Composition containing polyalkylene-oxide-containing compound and enzyme

Abstract

The purpose of the present invention is to provide a composition that contains an enzyme and a compound having a structural unit derived from a polyalkylene oxide, the composition having exceptional detergency. The present invention is a composition containing a polyalkylene-oxide-containing compound and an enzyme, wherein: the compound has a cationic group, a linking group, and a structural unit derived from a polyalkylene oxide; the linking group connects the cationic group and the structural unit derived from a polyalkylene oxide; and the cationic group has an NH group.

Description

Composition containing a polyalkylene oxide-containing compound and an enzyme

[0001] The present invention relates to a composition comprising a polyalkylene oxide-containing compound and an enzyme.

[0002] Conventionally, detergent builders (detergent auxiliaries) such as zeolite, carboxymethyl cellulose, polyethylene glycol, etc. have been blended into detergents used for clothing in order to improve the cleaning effect of the detergent. In addition to the various detergent builders described above, polymers have recently been blended into detergent compositions as detergent builders.

[0003] Regarding such polymers, polymers having a polyalkyleneimine as the main chain and ethylene oxide or the like added to a nitrogen atom in the polyalkyleneimine are also called polyethyleneimine ethoxylate modified products, and can act as polymer builders.

[0004] Enzymes are commonly used in laundry detergents. It is known that enzymes incorporated in laundry detergents act on proteinaceous and starch stains, providing high cleaning effectiveness even in small amounts. Furthermore, it is known that the detergency of enzymes can be improved by combining a polymer builder with an enzyme. For example, Patent Document 1 discloses the detergency of a laundry detergent composition that combines a polymer characterized by having a quaternary ammonium salt and a polyalkylene oxide structure in its side chain with an ester hydrolase. Furthermore, it discloses the use of ethoxylated polyethyleneimine to improve the detergency of protease contained in a laundry detergent composition.

[0005] WO 2023 / 064749 Chinese Patent Application Publication No. 109135960

[0006] As mentioned above, polymers that improve the detergency of enzymes in detergents have been developed, but there is still room for improvement in improving the detergency of compositions containing enzymes.

[0007] The present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide a composition containing a polyalkylene oxide-containing compound and an enzyme, which has excellent detergency.

[0008] The present inventors have conducted extensive research into compositions used in cleaning applications and have found that a composition containing an enzyme and a compound having a cationic group having an NH group, a linking group, and a structural unit derived from polyalkylene oxide, wherein the linking group links the cationic group and the structural unit derived from polyalkylene oxide, exhibits excellent detergency. They have come to the conclusion that the above-mentioned problems can be solved beautifully and have completed the present invention.

[0009] That is, the present invention is as follows: [1] A composition comprising a polyalkylene oxide-containing compound and an enzyme, wherein the compound has a cationic group, a linking group, and a structural unit derived from polyalkylene oxide, the linking group links the cationic group and the structural unit derived from polyalkylene oxide, and the cationic group has an NH group.

[0010] [2] The composition according to the above [1], wherein the linking group is a group having one or more substituents selected from an ester group, an amide group, and an ether group.

[0011] [3] The composition according to the above [1] or [2], wherein the amount of active hydrogen on the nitrogen atom of the cationic group is 1 mol % to 99 mol % based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

[0012] [4] The polyalkylene oxide-containing compound has a cation group represented by the following general formula (1): (In general formula (1), R １ is a hydrocarbon group having 3 to 6 carbon atoms, R ２ is a hydrocarbon group having 2 to 6 carbon atoms, R ３ are the same or different and represent a hydrogen atom and / or an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 300, and n is an integer of 1 to 300. X represents an organic group having 2 to 6 carbon atoms. G represents one or more selected from an oxygen atom, a nitrogen atom, an NH group, and a direct bond. d is an integer of 1 or 2, and when G is an oxygen atom or an NH group, d is 1, and when G is N, d is 2. The composition according to any of the above-mentioned [1] to [3], having a structure in which a substituent represented by

[0013] [5] The composition according to the above [4], wherein the amount of the substituent represented by the general formula (1) is 1 mol % to 99 mol % relative to 100 mol % of the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

[0014] [6] The composition according to any one of the above [1] to [5], wherein the content of the polyalkylene oxide-containing compound is 0.1 to 10% by mass, where the composition is taken as 100% by mass.

[0015] [7] The composition according to any one of the above [1] to [6], wherein the content of the enzyme is 0.01 to 10% by mass, when the composition is taken as 100% by mass.

[0016] [8] The composition according to any one of [1] to [7] above, comprising the polyalkylene oxide-containing compound, an enzyme, and a surfactant.

[0017] [9] The composition according to [8] above, wherein the surfactant comprises at least one selected from an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.

[0018] The composition of the present invention has good detergency and can therefore be suitably used as a component of laundry detergents.

[0019] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. Note that a combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of the present invention.

[0020] In the following description, unless otherwise specified, "%" means "% by mass", "parts" means "parts by mass", and the range "A to B" means A or more and B or less. In addition, in the present invention, "(meth)acrylate" means "acrylate" or "methacrylate", and "(meth)acrylic" means "acrylic" or "methacrylic".

[0021] The composition of the present invention contains a polyalkylene oxide-containing compound (hereinafter also referred to as the compound of the present invention) and an enzyme. By containing the compound, the composition of the present invention has excellent detergency against proteinaceous stains.

[0022] The content of the polyalkylene oxide-containing compound in the composition of the present invention is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 0.5 to 3.5% by mass, relative to 100% by mass of the composition.

[0023] The content of the enzyme in the composition of the present invention is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.01 to 2.0% by mass, even more preferably 0.05 to 1.0% by mass, and particularly preferably 0.05 to 0.80% by mass, relative to 100% by mass of the composition. In one embodiment, the content of the enzyme may be 0.05 to 0.75% by mass, or 0.05 to 0.55% by mass.

[0024] In the composition of the present invention, the content ratio of the polyalkylene oxide-containing compound relative to 100% by mass of the enzyme is preferably 10 to 100,000% by mass, more preferably 100 to 20,000% by mass, and even more preferably 300 to 6,000% by mass. In one aspect, the content ratio of the polyalkylene oxide-containing compound relative to 100% by mass of the enzyme may be 1 to 100% by mass, 1 to 75% by mass, or 1 to 50% by mass.

[0025] The content of the surfactant in the composition of the present invention is not particularly limited, but is preferably 5 to 80% by mass, more preferably 25 to 55% by mass, and even more preferably 25 to 40% by mass, relative to 100% by mass of the composition.

[0026] The composition of the present invention may contain other components in addition to the polyalkylene oxide-containing compound, enzyme, and surfactant. These other components are not particularly limited, but examples include water, detergent builders; stain inhibitors such as benzotriazole and ethylene-thiourea; soil release agents; color transfer inhibitors; softeners; alkaline substances for adjusting pH; fragrances; solubilizers; fluorescent agents; colorants; foaming agents; foam stabilizers; polishing agents; disinfectants; bleaching agents; bleaching aids; dyes; and solvents. The content of these other components is not particularly limited, but is preferably 25 to 75% by mass, and more preferably 30 to 70% by mass, relative to 100% by mass of the composition.

[0027] The essential and optional components contained in the composition of the present invention are further described below.

[0028] <Polyalkylene oxide-containing compound> The polyalkylene oxide-containing compound of the present invention has the following substituents and structural units 1) to 3): 1) Cationic group; 2) Linking group; 3) Structural unit derived from polyalkylene oxide: The linking group links the cationic group to the polyalkylene oxide, and the cationic group further has an NH group, which is a group having an amino group. It is believed that the polyalkylene oxide-containing compound of the present invention having such a structure exhibits excellent dirt dispersibility due to the structural unit 3), while the low steric hindrance in the cationic group portion allows for sufficient interaction with enzymes, resulting in excellent cleaning performance. The cationic group may be any group having an amino group with active hydrogen, and the NH group may be any group having an amino group with active hydrogen. ２The cationic group may have a group. The cationic group may have a secondary amino group, and may have a primary amino group, a tertiary amino group, or a quaternary ammonium group. In the polyalkylene oxide-containing compound of the present invention, the cationic group may have one amino group or two or more amino groups, but preferably 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. The number of structural units having amino groups in the polymer is more preferably 3 to 100, even more preferably 4 to 75, and particularly preferably 5 to 50. Specific examples of cationic groups will be described later.

