Liquid laundry detergent composition

Abstract

To provide a liquid laundry detergent composition that exhibits excellent soil-releasing properties against sebum stains. [Solution] A liquid laundry detergent composition comprising an amino group-containing copolymer as a first component, having structural units (a) derived from an amino group-containing monomer (A), structural units (b) derived from a monomer (B) having a polyalkylene glycol chain, and structural units (c) derived from an unsaturated carboxylic acid monomer (C), and possibly also having structural units (d) derived from an aromatic group-containing monomer (D), wherein the content ratios of structural units (a) and structural units (d) relative to 100% by mass of all structural units are 25-50% by mass and 0-20% by mass, respectively, and the total content ratio of structural units (a), structural units (b), structural units (c), and structural units (d) relative to 100% by mass of all structural units is 97% by mass or more, and a nonionic surfactant of a specific structure as a second component.

Description

[Technical Field]

[0001] This invention relates to a liquid detergent composition for clothing. More specifically, it relates to a liquid detergent composition for clothing that is useful for detergents and the like for clothing applications. [Background technology]

[0002] By pre-treating clothing fibers with compounds that adsorb to them, it is possible to make it easier to remove sebum and other stains during washing. This function is called soil-release properties. Conventionally, various compounds exhibiting soil-release properties have been proposed. For example, Patent Document 1 discloses an amino group-containing copolymer characterized by comprising a structural unit (a) derived from an amino group-containing monomer represented by a predetermined structure, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a structural unit (c) derived from a (meth)acrylic acid ester containing an aryl group which may have a substituent, wherein the proportion of the structural unit (a) derived from the amino group-containing monomer is 5 to 50% by weight with respect to 100% by mass of the total structural units. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2022 / 215652 [Overview of the project] [Problems that the invention aims to solve]

[0004] As mentioned above, although amino group-containing copolymers exhibiting soil-releasing properties have been developed, there has been a need to further improve the soil-releasing properties against sebum stains in liquid laundry detergent compositions.

[0005] This invention has been made in view of the above-mentioned circumstances, and aims to provide a liquid laundry detergent composition that exhibits excellent soil release properties against sebum stains. [Means for solving the problem]

[0006] The inventors of the present invention conducted various studies on liquid detergent compositions for clothing and discovered that by combining an amino group-containing copolymer of a predetermined structure with a nonionic surfactant, excellent soil-releasing properties against sebum stains can be achieved. This led to the realization that the above-mentioned problems could be successfully solved, and thus the present invention was arrived at.

[0007] The present invention includes the following liquid laundry detergent compositions, etc. [1] A liquid laundry detergent composition containing the following first and second components. First component: Formula (1) or (1') below; [ka] (R 1 , R 2 , R 3 R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. 4 , R 5 X represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, either identical or different. Y represents a direct bond or a divalent linking group. -represents an anion. However, the asterisk represents an atom contained in another identical or different structural unit to which the structural unit represented by the formula (1) or (1') is bonded. A structural unit (a) derived from an amino group-containing monomer (A) represented by (), a structural unit (b) derived from a monomer (B) having a polyalkylene glycol chain, and a structural unit (c) derived from an unsaturated carboxylic acid monomer (C), and may further have a structural unit (d) derived from an aromatic group-containing monomer (D). The content ratios of the structural unit (a) and the structural unit (d) with respect to 100% by mass of all the structural units are 25 to 50% by mass and 0 to 20% by mass, respectively, and the total content ratio of the structural unit (a), the structural unit (b), the structural unit (c) and the structural unit (d) with respect to 100% by mass of all the structural units is 97% by mass or more. An amino group-containing copolymer Component 2: A nonionic surfactant represented by the following formula (6-1) R 13 -(CO) q1 O-(A 2 O) q2 -R 14 (6-1) (In the formula, R 13 represents an aliphatic hydrocarbon group having 8 to 24 carbon atoms. R 14 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A 2 O represents, identically or differently, an oxyalkylene group having 2 to 4 carbon atoms. q1 represents a number of 0 or 1. q2 represents the average number of moles of addition of the oxyalkylene group represented by A 2 O, and is a number of 7 or more and 50 or less) 〔2〕The liquid detergent composition for clothing according to 〔1〕 above, wherein the weight average molecular weight of the first component is 4000 or more and 500000 or less. 〔3〕The liquid detergent composition for clothing according to 〔1〕 or 〔2〕 above, wherein the content ratio of the structural unit (b) of the first component is 25 to 70% by mass with respect to 100% by mass of all the structural units. 〔4〕The liquid detergent composition for clothing according to any one of 〔1〕 to 〔3〕 above, wherein the content ratio of the structural unit (c) is 1 to 10% by mass with respect to 100% by mass of all the structural units. [5] The liquid laundry detergent composition according to any one of [1] to [4] above, wherein the content of the nonionic surfactant is 5% by mass or more and 70% by mass or less based on 100% by mass of the liquid laundry detergent composition. [6] A cleaning method comprising the step of bringing a liquid laundry detergent composition described in any of [1] to [5] above into contact with an object. [7] A pretreatment method comprising the step of bringing a liquid laundry detergent composition described in any of [1] to [5] above into contact with an object. [Effects of the Invention]

[0008] The liquid laundry detergent composition of the present invention has the above-described configuration and exhibits excellent soil-releasing properties against sebum stains, making it suitable for use as a detergent for laundry. [Modes for carrying out the invention]

[0009] Preferred embodiments of the present invention will be described below in detail, but the present invention is not limited to the following descriptions and can be modified and applied as appropriate without changing the gist of the present invention. Furthermore, embodiments combining two or more of the individual preferred embodiments of the present invention described below also constitute preferred embodiments of the present invention.

[0010] [Liquid detergent composition for clothing] The liquid detergent composition for clothing of the present invention (hereinafter also simply referred to as the liquid detergent composition) contains the above-mentioned amino group-containing copolymer and a nonionic surfactant. By including these components, it exhibits excellent soil release properties and also excellent re-soiling prevention properties.

[0011] The content of the amino group-containing copolymer in the above liquid detergent composition is not particularly limited, but from the viewpoint of further enhancing soil release properties, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.15% by mass or more, and from the same viewpoint, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. In one embodiment, the proportion of the amino group-containing copolymer is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.15 to 1% by mass, based on 100% by mass of the liquid detergent composition. The "content ratio of amino group-containing copolymer" as used herein refers to the ratio assuming that all structural units (a) in the amino group-containing copolymer are amines represented by the above formula (1).

