water.
Decomposition rate (%)=(peak area derived from polymer before test−peak area derived from polymer after test)/(peak area derived from polymer before test)×100

<Stability test in surfactant blend>
Preparation of surfactant formulations:
First, 64.0g of propylene glycol and 16.0g of ethanol were mixed to prepare a compatibilizer. 269.2g of 65% linear alkylbenzenesulfonate sodium (LAS) (Neopelex G65, Kao) was mixed with 50.0g of the compatibilizer prepared above, and then 180.7g of pure water was added and stirred to prepare a 35% linear alkylbenzenesulfonate aqueous solution. 192.8g of 35% linear alkylbenzenesulfonate sodium and 22.5g of polyoxyethylene lauryl ether (PAE) (Emulgen 108, Kao) were mixed, and then 10.7g of the compatibilizer was added and stirred, and 64.9g of pure water was further added and stirred to obtain a surfactant blended aqueous solution blended with LAS:PAE=3:1 (wt).
Stability testing:
The surfactant-blended aqueous solution prepared above was diluted so that the polymer obtained in the examples and comparative examples was 5%, to obtain a surfactant aqueous solution containing 5% polymer. The 5% polymer solution was adjusted to 0.5% with a GPC eluent and subjected to GPC measurement. The 5% polymer solution was stored at 60°C for 24 hours, and then GPC measurement was performed again. The peaks at 16.0 min to 18.5 min in the GPC chart were regarded as polymer peaks (for polymers (9) and (11), the peaks were 16.0 min to 19.0 min), and the reduction rate of the peak area derived from the polymer before and after storage at 60°C was calculated as the polymer decomposition rate using the following formula, which was used as a stability test in the surfactant blend.
Decomposition rate (%)=(peak area derived from polymer before test−peak area derived from polymer after test)/(peak area derived from polymer before test)×100

<Biodegradability test>
The polyalkylene oxide-containing compounds obtained in the Examples and Comparative Examples were subjected to a biodegradability test in accordance with OECD 301F.
Preparation of medium:
Stock medium solutions A to D were prepared by the following method.
Solution A: 0.850 _g of potassium dihydrogen phosphate ( _KH2PO4 ), 2.175 g _of dipotassium hydrogen phosphate ( _K2HPO4 ), _6.7217 g of disodium hydrogen phosphate-12-hydrate ( _{Na2HPO4.12H2O} ), and 0.050 g of ammonium chloride ( _NH4Cl ) were weighed into a 50 ml sample bottle, dissolved in an appropriate amount of water _, and transferred to a 100 ml measuring flask, and then water was added up to the mark.
Solution B: 3.640 g of calcium chloride dihydrate (CaCl ₂ .2H ₂ O) was dissolved in an appropriate amount of water and transferred to a 100 ml measuring flask, and water was then added up to the marked line.
Solution C: 2.250 g of magnesium sulfate heptahydrate (MgSO ₄ .7H ₂ O) was dissolved in an appropriate amount of water and transferred to a 100 ml measuring flask, and water was then added up to the marked line.
Solution D: 0.025 g of iron chloride (III) hexahydrate (FeCl ₃ .6H ₂ O) was dissolved in an appropriate amount of water and transferred to a 100 ml measuring flask, and water was then added up to the marked line.
The above stock medium solutions A to D were adjusted to 25°C, and 10 ml of A was added to a 1 L volumetric flask using a whole pipette, and diluted with approximately 800 ml of water. Then, 1 ml each of B, C, and D was added using a whole pipette, and diluted to the mark with water adjusted to 25°C. Multiple portions of the above medium were prepared according to the amount required for the test. The prepared medium was transferred to a 5 L beaker, mixed, and bubbled for more than 1 hour while stirring.
Preparation of sludge solution:
The sludge used in the biodegradability test was obtained from Minami Suita Sewage Treatment Plant. First, the concentration of the obtained sludge was measured by the following method. The obtained sludge was bubbled while stirring, 5 ml was taken using a whole pipette, and suction filtered using filter paper. Five sheets of filter paper on which the sludge was collected in this way were prepared, and after drying in a dryer at 105°C for 1 hour, the concentration of the sludge was calculated from the average weight loss of the five sheets. This sludge was diluted with the medium prepared above to prepare a 1000 ppm sludge solution.
Preparation of polymer aqueous solution:
The polymers obtained in the Examples and Comparative Examples were diluted with pure water to obtain 2% by mass aqueous polymer solutions. As a standard substance, sodium benzoate was diluted with pure water to obtain a 2% by mass aqueous sodium benzoate solution.
BOD test:
A pressure sensor type BOD meter was used to measure the BOD. 144.75 g of the medium prepared above was weighed into a flanking bottle, and 0.75 g of a 2% polymer aqueous solution was added. 0.75 g of pure water was added for blank measurement, and 0.75 g of a 2% sodium benzoate aqueous solution was added for standard substance measurement. The pH of the solution was then measured, and the pH was adjusted with a 0.1 M hydrochloric acid aqueous solution so that the pH value of the solution was 7.4 ± 0.2. Then, 4.5 ml of 1000 ppm sludge solution was added to make a test solution. After placing a stirrer in the flanking bottle, 1.8 g of CO2 absorbent (Yabasirium) was placed in the CO2 absorbent holder, set it, and a BOD sensor was attached. The flanking bottle with the BOD sensor attached was stirred in a thermostatic bath at 22 ° C, and the BOD value was calculated from the pressure sensor.
Calculation of decomposition rate:
The theoretical oxygen demand (ppm) of the polymer was calculated, and the decomposition rate was calculated from the difference between the BOD value of the blank measurement and the BOD value measured using the polyalkylene oxide-containing compound. The decomposition rate 28 days after the start of the test was calculated as the biodegradation rate using the following formula.
Decomposition rate (%) = (biochemical oxygen consumption derived from polymer) / (theoretical oxygen demand of polymer) x 100