[0029] 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 linked via the linking group rather than being directly linked. Also, 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 possessed by the cationic group is linked to the linking group. A form in which some or all of the structural units derived from polyalkylene oxide are linked to the cationic group (structural unit having an amino group) via the linking group is one of the preferred forms of the polyalkylene oxide-containing compound of the present invention.

[0030] 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. The structural unit derived from polyalkylene oxide includes a structural unit derived from ethylene oxide, -CH ２ CH ２Preferably, the polyalkylene oxide-containing compound contains a - group, more preferably contains 70 mol % or more of structural units derived from ethylene oxide, and even more preferably contains 80 mol % or more of structural units derived from ethylene oxide. In the present invention, a structural unit derived from polyalkylene oxide typically represents a residue obtained by removing at least one hydrogen atom from polyalkylene oxide. The polyalkylene oxide-containing compound of the present invention typically contains a primary amino group and / or a secondary amino group.

[0031] The linking group in the present invention is preferably a group having one or more substituents selected from an ester group, an amide group, and an ether group. If the linking group is a group having an ether group, the stability of the polyalkylene oxide-containing compound during storage can be improved, which is preferable.

[0032] In recent years, detergent compositions are required to have not only excellent cleaning ability but also be easily degradable in nature due to environmental considerations. Therefore, in applications requiring biodegradability, the linking group is preferably a hydrolyzable group or a functional group that is degraded by extracellular enzymes, and among these linking groups, a group having an ester group or a group having an amide group is preferred. Note that biodegradability means that the linking group can be metabolized and decomposed by, for example, bacteria, fungi, and other organisms.

[0033] The polyalkylene oxide-containing compound of the present invention preferably has a linking group represented by the following general formula (1) and a substituent. １ -O-) ｍ , and (-R ２ -O-) ｎ and a linking group represented by -X-G-. 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.

[0034]

[0035] (In general formula (1), R １ is a hydrocarbon group having 3 to 6 carbon atoms, R ２is a hydrocarbon group having 2 to 6 carbon atoms, R ３ are the same or different and represent a hydrogen atom and / or an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 300, and n is an integer of 1 to 300. X represents an organic group having 2 to 6 carbon atoms. G represents one or more selected from an oxygen atom, a nitrogen atom, an NH group, and a direct bond. d is an integer of 1 or 2, and when G is an oxygen atom or an NH group, d is 1, and when G is N, d is 2.

[0036] X is not particularly limited as long as it is an organic group having 2 to 6 carbon atoms, and is preferably a hydrocarbon group having 2 to 6 carbon atoms, more preferably a hydrocarbon group having 2 to 4 carbon atoms, and particularly preferably a hydrocarbon group having 2 to 3 carbon atoms. It is more preferable that X contains an oxygen atom. Specific examples of X include -CH ２ -CH(OH)-CH ２ - group, -CH ２ -CHY-CO- group, -CH ２ CH ２ - group (wherein Y is a hydrogen atom and / or a methyl group). When the composition of the present invention contains moisture and storage stability of the polyalkylene oxide-containing compound of the present invention is required, a functional group that is less susceptible to hydrolysis by moisture contained in the composition of the present invention is preferred. X is a -CH ２ -CH(OH)-CH ２ On the other hand, for applications requiring biodegradability, suitable X is preferably a hydrolyzable group, a functional group that is decomposed by extracellular enzymes, and is preferably a -CH ２ -CH ２ A —CO— group is preferred.

[0037] G represents one or more selected from an oxygen atom, a nitrogen atom, an NH group, and a direct bond, preferably an oxygen atom. d is an integer of 1 or 2, and when G is an oxygen atom, an NH group, or a direct bond, d is 1, and when G is N, d is 2.

[0038] R １ is a hydrocarbon group having 3 to 6 carbon atoms, preferably a hydrocarbon group having 3 to 4 carbon atoms. ２ -CH２ When R is a —CO— group, this is preferred because it improves the storage stability of the polyalkylene oxide-containing compound of the present invention in the detergent composition. １ is more preferably a propylene group, an isopropylene group, a butylene group, or an isobutylene group, and even more preferably an isopropylene group. ２ 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. ２ When the number of carbon atoms in R is within the above-mentioned range, the water solubility of the polyalkylene oxide compound of the present invention is improved, and compatibility with liquid detergents can be improved, which is preferable. ２ More preferred are ethylene, propylene, isopropylene, butylene and isobutylene groups, and even more preferred is ethylene.

[0039] R ３ is not particularly limited as long as it is a hydrogen atom and / or an organic group having 1 to 30 carbon atoms, and the structure may be selected appropriately to adjust the hydrophilicity or hydrophobicity. The organic group is preferably a hydrocarbon group. More preferably, it is a linear or branched alkyl group, an alkenyl group, an alkynyl group, an aryl group, or an aralkyl group. Also preferred are organic groups having a structure in which a carboxyl group, a phosphate group, or a sulfonic acid group is bonded to the hydrocarbon group.

[0040] The organic group preferably has 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0041] Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (an amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosanyl group, an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methyl ... Examples of alkyl groups include 1-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and icosyl group.

[0042] Examples of the alkenyl group include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group.

[0043] Examples of the aryl group include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, a naphthyl group, etc. Examples of the aralkyl group include a benzyl group, a 1-phenylethyl group, a 2-phenylethyl group, a 3-phenylpropyl group, a 4-phenylbutyl group, etc.

[0044] The hydrocarbon group is preferably an alkyl group, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), or an n-hexyl group, and even more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.

[0045] m 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 even more preferably 1 to 3. m is an integer of 0 to 3, and is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. ２ -CH(OH)-CH ２ When it is a - group, it may be 0. n is not particularly limited as long as it is an integer of 1 to 300, and is preferably 1 to 200, more preferably 5 to 100, even more preferably 10 to 100, still more preferably 10 to 50, and particularly preferably 15 to 30. When m and n are within the above-mentioned ranges, the water solubility of the polyalkylene oxide compound of the present invention is improved, and compatibility with liquid detergents can be made even more excellent, which is preferable.

[0046] In addition, the R ２ is a hydrocarbon group having 2 carbon atoms, -R １ -O- group, -R ２ When the total amount of —O— groups is 100 mol %, —R ２ The content of —O— groups is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more. ２ is a hydrocarbon group having 2 carbon atoms, ２ When the content of —O— groups is within the above-mentioned range, the hydrophilicity of the polyalkylene oxide chain is improved, which is preferable in that the compatibility of the cleaning composition containing the polyalkylene oxide-containing compound of the present invention with liquid detergents is improved.

[0047] The amount of active hydrogen on the nitrogen atom of the cationic group contained in the polyalkylene oxide-containing compound of the present invention is not particularly limited as long as it is 1 mol % to 99 mol % relative to the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound, but is more preferably 20 mol % to 90 mol %, and even more preferably 40 mol % to 80 mol %. The active hydrogen on the nitrogen atom of the cationic group is the NH group and NH ２ The term "NH group" refers to a hydrogen atom in a group. The amount of NH groups in the cationic groups contained in the polyalkylene oxide-containing compound of the present invention is preferably 1 mol% to 99 mol%, more preferably 20 mol% to 90 mol%, and even more preferably 40 mol% to 80 mol%. The amount of NH groups may also be 55 mol% to 99 mol%, or may be 75 mol% to 99 mol%, based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

[0048] As described above, the number of NH groups in the cationic groups of the polyalkylene oxide-containing compound of the present invention is reduced by etherification with an epoxy compound or alkylation by Michael addition with an α,β-unsaturated carbonyl compound, etc. On the other hand, from the viewpoint of improving the detergency of the composition of the present invention, it is preferable that an appropriate amount of active hydrogen on the nitrogen atom remains.