[0012] The proportion of the nonionic surfactant represented by formula (6-1) in the above liquid detergent composition is not particularly limited, but from the viewpoint of further enhancing soil release properties, it is preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 10% by mass or more, based on 100% by mass of the liquid detergent composition, and from the same viewpoint, it is preferably 70% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less. In one embodiment, the proportion of the nonionic surfactant is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, even more preferably 10 to 60% by mass, even more preferably 10 to 50% by mass, even more preferably 10 to 40% by mass, and particularly preferably 10 to 30% by mass, based on 100% by mass of the liquid detergent composition. When the liquid detergent composition of the present invention contains a plurality of nonionic surfactants represented by formula (6-1), the above ratio is the total ratio of the nonionic surfactants represented by formula (6-1).

[0013] Furthermore, the proportion of nonionic surfactant in the above liquid detergent composition is not particularly limited, but from the viewpoint of further enhancing soil release properties, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 1 part by mass of amino group-containing copolymer, and from the same viewpoint, preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and 200 parts by mass or less. In one embodiment, the proportion of the nonionic surfactant is preferably 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, and even more preferably 10 to 200 parts by mass, per 1 part by mass of the amino group-containing copolymer.

[0014] The essential and optional components included in the liquid detergent composition of the present invention will be further described below.

[0015] <Component 1: Amino group-containing copolymer> The above amino group-containing copolymer is of the following formula (1) or (1');

[0016] [ka]

[0017] (R 1 , R 2 , R 3 R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. 4 , R 5 X represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, either identical or different. Y represents a direct bond or a divalent linking group. -represents an anion. However, an asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by formula (1) or (1') is bonded. The structural unit has a structural unit (a) derived from an amino group-containing monomer (A) represented by ), a structural unit (b) derived from a monomer having a polyalkylene glycol chain (B), and a structural unit (c) derived from an unsaturated carboxylic acid monomer (C), and may further have a structural unit (d) derived from an aromatic group-containing monomer (D), with the content ratios of structural unit (a) and structural unit (d) relative to 100% by mass of all structural units being 25-50% by mass and 0-20% by mass, respectively, and the total content ratio of structural unit (a), structural unit (b), structural unit (c), and structural unit (d) relative to 100% by mass of all structural units being 97% by mass or more.

[0018] In this specification, "atoms contained in other structural units of the same type" means, for example, if the structural unit is represented by formula (1), then atoms contained in another structural unit represented by formula (1), and "atoms contained in other structural units of a different type" means, for example, if the structural unit is represented by formula (1), then atoms contained in structural units other than the structural unit represented by formula (1).

[0019] The content of structural unit (a) in the above amino group-containing copolymer is 25 to 50% by mass, preferably 25 to 45% by mass, more preferably 27 to 40% by mass, and even more preferably 27 to 35% by mass, based on 100% by mass of all structural units. It is also preferable that it be 35 to 50% by mass, 35 to 45% by mass, or 35 to 40% by mass. In this context, "the proportion of structural unit (a) in the amino group-containing copolymer" refers to the proportion assuming that all structural unit (a) in the amino group-containing copolymer are amines represented by formula (1) above.

[0020] The content of structural unit (b) in the above amino group-containing copolymer is not particularly limited, but is preferably 25 to 70% by mass relative to 100% by mass of all structural units. More preferably 35 to 65% by mass, even more preferably 40 to 60% by mass, particularly preferably 45 to 55% by mass, and most preferably 45 to 50% by mass.

[0021] The content of structural unit (c) in the above amino group-containing copolymer is not particularly limited, but is preferably 1 to 10% by mass relative to 100% by mass of all structural units. More preferably 1 to 8% by mass, even more preferably 2 to 6% by mass, and particularly preferably 3 to 5% by mass.

[0022] The content of structural unit (d) in the above amino group-containing copolymer is 0 to 20% by mass, preferably 0 to 18% by mass, more preferably 0 to 15% by mass, even more preferably 5 to 15% by mass, and particularly preferably 8 to 13% by mass, based on 100% by mass of the total structural units.

[0023] The above amino group-containing copolymer has a total content ratio of structural unit (a), structural unit (b), structural unit (c), and structural unit (d) of 97% by mass or more relative to 100% by mass of all structural units. Preferably, it is 98-100% by mass, more preferably 99-100% by mass, and most preferably 100% by mass.

[0024] The above amino group-containing copolymer may have structural units (e) derived from monomers other than amino group-containing monomers (A), monomers having polyalkylene glycol chains (B), unsaturated carboxylic acid monomers (C), and aromatic group-containing monomers (D), other monomers (E). The content of structural unit (e) in the above amino group-containing copolymer may be 0 to 3% by mass, but is preferably 0 to 2% by mass, more preferably 0 to 1% by mass, even more preferably 0 to 0.5% by mass, particularly preferably 0 to 0.1% by mass, and most preferably 0% by mass.

[0025] The above amino group-containing copolymer preferably has a weight-average molecular weight (Mw) of 4,000 or more and 500,000 or less, more preferably 7,000 or more and 300,000 or less, even more preferably 10,000 or more and 100,000 or less, particularly preferably 15,000 or more and 50,000 or less, and most preferably 20,000 or more and 40,000 or less. Within this range, the soil release performance of the copolymer tends to improve.

[0026] (Structural unit (a) derived from amino group-containing monomer (A)) The structural unit derived from the above amino basic monomer is the structure represented by formula (1) or (1') above. In the above formula (1) or (1'), X is a direct bond or a divalent linking group, and there are no particular restrictions on the divalent linking group, but examples include organic groups such as -C(=O)-O-, -C(=O)-N(-H)-, -C(=O)-O-(CH2)n- (n is 1 to 5), and -C(=O)-N(-H)-(CH2)n- (n is 1 to 5). Preferably, -X- is -C(=O)-O-(CH2)n-, more preferably n=1 to 3, and particularly preferably n=2.

[0027] The above Y - These are not particularly limited, but examples include halide ions such as chloride ions, bromide ions, and iodide ions; alkyl sulfate ions such as methyl sulfate ions; and organic acid ions such as acetate ions and citrate ions.