The results in Table 1 make it clear that the polymers (2) to (6), (9) and (11), which are the polyalkylene oxide-containing compounds of the present invention, exhibit excellent stability and biodegradability.

Claims (8)

A polyalkylene oxide-containing compound having a cationic group, a linking group, and a structural unit derived from polyalkylene oxide,
the linking group is bonded to a structural unit derived from a polyalkylene oxide,
A polyalkylene oxide-containing compound, wherein the cationic group has at least one amide bond. 2. The polyalkylene oxide-containing compound according to claim 1, wherein the linking group is one or more groups selected from an ester group, a thioester group, an amide group, a thioamide group, an acetal group, a hemiacetal group, and a hemiketal group. A substituent represented by the following general formula (1),

In the general formula (1), R ¹ is the same or different and represents a hydrocarbon group having 2 to 6 carbon atoms. X is one or more selected from a -C(=α ¹ )-β ¹ - group, a >C=α ¹ group, a -α ¹ -CR ² R ³ -β ¹ - group, and a -CR ⁴ (OH)-α ¹ - group, and α ¹ and β ¹ are the same or different and represent a hetero atom or a group in which a hydrogen atom is bonded to a hetero atom. R ² , R ³ , and R ⁴ are the same or different and represent a hydrogen atom or an organic group having 1 to 10 carbon atoms. s is an integer from 1 to 300. Y is a direct bond, a linear or branched hydrocarbon group having 1 to 10 carbon atoms, or a substituent represented by the following general formula (2). Z is a direct bond, -(CH ₂ ) _n -(S) _m -(CH ₂ ) _p represents an -O- group, a -(CH ₂ ) _n -α ² - group, or a substituent represented by the following general formula (3). α ² represents a heteroatom or a group in which a hydrogen atom is bonded to a heteroatom. m is 0 or 1, and n is an integer from 1 to 10. p is an integer from 1 to 10. T represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.

(In the general formula (2), q is an integer of 1 to 300. R ⁵ and R ⁶ are the same or different and each represents a hydrocarbon group having 2 to 6 carbon atoms.)

(In general formula (3), n is an integer from 1 to 10.)
and a cationic group having two or more nitrogen atoms,
The polyalkylene oxide-containing compound according to claim 1, characterized in that the substituent represented by the general formula (1) is bonded to at least one of the nitrogen atoms contained in the cationic group. The polyalkylene oxide-containing compound according to claim 3, wherein the heteroatoms α ¹ and β ¹ of X in the substituent represented by the general formula (1) are oxygen atoms or nitrogen atoms. The polyalkylene oxide-containing compound according to claim 3, characterized in that Y in the substituent described in the general formula (1) is a hydrocarbon group having 2 to 4 carbon atoms. The polyalkylene oxide-containing compound according to claim 3, characterized in that the amount of NH groups contained in the polyalkylene oxide-containing compound is 80 mol % or less based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound. A method for producing the polyalkylene oxide-containing compound according to claim 1, comprising the steps of:
The production method includes a first step of subjecting an α,β-unsaturated carbonyl compound having a polyalkylene oxide chain to a cationic amino group by Michael addition;
and a second step of reacting an NH group in the structure of the cationic group portion of the product obtained in the first step with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound. A detergent or detergent composition comprising the polyalkylene oxide-containing compound of claim 1.