[0049] As described above, the NH group in the cationic group of the polyalkylene oxide-containing compound of the present invention is alkylated with an epoxy compound, a carboxyl group-containing compound, or the like to produce a structural unit of the following general formula (2):

[0050] For example, by carrying out alkylation treatment using an epoxy compound, it is possible to have a structural unit of the following general formula (2-1).

[0051] Alternatively, by carrying out alkylation treatment using a meth(acrylate) compound or a (meth)acrylamide compound, it is possible to have a structural unit of the following general formula (2-2).

[0052] (In general formula (2-2), Y is a hydrogen atom and / or a methyl group.)

[0053] The amount of the substituent represented by general formula (1) in the polyalkylene oxide-containing compound of the present invention is not particularly limited, but is preferably 1 mol% to 99 mol% relative to the total moles of nitrogen atoms contained in the polyalkylene oxide-containing compound (100 mol%). It is more preferably 5 to 80 mol%, even more preferably 10 to 70 mol%, even more preferably 15 to 65 mol%, and particularly preferably 20 to 60 mol%. In one embodiment, the amount of the substituent represented by general formula (1) may be 1 mol% to 45 mol%, or may be 1 mol% to 25 mol%, relative to the total moles of nitrogen atoms contained in the polyalkylene oxide-containing compound (100 mol%).

[0054] In the polyalkylene oxide-containing compound of the present invention, the average number of moles of alkylene oxide added in general formula (1) is preferably 1 to 300. It is more preferably 2 to 200, even more preferably 3 to 100, still more preferably 4 to 80, and particularly preferably 5 to 60.

[0055] As mentioned above, the cationic group possessed by 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 serving as a raw material for the structural unit having an amino group with a compound serving as a raw material for a linking group or a structural unit portion derived from polyalkylene oxide, and, if necessary, further reacting with a compound such as an acid anhydride to form an amide bond in the cationic group. Specific examples include structural units derived from amino group-containing compounds such as polyethylene polyamines (PEA) such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, tetrabutylenepentamine, polyethyleneimine (PEI), polyamidoamine, polyvinylamine, polyallylamine, and amino group-containing polysaccharides such as chitosan. In the present invention, the "structural unit derived from an amino group-containing compound" typically refers to a residue obtained by removing at least one hydrogen atom from the amino group-containing compound.

[0056] The precursor serving as a raw material for the structural unit having an amino group can be represented, for example, by the following general formula (5).

[0057]

[0058] (In general formula (5), R １０ are 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 is the same or different and represents a hydrogen atom or a structural unit having another amino group due to branching. a, b, and c are 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. The structural unit having an amino group contains at least one or more -N-R １０ When a precursor represented by the general formula (5) is used, the group obtained by removing a hydrogen atom bonded to a nitrogen atom from the precursor becomes the cationic group possessed by the polyalkylene oxide compound of the present invention. Note that, with respect to the precursor serving as a raw material for the structural unit having an amino group, the structural formula of the amino group constituting the precursor is, for example, as an example in the case of the general formula (5), ２ N-R １０ -, -NH-R １０ -, -N(-)-R １０ The cationic group (structural unit having an amino group) possessed by the polyalkylene oxide-containing compound of the present invention is preferably a form in which three other amino groups are bonded to the nitrogen atom of at least one amino group. An embodiment in which the above-mentioned a or b and c are 1 or more and P has a structural unit having another amino group due to branching is one of the preferred embodiments of the present invention.

[0059] R １０ is preferably an ethylene group, a propylene group, an isopropylene group, a butylene group, or an isobutylene group, and more preferably an ethylene group.

[0060] 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 R １０’It is preferred that the bond to the structure represented by formula (5) is via a group.

[0061]

[0062] (In general formula (6), a', b', c', P', R １０’ are a, b, c, P, and R in general formula (5), respectively. １０ (Similar to the above.)

[0063] In the precursor serving as a raw material for the structural unit having an amino group represented by the general formula (5) or (6), R １０ The alkylene group in R may be one type or two or more types, but it is preferably one type, and an ethylene group is preferred. １０ is a branched alkylene group having 3 to 6 carbon atoms, a 1,2-propylene group is preferred. In the general formula (5), a, b, and c may be the same or different and may be an integer of 0 or 1 or greater, but each is preferably an integer of 0 to 100. Furthermore, a + b + c may be a number of 1 or greater, but a + b + c of 1 to 4, 1 to 3, or 1 or 2 are all preferred forms of the precursor that serves as a raw material for the structural unit having an amino group. Furthermore, a + b + c of 5 or greater is also a preferred form of the precursor that serves as a raw material for the structural unit having an amino group. In the general formula (6), a', b', and c' are the same as a, b, and c in the general formula (5), and the above a' + b' + c' is the same as the above a + b + c.

[0064] In addition, the total number of nitrogen atoms contained in a, b, c, and P in the general formula (5) is preferably 4 to 100, more preferably 5 to 75, even more preferably 10 to 50, and particularly preferably 12 to 45. In one aspect, the number of nitrogen atoms contained in the cationic group may be 5 to 60, and an embodiment in which the number is 7 to 50 is also one of the preferred embodiments of the present invention.

[0065] The average molecular weight of the precursor serving as a raw material for the structural unit having an amino group is not particularly limited, but is preferably 50 to 10,000, more preferably 100 to 5,000, even more preferably 150 to 3,000, and particularly preferably 200 to 2,500. The average molecular weight can be measured by GPC.

[0066] Examples of the polyalkylene oxide-containing compound of the present invention (having a substituent represented by the general formula (1)) include compounds in which a linking group is bonded to the nitrogen atom of the amino group of a (poly)alkyleneamine having at least one 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 polyalkylene oxide is bonded to the other end of the linking group, and 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: (H ２ -N-R １０ )-R １０ is the same as general formula (5). In some cases, it also contains a structural unit represented by the following formula: ２ The amino group unit containing a secondary amine nitrogen atom is represented, for example, by the following general formula (7).

[0067]

[0068] The amino group unit containing a tertiary amine nitrogen atom is represented, for example, by the following general formula (8).

[0069]

[0070] (P and R in general formulas (7) and (8) １０ is the same as in general formula (5).

[0071] In the structural unit having an amino group, the form of the amino group unit is not particularly limited, and for example, the amino group unit (α) containing a primary amine nitrogen atom, the amino group unit (β) containing a secondary amine nitrogen atom, and the amino group unit (γ) containing a tertiary amine nitrogen atom may be randomly present. The nitrogen atom constituting the amino group may be quaternized or oxidized.

[0072] In the cationic group of the polyalkylene oxide-containing compound, the molar ratio of the amino group units (α), (β), and (γ) is preferably (α):(β):(γ)=10-80 / 10-80 / 10-80, and more preferably (α):(β):(γ)=20-50 / 20-50 / 20-50.

[0073] Furthermore, one example of a precursor that serves as a raw material for the structural unit having a cation group of the present invention represented by the general formula (5) is an amine compound represented by the following general formula (9).

[0074]

[0075] (In general formula (9), R １１ are 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.

[0076] 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).

[0077]

[0078] (In general formula (10), R １１ are 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.

[0079] The diamine compound serves as a precursor of the structural unit of the general formula (10). When a (meth)acrylic acid compound undergoes a Michael addition reaction with the diamine compound, which is the 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 of the following general formula (12) is produced.

[0080]

[0081]

[0082] (R in general formula (11) and general formula (12) １１ is the same as in general formula (9) and general formula (10). １２ are the same or different and represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; R １３ represents a hydrogen atom or a methyl group.