[0028] The structure derived from the above amino group-containing monomer (A) can be formed, for example, by radical polymerization of a monomer having an ethylenically unsaturated group and a primary to tertiary amino group represented by the following formula (2), or an acid-neutralized product of a primary to tertiary amino group, but is not limited thereto.

[0029] [ka]

[0030] R in equation (2) above 4 , R5 These are identical or different hydrogen atoms or organic groups having 1 to 12 carbon atoms. The above R 4 , R 5 The organic group in is not particularly limited, but a hydrocarbon group is preferred. The hydrocarbon group described above may have a chain-like structure or a cyclic structure, but a chain-like structure is preferred. When the hydrocarbon group has a chain-like structure, it may be linear or branched. The hydrocarbon group mentioned above is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, and more preferably an alkyl group. Furthermore, the number of carbon atoms in the above organic group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0031] The above R 4 , R 5 At least one of them is preferably a hydrocarbon group having 1 to 12 carbon atoms, R 4 and R 5 It is more preferable that both are hydrocarbon groups having 1 to 12 carbon atoms. In other words, among primary to tertiary amino groups, tertiary amino groups are preferred.

[0032] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, and t-amyl group. Examples include aliphatic alkyl groups such as 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, and dodecyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), and cyclopentylethyl group. The number of carbon atoms in the alkyl group having 1 to 12 carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 4.

[0033] Examples of the above-mentioned alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and dodecenyl groups. Examples of the alkynyl groups mentioned above include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desinyl group, and dodecynyl group. The number of carbon atoms in the above-mentioned alkenyl group and alkynyl group is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 6, and particularly preferably 2 to 4.

[0034] Examples of the aryl groups mentioned above include phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, propylphenyl group, naphthyl group, and the like. Examples of the above-mentioned aralkyl groups include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. The number of carbon atoms in the above-mentioned aryl group and aralkyl group is preferably 6 to 10, and more preferably 6 to 8.

[0035] The structural unit (a) derived from the above amino group-containing monomer (A) is formed, for example, by radical polymerization of the amino group-containing monomer (A). The above amino group-containing monomer (A) specifically includes N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, and their neutralization products with acids such as hydrochloric acid and acetic acid; N,N-dialkylamino group-containing (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide, and their neutralization products with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, and 2-(tert-butylamino) (meth)acrylic acid. (Meth)acrylates containing monoalkylamino groups such as ethyl and their neutralized products with acids such as hydrochloric acid and acetic acid; monoalkylamino group-containing (meth)acrylamides such as monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, monoethylaminopropyl (meth)acrylamide and their neutralized products with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid and aluminum compounds such as (meth)acrylic acid-2-aminoethyl. Examples include esters with canolamines and their neutralization products with acids such as hydrochloric acid and acetic acid; N,N-diallylmethylamine and its neutralization products with acids such as hydrochloric acid and acetic acid; allylamine and its neutralization products with acids such as hydrochloric acid and acetic acid; addition reaction products of unsaturated monomers having cyclic ether-containing groups with 2 to 8 carbon atoms, such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol, and amine compounds having 1 to 24 carbon atoms, and their neutralization products with acids such as hydrochloric acid and acetic acid.

[0036] The structural unit (a) derived from the above amino group-containing monomer (A) is, in particular, the structural unit derived from N,N-dimethylaminoethyl (meth)acrylate, as shown in formula (3) below;

[0037] [ka]

[0038] (In the formula, R 6 represents a hydrogen atom or a methyl group. However, an asterisk represents an atom included in another structural unit of the same or different type to which the structural unit represented by formula (3) is bonded. ) is preferred. The most preferred structural unit (a) is a structural unit derived from N,N-dimethylaminoethyl methacrylate.

[0039] (Structural unit (b) derived from monomer (B) having a polyalkylene glycol chain) The structural unit (b) derived from the monomer (B) having the polyalkylene glycol chain described above is characterized by containing a polyalkylene glycol chain in its structure. The structural unit (b) is preferably of the following formula (4);

[0040] [ka]

[0041] (In the formula, R 7 , R 8 , R 9 A represents an alkyl group having 1 to 5 carbon atoms, which may have a hydrogen atom or substituents, and may be identical or different. Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, as well as a carboxyl group, a sulfonic acid group, a phosphate group, an amino group, and salts thereof. 1 represents an alkylene group having 1 to 10 carbon atoms, which may have substituents. p is (A 1 This represents the average number of moles added (O), and is a number between 1 and 200. n represents a number between 0 and 4. m represents 0 or 1. This is a structural unit represented by ().

[0042] The above R 7 , R 8 , R 9Each of these is independently a hydrogen atom or a C1-C5 alkyl group which may have substituents, and the substituent is preferably at least one hydrophilic group selected from the group consisting of hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphate groups, amino groups and salts thereof.

[0043] The alkyl group is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. R 7 , R 8 , R 9 Each is preferably independently a hydrogen atom or a methyl group. More preferably R 7 , R 9 is a hydrogen atom, R 8 is a hydrogen atom or a methyl group. More preferably, R 7 , R 9 is a hydrogen atom, R 8 This is a methyl group.

[0044] Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, as well as a carboxyl group, sulfonic acid group, phosphoric acid group, amino group, and salts thereof. The hydrocarbon group is not particularly limited and includes chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aromatic groups, cycloalkyl groups, and cycloalkenyl groups. The hydrocarbon group may be branched, and in the case of branching, the number of carbon atoms in the hydrocarbon group refers to the total number of carbon atoms in the main chain and the branched chain.

[0045] Examples of the alkyl groups mentioned above include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, stearyl group, and eicosyl group.

[0046] Examples of the above alkenyl groups include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, and ecosenyl group. Examples of the above alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, decinyl group, dodecinyl group, octadecinyl group, and ecosenyl group.

[0047] Examples of the above aromatic groups include phenyl group, benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethylphenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl group, and the like.

[0048] Examples of the above-mentioned cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the above-mentioned cycloalkenyl groups include cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl groups.

[0049] The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. The hydrocarbon group has preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, even more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 5 carbon atoms. The above Z is preferably a hydrogen atom or a methyl group.