[0083] In the general formula (11), R １２ 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 30 carbon atoms, and may be appropriately selected to adjust the hydrophilicity or hydrophobicity. The organic group is preferably a hydrocarbon group.

[0084] The polyalkylene oxide-containing compound of the present invention can be obtained by addition reacting an epoxy compound or a glycidyl ether compound having a polyalkylene oxide structure with a polyamine compound represented by the general formula (12). In this case, the amino group moiety introduced by the reaction of a diamine compound with a 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 with the compound represented by the general formula (12).

[0085] 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 by 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 relative to the number average molecular weight before the decomposition test. More preferably, it is 0.4 or less, and even more preferably 0.2 or less. When the number average molecular weight after the decomposition test is smaller than the number average molecular weight before the decomposition test, this is preferable because, when the polyalkylene oxide-containing compound of the present invention is used, for example, as a detergent or detergent composition, the environmental burden caused by the compound discharged after washing is reduced.

[0086] 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. When the weight-average molecular weight of the polyalkylene oxide-containing compound of the present invention is within the above-mentioned range, it is preferable because the compound has compatibility with liquid detergents and reduces the environmental load due to the decomposition reaction.

[0087] The weight-average molecular weight of a polyalkylene oxide-containing compound can be measured by GPC under the following measurement conditions. <Measurement conditions for gel filtration chromatography (GPC)> Apparatus: EcoSEC HLC-8320GPC manufactured by Tosoh Corporation 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)

[0088] <Method for producing polyalkylene oxide-containing compound>

[0089] Another example of the method (I) for producing a polyalkylene oxide-containing compound of the present invention is a production method comprising a first step of Michael addition of an α,β-unsaturated carbonyl compound having a polyalkylene oxide chain to the amino group of a compound having an amino group that is a cationic group. In the production method (I), the first step and the addition of an NH group and / or NH ２ A preferred embodiment of the present invention also includes a second step of reacting the group with one or more compounds selected from acid anhydrides, acid halides, and cyclic compounds, or neutralizing the group with an acid compound, or both. In the above-mentioned production method (I), the second step may or may not be performed, and may be appropriately selected as needed. Note that, even if the step of neutralizing with an acid compound is performed in the above-mentioned production method (I), the amount of active hydrogen on the nitrogen atom does not change.

[0090] The α,β-unsaturated carbonyl compound having a polyalkylene oxide chain used in the first step of the production method (I) is preferably an (alkoxy)polyalkylene oxide (meth)acrylate or an (alkoxy)polyalkylene glycol (meth)acrylamide. The compound having an amino group, which is a cationic group, is not particularly limited, but specific examples and preferred forms are as described in the precursor that serves as the raw material for the structural unit having an amino group. The compound having an amino group is preferably a polyalkylene amine. 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 Michael addition of the double bond of an (alkoxy)polyalkylene oxide (meth)acrylate or an (alkoxy)polyalkylene glycol (meth)acrylamide to the amino group of the polyalkylene amine.

[0091] The (poly)alkyleneamine used in the production method (I) can 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 production method (I) can be represented by the following general formula (13).

[0092]

[0093] (In general formula (13), R １ is a hydrocarbon group having 3 to 6 carbon atoms, R ２ is a hydrocarbon group having 2 to 6 carbon atoms, R ３ are the same or different and represent a hydrogen atom and / or an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 300, and n is an integer of 1 to 300. Z represents a carbonyl group or a direct bond. G represents one or more selected from an oxygen atom, a nitrogen atom, and an NH group. d is an integer of 1 or 2, and when G is an oxygen atom or an NH group, d is 1, and when G is N, d is 2. Z represents a carbonyl group or a direct bond.

[0094] R in the general formula (13) １ , R ２ , R ３ , m, n, and d are the same as those in the general formula (1), and the preferred forms are also the same. Z is not particularly limited as long as it is a carbonyl group or a direct bond, and is preferably a carbonyl group. When Z is a carbonyl group, it exhibits hydrolysis, and therefore is a preferred chemical structure for uses requiring biodegradability.

[0095] In general formula (13), specific examples of polyalkylene oxide (meth)acrylate compounds when m 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 esters and (alkoxy)polyethylene glycol (poly)butylene glycol (meth)acrylic acid esters. Particularly preferred are (alkoxy)polyethylene glycol (poly)propylene glycol acrylic acid esters, (alkoxy)polyethylene glycol (poly)butylene glycol acrylic acid esters, methoxypolyethylene glycol (poly)propylene glycol acrylic acid esters, and methoxypolyethylene glycol (poly)butylene glycol acrylic acid esters. When m is 0, (alkoxy)polyethylene glycol (meth)acrylic acid esters, methoxypolyethylene glycol methacrylic acid esters, and methoxypolyethylene glycol acrylic acid esters are preferred. When the value of m 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.

[0096] In general formula (13), n is not particularly limited as long as it is an integer of 1 to 300, and is preferably 1 to 200, more preferably 5 to 100, and even more preferably 10 to 50. When the value of n is within the above-mentioned range, the compatibility of the polyalkylene oxide-containing compound produced using the compound as a raw material with liquid detergents and the blending stability into liquid detergents are improved, which is preferable.

[0097] Also, R ２ is a hydrocarbon group having 2 carbon atoms, -R ２ When the total amount of —O— groups is 100 mol %, —R ２ The content of —O— groups is preferably 70 mol % or more, more preferably 75 mol % or more, and even more preferably 80 mol % or more. ２ is a hydrocarbon group having 2 carbon atoms, -R in the general formula (3) ２When the content of the —O— group is within the above-mentioned range, the hydrophilicity of the polyalkylene oxide chain is improved, and therefore, the compatibility of a polyalkylene oxide-containing compound produced using the compound as a raw material with a liquid detergent and the blending stability into the liquid detergent are improved, which is preferable.

[0098] In the first step of the production method (I), when the (alkoxy)polyalkylene oxide (meth)acrylate or (alkoxy)polyalkylene glycol (meth)acrylamide represented by the general formula (13) is bonded to the hydrogen atom of the amino group of the (poly)alkyleneamine represented by the general formula (5) by a Michael addition reaction, a (poly)alkyleneamine-(alkoxy)polyalkylene oxide (meth)acrylate adduct or a (poly)alkyleneamine-(alkoxy)polyalkylene oxide (meth)acrylamide adduct is obtained.

[0099] Furthermore, in the first step of the production method (I), 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 (13) is preferably 20 to 100°C. More preferably, it is 40 to 80°C. Furthermore, the reaction time for the first step is preferably 1 hour or longer, more preferably 5 hours or longer, and even more preferably 10 hours or longer. When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively, improving the reaction and reducing unreacted raw materials, which is preferable.

[0100] When the production process of the (alkoxy)polyalkylene oxide (meth)acrylate used in production method (I) includes a step of esterification between (meth)acrylic acid and (alkoxy)polyalkylene oxide, (meth)acrylic acid may remain. In this case, the Michael addition reaction of the (alkoxy)polyalkylene oxide (meth)acrylate proceeds more easily than that of (meth)acrylic acid. Therefore, by carrying out the reaction of the (poly)alkylene amine represented by the general formula (5) with the (alkoxy)polyalkylene oxide (meth)acrylate at a low temperature, 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 when using (alkoxy)polyalkylene glycol (meth)acrylamide instead of the (alkoxy)polyalkylene oxide (meth)acrylate.

[0101] In the production method (I), the (poly)alkyleneamine represented by the general formula (5) may be reacted with the (alkoxy)polyalkylene oxide (meth)acrylate or (alkoxy)polyalkylene glycol (meth)acrylamide represented by the general formula (13) without using 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.

[0102] In the production method (I), the NH group and / or NH 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 ２A second step may be carried out in which the group is reacted with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound, or neutralized with an acid compound. The second step is not necessarily carried out in production method (I), and may be appropriately selected as necessary.

[0103] Specific examples of the acid anhydride, acid halide, and cyclic compound used in the second step of production method (I) include acid anhydrides such as acetic anhydride, succinic anhydride, and maleic anhydride; acid halides such as acetic acid chloride and propionic acid chloride; and cyclic compounds such as caprolactone compounds and caprolactam compounds. The amount of the acid anhydride, acid halide, and cyclic compound used in the second step may be adjusted so that the proportion of NH groups in the resulting polyalkylene oxide-containing compound falls within a preferred range. Preferably, the molar ratio of the acid anhydride, acid halide, and cyclic ester compound used in the second step is 10 to 100 mol% relative to 100 mol% of the active hydrogen on nitrogen atoms contained in the (poly)alkyleneamine used in the first step. More preferably, the ratio is 15 to 90 mol%, and even more preferably, the ratio is 20 to 80 mol%.

[0104] Specific examples of the acid compound used in the second step of production method (I) include acetic acid, citric acid, phosphoric acid, nitric acid, sulfuric acid, p-toluenesulfonic acid, etc. There are no particular limitations on the acid compound as long as it is capable of reacting with an amino group. Organic acids such as acetic acid and citric acid are preferred, and citric acid is more preferred. The amount of the acid compound used in the second step is preferably such that the number of moles of the acid compound used in the second step is 10 to 100 mol % relative to 100 mol % of the active hydrogen on the nitrogen atom contained in the (poly)alkyleneamine used in the first step. A more preferred ratio is 15 to 90 mol %, and even more preferred is a ratio of 20 to 80 mol %.

[0105] In addition, a production method similar to production method (I) includes 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 and / or NH ２and a second step of reacting the cationic amino group with one or more compounds selected from an acid anhydride, an acid halide, and a cyclic ester compound to obtain the polyalkylene oxide-containing compound of the present invention. Another production method similar to production method (I) includes a first step of Michael addition of an α,β-unsaturated carbonyl compound to the cationic amino group, a second step of introducing a polyalkylene oxide chain into the product obtained in the first step, and a second step of reacting an NH group and / or NH ２ and a third step of reacting the group with one or more compounds selected from acid anhydrides, acid halides, and cyclic ester compounds to obtain the polyalkylene oxide-containing compound of the present invention.

[0106] In another production method (II), the polyalkylene oxide-containing compound of the present invention can be obtained by carrying out a step of subjecting a hydrogen atom of an amino group of a (poly)alkyleneamine to a ring-opening addition reaction with an epoxy compound (an epoxy compound having a polyalkylene oxide) such as ethylene oxide represented by the following general formula (14):

[0107] (In general formula (14), R １ , R ２ , R ３ , m, and n are the same as in general formula (1).

[0108] In general formula (14), n is not particularly limited as long as it is an integer from 1 to 300, and is preferably 1 to 200, more preferably 5 to 100, and even more preferably 10 to 50. It is preferable for the value of n to be within the above-mentioned range because this improves the compatibility of the polyalkylene oxide-containing compound produced using that compound as a raw material with liquid detergents. m is not particularly limited as long as it is an integer from 0 to 300, and is preferably 0 to 10, more preferably 0 to 5, and even more preferably 0.

[0109] In the first step of the production method (II), an epoxy compound having a polyalkylene oxide represented by the general formula (14) is bonded to a hydrogen atom of an amino group of a (poly)alkyleneamine represented by the general formula (5) by a ring-opening addition reaction, thereby obtaining a (poly)alkyleneamine-epoxy adduct.

[0110] Furthermore, in the first step of the production method (I), the reaction temperature for the ring-opening addition reaction of the (poly)alkyleneamine represented by the general formula (5) and the epoxy compound having the polyalkylene oxide represented by the general formula (14) is preferably 50 to 80°C. More preferably, it is 60 to 70°C. Furthermore, the reaction time for the first step is preferably 1 hour or longer, more preferably 5 hours or longer, and even more preferably 10 hours or longer. When the reaction temperature and reaction time are within the above-mentioned ranges, the reaction proceeds almost quantitatively, improving the reaction and reducing the amount of unreacted raw materials, which is preferable.

[0111] When the production process of the epoxy compound having a polyalkylene oxide used in the production method (I) includes a step of ether synthesis using epichlorohydrin and an alkoxypolyalkylene glycol, epichlorohydrin may remain. In this case, it is possible to remove unreacted epichlorohydrin by vacuum distillation or washing with diethyl ether, which makes it possible to increase the purity of the epoxy compound having a polyalkylene oxide and improve the reaction rate with the (poly)alkyleneamine represented by the general formula (5), which is preferable.

[0112] In the production method (II), the (poly)alkyleneamine represented by the general formula (5) may be reacted with the epoxy compound having the polyalkylene oxide represented by the general formula (14) without using a solvent. When the reaction is carried out using a reaction solvent, one or a mixture of one or more solvents selected from ethers such as diethyl ether, dioxane, and tetrahydrofuran; and polar solvents such as dimethyl sulfoxide and dimethylformamide may be used.

[0113] Another example of the method (III) for producing a polyalkylene oxide-containing compound of the present invention includes a first step of Michael addition of an unsaturated ester compound to the amino group of a compound having an amino group, and a second step of introducing a polyalkylene oxide chain into the group derived from the unsaturated ester compound of the product obtained in the first step. The compound having an amino group is as described above.

[0114] The unsaturated ester compound used in the first step may be any compound having an unsaturated group and an ester group, but is preferably an ester of an unsaturated carboxylic acid with an alcohol having 1 to 30 carbon atoms. Examples of the alcohol having 1 to 30 carbon atoms include alkyl alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, lauryl alcohol, and stearyl alcohol; aryl alcohols such as benzyl alcohol; and unsaturated alcohols such as allyl alcohol, methallyl alcohol, propargyl alcohol, crotyl alcohol, pentenol, hexenol, heptenol, octenol, nonenol, decenol, dodecenol, and octadecenol. The number of carbon atoms in the alcohol is preferably 1 to 20, more preferably 1 to 15, even more preferably 1 to 10, even more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 4. The alcohol is preferably an alkyl alcohol.

[0115] Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, and itaconic acid; unsaturated dicarboxylic acids such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, and fumaric acid; and salts, anhydrides, and half esters thereof. Preferred as the unsaturated carboxylic acid is (meth)acrylic acid.

[0116] The ester of the unsaturated carboxylic acid and the alcohol is preferably an alkyl (meth)acrylate having an alkyl group having 1 to 30 carbon atoms (alkyl (meth)acrylate).

[0117] Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and icosyl (meth)acrylate. Of these, preferred are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate, with methyl (meth)acrylate and ethyl (meth)acrylate being more preferred.

[0118] The amount of the unsaturated ester compound used in the first step may be adjusted so that the proportion of NH groups in the resulting polyalkylene oxide-containing compound falls within a preferred range, and is preferably 1 to 99 mol %, more preferably 10 to 80 mol %, and even more preferably 15 to 60 mol %, relative to 100 mol % of the total number of moles of nitrogen atoms (amount of active hydrogen on nitrogen atoms) in the amino group-containing compound.

[0119] In the first step, the double bond of the unsaturated ester compound can be subjected to Michael addition with the amino group of the amino group-containing compound to bond an ester bond-containing group to the amino group.

[0120] The reaction temperature and reaction time of the Michael addition reaction in the first step are the same as those in the Michael addition reaction in the first step of the above-mentioned production method (I). The Michael addition reaction may be carried out in a solvent or without a solvent. Specific examples and preferred forms of the solvent are also the same as those in the Michael addition reaction in the first step of the above-mentioned production method (I).

[0121] The second step is not particularly limited as long as it introduces a polyalkylene oxide chain into at least a portion of the groups derived from the unsaturated ester compound in the product obtained in the first step. However, it is preferable to introduce the polyalkylene oxide chain by transesterification of the groups derived from the unsaturated ester compound with a polyalkylene glycol compound as a polyalkylene oxide raw material. In this case, the group derived from the unsaturated ester compound becomes a linking group represented by -X-G- in general formula (1) that bonds to the nitrogen atom of the amino group. In one embodiment, in the second step of the method for producing a polyalkylene oxide-containing compound of the present invention, polyalkylene oxide chains may be introduced into all of the groups derived from the unsaturated ester compound in the product obtained in the first step.