[0050] A 1 represents an alkylene group having 1 to 10 carbon atoms, which may have substituents. Preferably, the substituent is at least one hydrophilic group selected from the group consisting of a hydroxyl group and groups consisting of a carboxyl group, a sulfonic acid group, a phosphate group, a secondary or tertiary amino group, and salts thereof. (A1 O) p p A atoms present in the polyalkylene glycol represented by 1 The oxyalkylene groups of O may all be the same or they may be different. A above 1 The alkylene group represented by preferably has 2 to 10 carbon atoms, and more preferably has 2 to 4 carbon atoms.

[0051] A 1 Examples of oxyalkylene groups represented by O include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy2,3-butylene, oxystyrene, and oxyalkylenes having 2 to 10 carbon atoms. More preferably, alkylene oxides having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene are used, and even more preferably, oxyethylene and oxypropylene. 1 The oxyalkylene group represented by O is not limited to a group formed by the addition reaction of alkylene oxide. Furthermore, if the polyalkylene glycol is a compound of two or more alkylene oxide adducts, it may be in any form such as random addition, block addition, or alternating addition. It is preferable that the polyalkylene glycol contains an oxyethylene group as an essential component, more preferably 50 mol% or more being oxyethylene groups, and even more preferably 90 mol% or more being oxyethylene groups.

[0052] The above p is A 1 This represents the average number of moles of O added, and is a number between 1 and 200. Preferably it is between 2 and 150, more preferably 3 and 100, even more preferably 4 and 50, even more preferably 9 and 50, and especially preferably 15 and 30.

[0053] In the above example, n represents a number between 0 and 4, and m represents 0 or 1. n is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0. m is more preferably 1.

[0054] The structural unit (b) having the polyalkylene glycol chain described above is formed, for example, by radical polymerization of a monomer having a polyalkylene glycol chain. Specifically, preferred monomers having the polyalkylene glycol chain include, for example, polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; alkoxy polyalkylene glycol mono(meth)acrylates such as methoxy(poly)ethylene glycol mono(meth)acrylate and methoxy(poly)propylene glycol mono(meth)acrylate; and (poly)alkylene glycol monomers such as vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, and 2-methyl-3-buten-1-ol, to which 1 to 200 moles of alkylene oxide are added. Particularly preferred are (poly)ethylene glycol mono(meth)acrylate and methoxy(poly)ethylene glycol mono(meth)acrylate.

[0055] (Structural unit (c) derived from unsaturated carboxylic acid monomer (C)) The structural unit (c) derived from the above unsaturated carboxylic acid monomer (C) is not particularly limited as long as it is a structural unit derived from a monomer having a carboxyl group and an ethylenically unsaturated hydrocarbon group (unsaturated group), as shown in formula (5);

[0056] [ka]

[0057] (In the formula, R 10 R represents a hydrogen atom, a methyl group, or a -CH2COOH group. 11 , R 12 It is preferable that the structural unit is represented by (which may be the same or different, and represents a hydrogen atom, a methyl group, an ethyl group, a carboxyl group, or a -CH2COOH group).

[0058] A preferred form of the above formula (5) is R 10 However, it is a hydrogen atom or a methyl group, R 11 , R 12 These are either the same or different hydrogen atoms or carboxyl groups. A more preferred form is R 10 is a hydrogen atom or a methyl group, R 11 , R 12 This is a hydrogen atom.

[0059] Examples of unsaturated carboxylic acid monomers used as precursors for the polymerization reaction of structural units (c) derived from unsaturated carboxylic acid monomers (C) include (meth)acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, their anhydrides, or half-esters. Among these, (meth)acrylic acid, maleic acid, and their salts are preferred, and (meth)acrylic acid is more preferred.

[0060] (Structural unit (d) derived from aromatic group-containing monomer (D)) The structural unit (d) derived from the above aromatic group-containing monomer (D) is characterized by being derived from a monomer having an aryl group which may have substituents in its structure. Preferably, it is a (meth)acrylic acid ester having an aromatic group which may have substituents. The substituent is preferably a hydrophobic group, and more preferably a hydrocarbon group having 1 to 18 carbon atoms. The above aromatic group-containing monomer (D) preferably has an aryl group having 6 to 30 carbon atoms.

[0061] The structural unit (d) derived from the above aromatic group-containing monomer (D) is preferably formed by radical polymerization of a (meth)acrylic acid ester having an aromatic group which may have substituents. Examples of (meth)acrylic acid esters having an aromatic group which may have substituents in the structure include esters of (meth)acrylic acid with an aromatic alcohol having 6 to 30 carbon atoms which may have substituents. Examples of the above aromatic alcohols having 6 to 30 carbon atoms include phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butylmethylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethylnaphthalene, 1-hydroxyethylnaphthalene, 2-hydroxymethylnaphthalene, 2-hydroxyethylnaphthalene, and the like.

[0062] Examples of the above aromatic (meth)acrylates include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylphenyl (meth)acrylate, propylphenyl (meth)acrylate, butylphenyl (meth)acrylate, pentylphenyl (meth)acrylate, hexylphenyl (meth)acrylate, butylmethylphenyl (meth)acrylate, dimethylphenyl (meth)acrylate, diethylphenyl (meth)acrylate, dibutylphenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, and 4-methylphenyl (meth)acrylate. Examples include acrylate, 4-methylbenzyl(meth)acrylate, 1-methoxy-4-methylphenyl(meth)acrylate, 2-(2-methylphenyl)ethyl(meth)acrylate, 2-(3-methylphenyl)ethyl(meth)acrylate, 2-(4-methylphenyl)ethyl(meth)acrylate, 2-(4-propylphenyl)ethyl(meth)acrylate, biphenylmethyl(meth)acrylate, biphenylethyl(meth)acrylate, naphthyl(meth)acrylate, naphthylmethyl(meth)acrylate, naphthylethyl(meth)acrylate, etc. Among these, phenyl(meth)acrylate and benzyl(meth)acrylate are preferred.

[0063] (Other monomer-derived structural units (e)) The above amino group-containing copolymer may have structural units (a) derived from an amino group-containing monomer (A), structural units (b) derived from a monomer having a polyalkylene glycol chain, structural units (c) derived from an unsaturated carboxylic acid monomer (C), and structural units (d) derived from an aromatic group-containing monomer (D), as well as structural units (e) derived from other monomers (E).

[0064] The above-mentioned other monomers (E) are not particularly limited, but examples include (meth)acrylic acid esters that do not have aromatic groups; olefin monomers having 2 to 4 carbon atoms such as ethylene and propylene; vinyl halides such as vinyl chloride; methyl vinyl ethers; ethyl vinyl ethers; acrylonitrile, etc.