[0122] The polyalkylene glycol compound used in the second step may be any compound as long as it has a polyalkylene oxide chain and undergoes an ester exchange reaction with a group derived from the unsaturated ester compound. １ -O) ｍ - (R ２ -O) ｎ -R ３ (15) (In general formula (15), R １ represents a hydrocarbon group having 3 to 6 carbon atoms. ２ represents a hydrocarbon group having 2 to 6 carbon atoms. ３ are the same or different and represent a hydrogen atom and / or an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 300, and n is an integer of 1 to 300. １ , R ２ , R ３ , m, and n are the same as in general formula (1).

[0123] The amount of polyalkylene glycol compound used in the second step is not particularly limited, but is preferably 1 to 100 mol% relative to 100 mol% of the total moles of nitrogen atoms in the amino group-containing compound. The amount of polyalkylene glycol compound used is more preferably 5 to 90 mol%, and even more preferably 10 to 80 mol%. Furthermore, the amount of polyalkylene glycol compound used is preferably 1 to 100 mol% relative to 100 mol% of the groups derived from the unsaturated ester compound in the product obtained in the first step. More preferably, it is 5 to 90 mol%, and even more preferably 10 to 80 mol%.

[0124] <Enzymes> The enzymes contained in the composition of the present invention are not particularly limited as long as they exhibit cleaning performance, and examples thereof include protease, lipolytic enzyme, carbohydrate-degrading enzyme, oxidoreductase, and other degrading enzymes, which can be used alone or in combination of two or more. Examples of the protease include, but are not particularly limited to, proteases such as pepsin, trypsin, and peptidase. Examples of the lipolytic enzyme include, but are not particularly limited to, lipase, phospholipase, and lipoxygenase.

[0125] The carbohydrate-degrading enzyme is not particularly limited, but examples thereof include hemicellulase, cellulase, xylanase, pectinase, pullulanase, pentosanase, malanase, β-glucanase, arabinosidase, amylase, sucrase, maltase, and fructofuranosidase.

[0126] The oxidoreductase is not particularly limited, but examples thereof include peroxidase, reductase, oxidase, phenol oxidase, and laccase.

[0127] The other decomposing enzymes include, but are not limited to, esterase, cutinase, keratanase, ligninase, tannase, hyaluronidase, chondroitinase, and the like.

[0128] The enzyme is preferably a protease or a carbohydrate-degrading enzyme, more preferably a protease or an amylase, and even more preferably a protease.

[0129] <Surfactant> The surfactant contained in the composition of the present invention is not particularly limited, and examples thereof include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants can be used alone or in combination of two or more. Preferably, the composition contains an anionic surfactant and / or a nonionic surfactant. When two or more surfactants are used, the combined amount of the anionic surfactant and the nonionic surfactant is preferably 5 to 100% by mass relative to 100% by mass of the total surfactants. More preferably, it is 50 to 100% by mass, even more preferably 75 to 100% by mass, and particularly preferably 80 to 100% by mass.

[0130] The composition of the present invention preferably contains an anionic surfactant as a surfactant. Among surfactants, anionic surfactants have the greatest effect on enzyme activity, and therefore, in a composition containing an anionic surfactant, stabilizing the enzyme with the polyalkylene oxide-containing compound of the present invention is of great technical significance. The content of the anionic surfactant is preferably 10 to 100% by mass relative to 100% by mass of the total surfactant. More preferably, it is 10 to 50% by mass, even more preferably 10 to 45% by mass, and particularly preferably 10 to 40% by mass.

[0131] Suitable examples of the anionic surfactant include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, α-olefin sulfonates, α-sulfofatty acid or ester salts, alkanesulfonates, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl phosphates or salts thereof, alkenyl phosphates or salts thereof, etc. In the alkyl and alkenyl groups in the anionic surfactants, the alkyl group, such as a methyl group, may be branched.

[0132] Suitable nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, alkylamine oxides, etc. The alkyl and alkenyl groups in the nonionic surfactants may have branched alkyl groups such as methyl groups.

[0133] The cationic surfactant is preferably a quaternary ammonium salt, etc. The amphoteric surfactant is preferably a carboxyl-type amphoteric surfactant, a sulfobetaine-type amphoteric surfactant, etc. The alkyl group or alkenyl group in the cationic surfactant or amphoteric surfactant may be a branched alkyl group such as a methyl group.

[0134] <Other Components> The composition of the present invention may contain other components in addition to the polyalkylene oxide-containing compound of the present invention, enzymes, and surfactants. These other components are not particularly limited, and examples thereof include detergent builders; stain inhibitors such as benzotriazole and ethylene-thiourea; soil release agents; color transfer inhibitors; fabric softeners; alkaline substances for adjusting pH; fragrances; solubilizing agents; fluorescent agents; colorants; foaming agents; foam stabilizers; polishing agents; disinfectants; antibacterial agents; preservatives; thickeners; bleaching agents; bleaching aids; dyes; solvents, etc.

[0135] The detergent builder is not particularly limited, but examples thereof include alkali builders such as carbonates, hydrogen carbonates, and silicates; chelating builders such as tripolyphosphates, pyrophosphates, Glauber's salt, nitrilotriacetates, ethylenediaminetetraacetates, citrates, (meth)acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, fumarates, and zeolites; and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Counter salts used in the detergent builders include alkali metals such as sodium and potassium, and alkaline agents such as sodium hydroxide, ammonium, and amines. One or more of these can be used as other components.

[0136] The solvent is not particularly limited, and examples thereof include water; alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monobutyl ether; Preferred hydrophilic solvents include alkyl ethers such as alkyl ethers; sulfoxides (e.g., dimethyl sulfoxide) such as sulfone, diethyl sulfone, and bis(2-hydroxyethyl) sulfone; cyclic ethers (e.g., tetrahydrofuran and tetrahydropyran); nitriles (e.g., acetonitrile, propionitrile, butyronitrile, acrylonitrile, and methacrylonitrile); carbonates (e.g., ethylene carbonate and propione carbonate); and ketones (e.g., acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and diacetone alcohol).

[0137] When the composition contains a detergent builder, the blending ratio thereof is usually preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass, more preferably 0.3 to 10% by mass, even more preferably 0.4 to 8% by mass, and particularly preferably 0.5 to 5% by mass, relative to 100% by mass of the composition.

[0138] When the composition is a liquid detergent, the amount of water contained in the liquid detergent is usually preferably 0.1 to 75% by mass, more preferably 0.5 to 65% by mass, and particularly preferably 1 to 55% by mass, relative to 100% by mass of the liquid detergent.

[0139] <Uses of the Composition of the Present Invention> The composition 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. In particular, it can be suitably used for detergent builders, detergents, and dispersants. The composition of the present invention can also be a cleaning composition. The present invention also relates to a method for using the composition, which includes a step of mixing the composition with a polyalkylene oxide-containing compound and other detergent additives other than enzymes contained in the composition. The present invention also relates to a method for producing a detergent composition, which includes a step of mixing the composition with a polyalkylene oxide-containing compound and other detergent additives other than enzymes contained in the composition. Examples of other detergent additives include the surfactants and other components described above.