[0065] The above-mentioned (meth)acrylic acid esters that do not have aromatic groups can be any ester of an alcohol that does not have aromatic groups with (meth)acrylic acid, for example, 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, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate and other cycloalkyl (meth)acrylates, n-lauryl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, isobornyl methacrylate, etc.

[0066] (Method for producing amino group-containing copolymers) The method for producing the above amino group-containing copolymer is not particularly limited, but it can be produced by polymerizing monomer components. Specific examples and preferred examples of monomer components, as well as preferred proportions of each monomer, are as described above. The above amino group-containing copolymer is preferably produced by a manufacturing method that includes polymerizing a monomer component containing an unsaturated carboxylic acid monomer (C) and, if necessary, an aromatic group-containing monomer (D) to the above amino group-containing monomer (A) and a monomer (B) having a polyalkylene glycol chain.

[0067] Methods for initiating the polymerization of monomer components in the above polymerization process include, for example, adding a polymerization initiator, irradiating with UV light, applying heat, or irradiating with light in the presence of a photopolymerization initiator. In particular, the use of a polymerization initiator is preferred.

[0068] Examples of polymerization initiators include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), and 2,2'-azobis(2-methylpropionamidine) dihydrochloride; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, and cumene hydroperoxide; and redox initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, or persulfates and metal salts. Among these, persulfates and azo compounds are preferred, and more preferably azo compounds, because they tend to reduce the amount of residual monomers. These polymerization initiators may be used alone or in the form of a mixture of two or more.

[0069] The amount of polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 8% by mass or less, even more preferably 0.03% by mass or more and 7% by mass or less, and most preferably 0.04% by mass or more and 4% by mass or less, relative to the total amount of monomers constituting the structural units.

[0070] In the polymerization step described above, a chain transfer agent may be used as a molecular weight modifier of the polymer as needed. Examples of chain transfer agents include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid and their salts, as well as mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, secondary alcohols such as isopropanol and glycerin, phosphorous acid, hypophosphorous acid, hypophosphites and their hydrates, etc., and compounds that can generate bisulfite (salt) or bisulfite (salt) (bisulfite (salt), pyrosulfite (salt), dithionic acid (salt), sulfite (salt), etc.). Among these, compounds having a mercapto group are preferred, and more preferably mercapto group-containing compounds having a carboxyl group.

[0071] The amount of chain transfer agent used in the production of the above copolymer is preferably 0.1 mol% to 20 mol%, more preferably 0.2 mol% to 15 mol%, even more preferably 0.3 mol% to 10 mol%, and most preferably 0.5 mol% to 5 mol%, based on 100 mol% of the total amount of monomers constituting the structural unit.

[0072] The solvent used during polymerization can be selected as needed from those that can dissolve the monomer components, polymerization initiator, chain transfer agent, and the copolymer after production. There are no particular restrictions, but water, ethanol, C1-C8 alcohols such as 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol, glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, and glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferably used. In particular, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and mixtures of two or more of these may also be used.

[0073] In the polymerization process described above, the polymerization temperature is preferably 40°C or higher, and preferably 150°C or lower. More preferably 45°C or higher, and even more preferably 50°C or higher. Furthermore, it is more preferably 100°C or lower, and even more preferably 90°C or lower.

[0074] In the polymerization process described above, the method of adding the monomer components, polymerization initiator, and chain transfer agent to the reaction vessel is not particularly limited. Examples include adding the entire amount to the reaction vessel all at once at the beginning, adding the entire amount to the reaction vessel in installments or continuously, adding a portion to the reaction vessel initially and then adding the remainder in installments or continuously. Preferably, the solvent described later is charged at the beginning, and the monomer components, polymerization initiator, and chain transfer agent are added continuously.

[0075] Alternatively, the monomer components may be neutralized with organic acids such as acetic acid and propionic acid, or mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid, before polymerization.

[0076] The copolymer obtained by polymerization can be used as is as a detergent additive, such as an additive for liquid detergents, but it may also be neutralized with an alkaline substance if necessary. Suitable alkaline substances include inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines. The concentration of the copolymer can also be adjusted after the reaction is complete if necessary.

[0077] <Second component: Nonionic surfactant> The second component is a nonionic surfactant represented by the following formula (6-1). The soil-releasing properties can be further enhanced by using the second component in combination with the amino group-containing copolymer. R 13 -(CO) q1 O-(A 2 O) q2 -R 14 (6-1) (In the formula, R 13 R represents an aliphatic hydrocarbon group with 8 to 24 carbon atoms. 14 This represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2 O represents an oxyalkylene group having 2 to 4 carbon atoms, either identical or different. q1 represents the number of 0s or 1s. q2 is A 2 (This represents the average number of moles of oxyalkylene groups represented by O, and is a number between 7 and 50.)

[0078] The above R 13 The aliphatic hydrocarbon group in is not particularly limited, but examples include alkyl groups and alkenyl groups. The alkyl and alkenyl groups may be linear or branched.

[0079] The above R 13 From the viewpoint of further enhancing soil release properties, the number of carbon atoms in the aliphatic hydrocarbon group is preferably 9 or more, more preferably 10 or more, even more preferably 11 or more, and from the same viewpoint, preferably 20 or less, more preferably 18 or less, and even more preferably 16 or less.

[0080] Preferably, the above aliphatic hydrocarbon group is an alkyl group. Specifically, alkyl groups having 8 to 24 carbon atoms include n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group Syl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, ter t-Hexadecyl group, neohexadecyl group, n-heptadecyl group, isoheptadecyl group, sec-heptadecyl group, tert-heptadecyl group, neoheptadecyl group, n-octadecyl group, isooctadyl group, sec-octadecyl group, tert-octadecyl group, neoooctadyl group, n-nonadecyl group, isononadecyl group, sec-nonadecyl group, tert-nonadecyl group, neononadecyl group, n-icosyl group, isoicosyl group, sec-icosyl group, tert-icosyl group, Examples include eucosyl group, n-hexicosyl group, isohexicosyl group, sec-hexicosyl group, tert-hexicosyl group, neohexicosyl group, n-docosyl group, isodocosyl group, sec-docosyl group, tert-docosyl group, neodocosyl group, n-tricosyl group, isotrichosyl group, sec-tricosyl group, tert-tricosyl group, neotricosyl group, n-tetracosyl group, isotetracosyl group, sec-tetracosyl group, tert-tetracosyl group, neotetracosyl group, etc.Preferably n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, n-nonyl group, isononyl group, sec-nonyl group, tert-nonyl group, neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, These include n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert-pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, n-heptadecyl group, isoheptadecyl group, sec-heptadecyl group, tert-heptadecyl group, neoheptadecyl group, n-octadecyl group, isooctadyl group, sec-octadecyl group, tert-octadecyl group, neooctadecyl group, etc.

[0081] A above 2 O is an oxyalkylene group having 2 to 4 carbon atoms, either identical or different, and from the viewpoint of further enhancing soil release properties, the number of carbon atoms in the oxyalkylene group is preferably 2 or 3. These oxyalkylene groups are alkylene oxide adducts, and the alkylene oxides are preferably ethylene oxide, propylene oxide, and butylene oxide, and more preferably ethylene oxide and propylene oxide from the viewpoint of further enhancing soil release properties. Furthermore, if the oxyalkylene group is any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, etc., it may be in any form such as random addition, block addition, or alternating addition. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group in the polyalkylene glycol contains an oxyethylene group as an essential component, more preferably 50 mol% or more being oxyethylene groups, even more preferably 80 mol% or more being oxyethylene groups, and particularly preferably 90 mol% or more being oxyethylene groups.

[0082] The above q1 is preferably a number of 1. The above q2 is the average number of moles of oxyalkylene groups added, and from the viewpoint of further improving soil release properties, it is preferably 7.5 or more, more preferably 8.0 or more, even more preferably 8.5 or more, even more preferably 9.0 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 35 or less, even more preferably 30 or less, and even more preferably 25 or less. In one embodiment, q2 is preferably 7.5 to 40, more preferably 8.0 to 35, even more preferably 8.5 to 30, and even more preferably 9.0 to 25.

[0083] -(A in equation (6) above) 2 O) q2 -but, -[(EO)] q2’ (PO) q2’’ The form ]- is one of the preferred embodiments of the present invention, where " / " represents a block-type join or a random-type join. In the above formula, q2' is the average number of moles of EO added, and is a number between 4 and 50. From the viewpoint of further improving soil release properties, q2' is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and from the same viewpoint, preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. In one embodiment, q2' is preferably 5 to 40, more preferably 6 to 35, and even more preferably 7 to 30. The above q2'' is the average number of moles of PO added, and is a number between 0 and 20. From the viewpoint of further improving soil release properties, it is preferably 1 or more, more preferably 2 or more, and from the same viewpoint, it is preferably 15 or less, and more preferably 10 or less. In one embodiment, q2'' is preferably 1 to 15, and more preferably 2 to 10.

[0084] The second component, from the perspective of further enhancing soil release properties, is -(A in general formula (6-1) 2 O) q2 -but, -[(EO)] q2’ (PO) q2’’ Preferably, the second component is a nonionic surfactant (6-1') in which q2'' is a number between 1 and 20. When the second component, a nonionic surfactant of general formula (6-1), is taken as 100% by mass, the content of the nonionic surfactant (6-1') is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

[0085] Specifically, as the nonionic surfactant described above, compounds obtained by adding ethylene oxide (EO) and / or propylene oxide (PO) to an aliphatic alkyl alcohol having 8 to 24 carbon atoms in 7 to 50 moles are preferred. From the viewpoint of further enhancing soil release properties, the number of moles of EO and / or PO added is preferably 7.5 moles or more, more preferably 8.0 moles or more, even more preferably 8.5 moles or more, even more preferably 9.0 moles or more, and from the same viewpoint, preferably 40 moles or less, more preferably 35 moles or less, even more preferably 30 moles or less, and even more preferably 25 moles or less. The aliphatic alkyl alcohol may be linear or branched, and a form in which the aliphatic alkyl alcohol is a primary or secondary alcohol is one of the preferred embodiments of the present invention. Furthermore, a form in which only ethylene oxide is added to the above-mentioned aliphatic alkyl alcohol, and a form in which propylene oxide and ethylene oxide are block-added to the above-mentioned alkyl alcohol in that order, are among the preferred embodiments of the present invention. A form that includes both the above-mentioned aliphatic alkyl alcohol to which only ethylene oxide is added, and the above-mentioned alkyl alcohol to which propylene oxide and ethylene oxide are block-added in that order, is also one of the preferred embodiments of the present invention.

[0086] The above liquid detergent composition may contain other components besides the amino group-containing copolymer and nonionic surfactant. The other components are not particularly limited, but examples include the following components (1) to (15).

[0087] (1) Nonionic surfactants other than the second component From the viewpoint of further enhancing soil-releasing properties, the liquid laundry detergent composition of the present invention may contain a nonionic surfactant represented by the following formula (6-2) in addition to the second nonionic surfactant component. R 15 -O-(A 3 O) q3 -R 16 (6-2) (wherein, R 15 represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. R 16 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. A 3 O, which may be the same or different, represents an oxyalkylene group having 2 to 4 carbon atoms. q3 represents the average number of moles of addition of the oxyalkylene group represented by A 3 O, and is a number of 1 or more and less than 7)

[0088] The aliphatic hydrocarbon group in the above R 15 is not particularly limited, and examples thereof include an alkyl group and an alkenyl group. The alkyl group and the alkenyl group may be linear or branched.

[0089] The number of carbon atoms of the aliphatic hydrocarbon group in the above R 15 is preferably 9 or more, more preferably 10 or more, still more preferably 11 or more, and from the same viewpoint, is preferably 16 or less, and more preferably 14 or less, from the viewpoint of further enhancing the soil releasability.

[0090] The above A 3 O, which may be the same or different, is an oxyalkylene group having 2 to 3 carbon atoms. These oxyalkylene groups are alkylene oxide adducts, and specific examples of the alkylene oxide are preferably ethylene oxide and propylene oxide, and more preferably ethylene oxide from the viewpoint of further enhancing the soil releasability. Further, when the above oxyalkylene group is any two or more kinds of alkylene oxide adducts selected from ethylene oxide and propylene oxide, it may be in any form such as random addition, block addition, or alternating addition. In addition, in order to ensure the balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group in the polyalkylene glycol has an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, still more preferably 80 mol% or more is an oxyethylene group, and particularly preferably 90 mol% or more is an oxyethylene group.