[0140] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0141] <Test 1 for evaluating cleaning power for protein stains> 1. The reflectance (Z value) of protein-stained fabric EMPA-117 (Swissates) was measured using a reflectometer (spectrophotometric color difference meter, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). 2. 500 g of hard water mother liquor (1) was prepared by adding pure water to 29.5 g of calcium chloride dihydrate and 13.6 g of magnesium chloride hexahydrate. 3. 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (2). 4. 4 g of hard water mother liquor (1) and 8 g of base solution (2) were added to 3,987 g of pure water and stirred to prepare cleaning solution (3). 5. For rinsing, 4 g of hard water mother liquor (1) was added to 3,996 g of pure water and stirred to prepare rinse solution (4). 6. 5 g of polyoxyethylene lauryl ether (Emulgen 108, manufactured by Kao Corporation, hereinafter also abbreviated as PAE) and 45 g of pure water were added and stirred to prepare a 10% nonionic surfactant aqueous solution (5). 7. 19.8 g of pure water was added to 0.2 g of Protease Progress Uno 101L (manufactured by Novozymes) to prepare a 1% protease solution (6). 8. 10 g of 10-fold diluted detergent solution (7) was prepared by mixing 0.25 g of 1% protease solution (6), pure water, 0.3 g of a 10% polymer aqueous solution containing the active ingredient, and 3 g of 10% nonionic surfactant aqueous solution (5). The amount of pure water added was calculated so that the 10-fold diluted detergent solution would be 10 g. For evaluation without polymer addition, a 10-fold diluted detergent solution (7) was prepared without adding an aqueous polymer solution. 9. 994.2 g of cleaning solution (3) was added to each of the four pots in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15°C. 5.8 g of 10-fold diluted detergent solution (7) was then added to each pot and stirred for 1 minute. 10. Seven EMPA-117 sheets were placed in each pot and stirred at 120 rpm for 15 minutes. 11. The soiled cloths were removed from each pot, the water was drained by hand, and 1000 g of rinse solution (4) was added to each pot. The temperature was adjusted to 15°C and the mixture was stirred at 120 rpm for 5 minutes. 12. The procedure of 11 was repeated once more.13. After drying at room temperature, the reflectance (Z value) of the soiled cloth was measured again using the above-mentioned spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the Δ cleaning rate was calculated using the following formula.

[0142] Δ cleaning rate (%) = [cleaning rate (%) with polymer added] - [cleaning rate (%) without polymer added] A larger cleaning rate value indicates better cleaning power, and a larger Δ cleaning rate indicates a greater effect of the polymer.

[0143] <Test 2 for Detergency Evaluation of Protein Stain> 1. The reflectance (R460) at a wavelength of 460 nm was measured for protein-stained fabric EMPA-117 (manufactured by Swissates) using a reflectometer (spectrophotometric colorimeter, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). 2. 500 g of hard water mother liquor (1) was prepared by adding 29.5 g of calcium chloride dihydrate and 13.6 g of magnesium chloride hexahydrate to prepare 500 g of hard water mother liquor (1). 3. 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (2). 4.4 g of hard water mother liquor (1) and 8 g of base solution (2) were added to 3,987 g of pure water and stirred to prepare cleaning solution (3). 5. For rinsing, 4 g of hard water mother liquor (1) was added to 3,996 g of pure water and stirred to prepare rinse solution (4). 6. 5 g of polyoxyethylene lauryl ether (Emulgen 108, manufactured by Kao Corporation, hereinafter also abbreviated as PAE) and 45 g of pure water were added and stirred to prepare a 10% nonionic surfactant aqueous solution (5). 7. 1% protease solution (6) was prepared by adding 19.8 g of pure water to 0.2 g of protease Progress Uno 101L (manufactured by Novozymes). 8. 10 g of 10-fold diluted detergent solution (7) was prepared by mixing 0.25 g of 1% protease solution (6), pure water, a polymer aqueous solution containing approximately 1% of the active ingredient adjusted to a pH of 7.5-8.5, and 3 g of 10% nonionic surfactant aqueous solution (5). The amount of polymer aqueous solution containing approximately 1% active ingredient was calculated to achieve a polymer active ingredient concentration of 0.3%, and the amount of pure water was calculated to provide a 10-fold diluted detergent solution (7) of 10 g. For evaluation without polymer addition, a 10-fold diluted detergent solution (7) was prepared without adding the polymer aqueous solution containing approximately 1% active ingredient. 9. 994.2 g of cleaning solution (3) was added to each of the four pots in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15°C. 5.8 g of 10-fold diluted detergent solution (7) was then added to each pot and stirred for 1 minute. 10. Seven sheets of EMPA-117 were placed in each pot and stirred at 120 rpm for 10 minutes. 11. The soiled cloths were removed from each pot, the water was drained by hand, and 1,000 g of rinse solution (4) was added to each pot. The temperature was adjusted to 15°C and the mixture was stirred at 120 rpm for 5 minutes. 12. The procedure in 11 was repeated once more.13. After drying at room temperature, the reflectance (R460) of the stained cloth at a wavelength of 460 nm was measured again using the above-mentioned spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the Δ cleaning rate was calculated using the following formula.

[0144] Δ cleaning rate (%) = [cleaning rate (%) with polymer added] - [cleaning rate (%) without polymer added] A larger cleaning rate value indicates better cleaning power, and a larger Δ cleaning rate indicates a greater effect of the polymer.

[0145] <Test 3 for evaluating cleaning power for protein stains> 1. The reflectance (Z value) of protein-stained fabric EMPA-117 (Swissates) was measured using a reflectometer (spectrophotometric color difference meter, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000). 2. 500 g of hard water mother liquor (1) was prepared by adding 29.5 g of calcium chloride dihydrate and 13.6 g of magnesium chloride hexahydrate to prepare 500 g of hard water mother liquor (1). 3. 15.5 g of sodium bicarbonate, 884.5 g of pure water, and 100 g of 0.1 M HCl aqueous solution were mixed to prepare 1,000 g of base solution (2). 4.4 g of hard water mother liquor (1) and 8 g of base solution (2) were added to 3,987 g of pure water and stirred to prepare cleaning solution (3). 5. For rinsing, 4 g of hard water mother liquor (1) was added to 3,996 g of pure water and stirred to prepare rinse solution (4). 6. 45 g of polyoxyethylene lauryl ether (Emulgen 108, manufactured by Kao Corporation, hereinafter also abbreviated as PAE), 23 g of sodium dodecylbenzenesulfonate (65%, Neopelex G-65, manufactured by Kao Corporation, hereinafter also abbreviated as LAS), 16 g of propylene glycol, 4 g of ethanol, and 112 g of pure water were added and stirred to prepare a 30% PAE / LAS aqueous solution (5). 7. 19.8 g of pure water was added to 0.2 g of protease Progress Uno 101L (manufactured by Novozymes) to prepare a 1% protease solution (6). 0.25 g of 8.1% protease solution (6), pure water, 0.3 g of a polymer aqueous solution containing 10% of the active ingredient, and 1 g of a 30% PAE / LAS aqueous solution (5) were mixed to prepare 10 g of a 10-fold diluted detergent solution (7). The amount of pure water was calculated so that the 10-fold diluted detergent solution (7) would be 10 g. For evaluation without adding a polymer, a 10-fold diluted detergent solution (7) was prepared without adding an aqueous polymer solution. 9. 994.2 g of cleaning solution (3) was added to each of the four pots in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15°C. 5.8 g of the 10-fold diluted detergent solution (7) was then added to each pot and stirred for 1 minute. 10. Seven sheets of EMPA-117 were placed in each pot and stirred at 120 rpm for 15 minutes. 11. The soiled cloth was removed from each pot, and the water was drained by hand. 1,000 g of the rinse solution (4) was added to each pot, and the temperature was adjusted to 15° C., followed by stirring at 120 rpm for 5 minutes. The procedure in 12.11 was repeated once more.13. After drying at room temperature, the reflectance (Z value) of the soiled cloth was measured again using the above-mentioned spectrophotometer (spectrophotometer, manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE6000), and the Δ cleaning rate was calculated using the following formula.

[0146] Δ cleaning rate (%) = [cleaning rate (%) with polymer added] - [cleaning rate (%) without polymer added] A larger cleaning rate value indicates better cleaning power, and a larger Δ cleaning rate indicates a greater effect of the polymer.