[0091] Said q3 is the average number of moles of oxyalkylene groups added, and from the viewpoint of further enhancing the soil releasability, it is preferably 1.5 or more, more preferably 2 or more, and from the same viewpoint, it is preferably 6 or less, more preferably 5 or less.

[0092] -(A 3 O) q3 - in the above formula (6-2) being -〔(EO) q3’ / (PO) q3’’ 〕- is one of the preferred embodiments of the present invention. In the above formula, q3' is the average number of moles of EO added, and is a number of 1 or more and less than 7. From the viewpoint of further enhancing the soil releasability, q3' is preferably 1.2 or more, more preferably 1.5 or more, still more preferably 2 or more, even more preferably 2.5 or more, and from the same viewpoint, it is preferably 6.5 or less, more preferably 6 or less, still more preferably 5 or less, and even more preferably 4 or less.

[0093] Said q3'' is the average number of moles of PO added, and is a number of 0 or more and less than 6. From the viewpoint of further enhancing the soil releasability, it is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, and even more preferably 2 or less. q3'' may be 0.

[0094] Specifically, the nonionic surfactant is a compound obtained by adding 1 mole or more and less than 7 moles of ethylene oxide (EO) and / or propylene oxide (PO) to an aliphatic alkyl alcohol having 8 to 18 carbon atoms. From the viewpoint of further enhancing the soil releasability, the number of moles of EO and / or PO added is preferably 1.5 moles or more, more preferably 2.0 moles or more, and from the same viewpoint, it is preferably 6 moles or less, more preferably 5 moles or less. The above-mentioned aliphatic alkyl alcohol may be linear or branched, and a form in which the aliphatic alkyl alcohol is a primary or secondary alcohol is one of the preferred embodiments of the present invention.

[0095] The content ratio of the nonionic surfactant represented by general formula (6-2) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, per 100 parts by mass of the nonionic surfactant represented by general formula (6-1), from the viewpoint of further enhancing the imparting of soil-releasing properties to clothing, and from the same viewpoint, preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less.

[0096] The content of the nonionic surfactant represented by general formula (6-2) contained in the liquid laundry detergent composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and from the viewpoint of further enhancing the imparting of soil-releasing properties to clothing, and from the same viewpoint, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

[0097] (2) Anionic surfactants The above anionic surfactant is not particularly limited as long as it is a surfactant having a hydrophobic group and a hydrophilic group that dissociates into an anion, for example, the following formula (7); R 17 -(O) y -( A 4 O) q4 -W (7) (In the formula, R 17 This represents a hydrocarbon group with 8 to 24 carbon atoms, which may be the same or different. 4 O represents an oxyalkylene group with 2 to 18 carbon atoms, either identical or different. q4 is A 4 The O represents the average number of moles of oxyalkylene groups added, and is an integer from 0 to 50. y is 0 or 1. W represents a hydrophilic group that dissociates into an anion. The structure represented by ( is preferable.) is preferred.

[0098] A above 4 Specific examples and preferred forms of O are A 2 It is the same as O.

[0099] R 17 The hydrocarbon group in is not particularly limited, but examples include alkyl groups, alkenyl groups, and aryl groups. Alkyl and alkenyl groups may be linear or branched. Specific examples of alkyl, alkenyl, and aryl groups are as described above.

[0100] R 17 The number of carbon atoms in the hydrocarbon group is 8 to 24, preferably 10 to 20, more preferably 12 to 18, and even more preferably 12 to 16.

[0101] The hydrophilic group that dissociates into an anion in W is not particularly limited, but examples include sulfate(salt) groups, sulfonic acid(salt) groups, carboxylic acid(salt) groups, and phosphoric acid(salt) groups. Preferably, it is a sulfate base, a sulfonic acid base, or a carboxylic acid base.

[0102] Examples of anionic surfactants include alkyl or alkenyl sulfate salts; polyoxyalkylene alkyl or alkenyl ether sulfate salts having an oxyalkylene group; anionic surfactants having a sulfonic acid base; fatty acids or salts thereof. A form of the present invention that includes a fatty acid or a salt thereof as the anionic surfactant is one of the preferred embodiments. This makes it possible to further improve soil release properties compared to cases that include anionic surfactants other than fatty acids or salts thereof.

[0103] More specifically, examples of the alkyl or alkenyl sulfate ester salts mentioned above include alkyl sulfate ester salts in which the alkyl group has 10 to 18 carbon atoms, and alkenyl sulfate ester salts in which the alkenyl group has 10 to 18 carbon atoms.

[0104] More specifically, examples of polyoxyalkylene alkyl or alkenyl ether sulfate salts having the above-mentioned oxyalkylene group include polyoxyalkylene alkyl ether sulfate salts in which the alkyl group has 10 to 18 carbon atoms and the average number of added moles of alkylene oxide is 1 to 5; and polyoxyalkylene alkenyl ether sulfate salts in which the alkenyl group has 10 to 18 carbon atoms and the average number of added moles of alkylene oxide is 1 to 5. Among these, polyoxyethylene alkyl ether sulfate salts in which the average number of added moles of ethylene oxide is 1 to 3 are preferred, polyoxyethylene alkyl ether sulfate salts in which the alkyl group has 12 to 14 carbon atoms and the average number of added moles of ethylene oxide is 1 to 3 are more preferred, and sodium salts of these are even more preferred.

[0105] More specifically, an anionic surfactant having the above-mentioned sulfonic acid base can be one or more anionic surfactants selected from alkylbenzene sulfonates with 10 to 18 carbon atoms in the alkyl group, alkenylbenzene sulfonates with 10 to 18 carbon atoms in the alkenyl group, alkane sulfonates with 10 to 18 carbon atoms in the alkyl group, α-olefin sulfonates with 10 to 18 carbon atoms in the α-olefin portion, α-sulfo fatty acid salts with 10 to 18 carbon atoms in the fatty acid portion, α-sulfo fatty acid lower alkyl ester salts with 10 to 18 carbon atoms in the fatty acid portion and 1 to 5 carbon atoms in the ester portion, and internal olefin sulfonates with 12 to 16 carbon atoms. Among these, polyoxyethylene alkyl ether sulfate ester salts with 10 to 18 carbon atoms in the alkyl group, or internal olefin sulfonate potassium salts with 10 to 18 carbon atoms in the alkyl group, or polyoxyalkylene alkyl ether sulfate monoethanolamine salts with 10 to 18 carbon atoms in the alkyl group are preferred.