[0147] Synthesis Example 1: A glass reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 166.0 g of tetrahydrofuran, and 135.8 g of methoxypoly(n = 25)ethylene glycol was dissolved therein. 5.27 g of a 60% THF solution of sodium hydride was dissolved therein and heated to 70 ° C. 44.3 g of epichlorohydrin (Tokyo Chemical Industry Co., Ltd.) was then added dropwise over 30 minutes using a dropping funnel, and the mixture was stirred under reflux for 6 hours. After the reaction was completed, the epichlorohydrin was removed using an evaporator, and the resulting solid was washed twice with diethyl ether to obtain methoxypolyethylene glycol monoglycidyl ether (average number of moles of ethylene oxide added: 25, hereinafter also referred to as ePEG25) with a purity of 66.3%.

[0148] Example 1: A thermometer and a glass reactor equipped with a stirrer were charged with 0.53 g of polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006) and 4.47 g of ePEG25 with a purity of 66.3%, and stirred for 30 hours at 60 ° C. to obtain a polymer (1) in which 20 mol % of the NH groups of the polyethyleneimine were modified with PEG, with an active ingredient content of 69.9%. Example 2: A thermometer and a glass reactor equipped with a stirrer were charged with 0.28 g of polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006) and 4.72 g of ePEG25 with a purity of 66.3%, and stirred for 30 hours at 60 ° C. to obtain a polymer (2) in which 40 mol % of the NH groups of the polyethyleneimine were modified with PEG, with an active ingredient content of 68.2%. Example 3 A glass reactor equipped with a thermometer and a stirrer was charged with 0.21 g of polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006) and 4.81 g of ePEG25 with a purity of 66.3%, and the mixture was stirred at 60°C for 30 hours to obtain a polymer (3) in which 60 mol % of the NH groups of the polyethyleneimine were modified with PEG, with an active ingredient content of 67.6%.

[0149] Example 4: A glass reactor equipped with a thermometer and a stirrer was charged with 8.9 g of polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd.) and 91.1 g of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added: 23, trade name "AM-230G" manufactured by Shin-Nakamura Chemical Co., Ltd.), and stirred at 60°C for 2 hours to obtain a polymer (4) in which 40 mol% of the NH groups of the polyethyleneimine were modified with PEG, with an active ingredient content of 100%. Example 5: A glass reactor equipped with a thermometer and a stirrer was charged with 18.5 g of polymer (4) and 1.5 g of citric acid, and stirred at 60°C for 2 hours. Thereafter, 5 g of pure water was added to obtain a polymer (5) in which the polymer (4) was neutralized with citric acid, with an active ingredient content of 80.0%. In polymer (5), the neutralized product was the active ingredient.

[0150] The polymers (1) to (5) obtained in Examples 1 to 5 were subjected to Test 1 to evaluate the detergency for protein soils, and the results are shown in Table 1. Comparative Example 1 used polyethyleneimine-ethylene oxide copolymer obtained by ethoxylating polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006) with 20 moles of ethylene oxide per mole of active hydrogen bonded to nitrogen atoms. Comparative Example 2 used polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006).

[0151]

[0152] For the polymer (2) obtained in Example 2, the amount of enzyme used in preparing the 10-fold diluted detergent solution (7) was changed, and the results of the protein stain detergency evaluation test 1 were carried out. The results are shown in Table 2.

[0153]

[0154] Example 6 A glass reactor equipped with a thermometer and a stirrer was charged with 2.4 g of polyethyleneimine (PEI) (average molecular weight 300, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP003) and 9.57 g of methoxypolyethylene glycol monoglycidyl ether (average number of moles of ethylene oxide added: 9, hereinafter also abbreviated as ePEG9) having a purity of 84.9%, and the mixture was stirred at 70°C for 12 hours, thereby obtaining a polymer (6) in which 30 mol % of the NH groups of the polyethyleneimine were modified with PEG, with an active ingredient amount of 87.9%.

[0155] Various polymers were synthesized by varying the polyamine, methoxypolyethylene glycol monoglycidyl ether, and PEG modification rate relative to the NH group of the polyamine. Table 3 shows a list of the polymers synthesized in Examples 6 to 17. The polyamines used were Epomin SP003 (polyethyleneimine (PEI), average molecular weight 300, manufactured by Nippon Shokubai Co., Ltd.), Epomin SP006 (polyethyleneimine (PEI), average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd.), and Epomin SP018 (polyethyleneimine (PEI), average molecular weight 1800, manufactured by Nippon Shokubai Co., Ltd.). The methoxypolyethylene glycol monoglycidyl ethers used had average ethylene oxide addition moles of 9, 25, and 45 (also abbreviated as ePEG9, ePEG25, and ePEG45, respectively). The purity of the ePEG used was 84.9%, 78.3%, and 70.6%, respectively. The reaction was continued for a sufficient time until the raw ePEG was completely consumed.

[0156]

[0157] The polymers obtained in Examples 6 to 17 were subjected to Test 2 to evaluate the detergency for proteinaceous soils, and the results are shown in Table 4. As Comparative Examples 1 to 4, polyethyleneimine-ethylene oxide copolymers SP003, SP006, and SP018 obtained by ethoxylating 20 moles of ethylene oxide per mole of active hydrogen bonded to the nitrogen atom of polyethyleneimine SP006 were used.

[0158]

[0159] The polymer obtained in Example 2 was subjected to Test 3 for evaluating the detergency for protein soils, and the results are shown in Table 5. As Comparative Example 1, a polyethyleneimine-ethylene oxide copolymer was used, which was obtained by ethoxylating polyethyleneimine (PEI) (average molecular weight 600, manufactured by Nippon Shokubai Co., Ltd., product name: Epomin SP006) with 20 moles of ethylene oxide per mole of active hydrogen bonded to nitrogen atoms.

[0160]

Claims

1. A composition comprising a polyalkylene oxide-containing compound and an enzyme, the compound having a cationic group, a linking group, and a structural unit derived from a polyalkylene oxide, the linking group connecting the cationic group and the structural unit derived from a polyalkylene oxide, and the cationic group having an NH group.

2. The composition according to claim 1, wherein the linking group is a group having one or more substituents selected from an ester group, an amide group, and an ether group.

3. The composition according to claim 1 or 2, wherein the amount of active hydrogen on the nitrogen atom of the cationic group is 1 mol % to 99 mol % based on the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

4. The polyalkylene oxide-containing compound has a cation group represented by the following general formula (1): (In general formula (1), R １ is a hydrocarbon group having 3 to 6 carbon atoms, R ２ is a hydrocarbon group having 2 to 6 carbon atoms, R ３ are the same or different and represent a hydrogen atom and / or an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 300, and n is an integer of 1 to 300. X represents an organic group having 2 to 6 carbon atoms. G represents one or more selected from an oxygen atom, a nitrogen atom, an NH group, and a direct bond. d is an integer of 1 or 2, and when G is an oxygen atom or an NH group, d is 1, and when G is N, d is 2. The composition according to any one of claims 1 to 3, having a structure in which a substituent represented by 5. The composition according to claim 4, wherein the amount of the substituent represented by the general formula (1) is 1 mol % to 99 mol % relative to 100 mol % of the total number of moles of nitrogen atoms contained in the polyalkylene oxide-containing compound.

6. The composition according to any one of claims 1 to 5, wherein the content of the polyalkylene oxide-containing compound is 0.1 to 10 mass % when the composition is taken as 100 mass %.

7. The composition according to any one of claims 1 to 6, wherein the content of the enzyme is 0.01 to 10% by mass, relative to 100% by mass of the composition.

8. The composition according to any one of claims 1 to 7, comprising the polyalkylene oxide-containing compound, an enzyme, and a surfactant.

9. The composition according to claim 8, wherein the surfactant comprises one or more selected from anionic surfactants, nonionic surfactants, and amphoteric surfactants.

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