[0106] The content of an anionic surfactant in the liquid laundry detergent composition, in which W in the general formula (7) is a sulfate (salt) group, a sulfonic acid (salt) group, or a phosphoric acid (salt) group, is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and preferably 0% by mass or more, based on 100% by mass of the liquid laundry detergent composition, from the viewpoint of further enhancing soil release properties. The content of an anionic surfactant in which W in the general formula (7) is a sulfate (salt) group, a sulfonic acid (salt) group, or a phosphoric acid (salt) group is calculated as a value obtained by converting the counterion to the Na salt type.

[0107] Examples of the above-mentioned fatty acids or salts thereof include fatty acids or salts thereof having 10 to 20 carbon atoms. The number of carbon atoms in the above-mentioned fatty acids or salts thereof is preferably 12 to 18, and more preferably 14 to 18.

[0108] (3) Fatty acids or salts thereof with 10 to 22 carbon atoms The liquid laundry detergent composition of the present invention preferably contains a surfactant as an ingredient that does not inhibit the imparting of soil-releasing properties to the garment, even when the garment is washed under strong mechanical force. It is preferable to contain a fatty acid or a salt thereof having 10 to 22 carbon atoms. From the above viewpoint, it is preferable that the number of carbon atoms is 11 or more, more preferably 12 or more, and preferably 20 or less, and more preferably 18 or less. From the above viewpoint, it is preferable that the fatty acid is a mixture of fatty acids or salts thereof having multiple carbon atoms, and it is preferable that the fatty acid or salt thereof having 10 to 22 carbon atoms contains two or more fatty acids selected from fatty acids with 12 carbon atoms, fatty acids with 14 carbon atoms, and fatty acids with 16 carbon atoms. For 100% by mass of fatty acid with 10 to 22 carbon atoms, it is preferable that two or more fatty acids selected from fatty acids with 12 carbon atoms, fatty acids with 14 carbon atoms, and fatty acids with 16 carbon atoms make up 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and preferably 100% by mass or less, and more preferably 90% by mass or less. Preferably, the salt is one or more salts selected from alkali metal salts, alkali metal salts, and alkanolamine salts having 2 to 6 carbon atoms. Examples of alkali metal salts include sodium salts and potassium salts, examples of alkali metal salts include magnesium salts, and examples of alkanolamine salts having 2 to 6 carbon atoms include monoethanolamine salts, diethanolamine salts, methyldiethanolamine salts, and triethanolamine salts. In this invention, when dealing with the mass of fatty acids or salts thereof having 10 to 22 carbon atoms, the mass used shall be the mass converted to the form with a hydrogen counterion, i.e., the acid form.

[0109] The content of fatty acids or salts thereof having 10 to 22 carbon atoms in the liquid laundry detergent composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.7% by mass or more, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the liquid laundry detergent composition. The content of fatty acids or salts thereof having 10 to 22 carbon atoms in the liquid laundry detergent composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the second component, a nonionic surfactant represented by general formula (6-1).

[0110] (4) Cationic surfactants Cationic surfactants are not particularly limited as long as they have a hydrophobic group and a hydrophilic group that dissociates into a cation, but examples include quaternary ammonium salt type cationic surfactants. Examples of quaternary ammonium salt-type cationic surfactants include quaternary ammonium salts in which, among the four groups bonded to the nitrogen atom, one or two are hydrocarbon groups having 8 to 24 carbon atoms, and the remaining group is a hydrocarbon group having 1 to 3 carbon atoms. Examples of cationic surfactants include those shown in formula (8) below;

[0111] [ka]

[0112] (In the formula, R 18 R is a chain-type hydrocarbon group having 8 to 24 carbon atoms. 19 R is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. 20 and R 21 X is the same or different alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and - A compound represented by (where is an alkyl sulfate ion or halide ion having 1 to 3 carbon atoms) is an example.

[0113] In the above equation (8), R 18 The number of carbon atoms in the chain-like hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. 19 R is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms or less, or a hydroxyalkyl group having 1 to 3 carbon atoms or less. 19 The number of carbon atoms in the chain-like hydrocarbon group is preferably 9 to 18, more preferably 10 to 14, and even more preferably 10 to 12. R 19 The chain-like hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. 20 , R 21 These are, either identical or different, a methyl group, an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms. 18 , R 19 Specific examples of the chain-like hydrocarbon group are the octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, and hexadecyl group, with the nonyl group and decyl group being preferred, and the decyl group being even more preferred. Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include the hydroxymethyl group, hydroxyethyl group, and hydroxypropyl group. X - is CH3SO4 -CH3CH2SO4 - , or halide ions.

[0114] More specific compounds represented by formula (8) above include one or more compounds selected from N-ethyl-N,N-dimethyltetradecylammonium salt, trimethylhexadecylammonium salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dinonyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, N,N-dioctyl-N-ethyl-N-methylammonium salt, N,N-dinonyl-N-ethyl-N-methylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt, and mono-long-chain ammonium salts and di-long-chain ammonium salts can also be used in combination. Among these, N,N-didecyl-N-ethyl-N-methylammonium salt is preferred. The counterions that form these salts are CH3SO4 - CH3CH2SO4 - or halide ions such as chlorine ions.

[0115] The content ratio of the cationic surfactant is not particularly limited, but it can be contained in a ratio of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on 100% by mass of the composition. When the nonionic surfactant represented by general formula (6-1), which is the second component contained in the composition, is taken as 100% by mass, the content of the cationic surfactant can be preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, from the viewpoint of further enhancing soil release properties.

[0116] (5) Alkaline agents The liquid detergent composition of the present invention preferably contains an alkaline agent from the viewpoint of improving cleaning power. Examples of the alkaline agent include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which one to three of the groups bonded to the nitrogen atom are alkanol groups having 2 to 4 carbon atoms, and the remaining groups are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms. Of these, the alkanol groups are preferably hydroxyalkyl groups, and more preferably hydroxyethyl groups. Other than the alkanol groups, hydrogen atoms or methyl groups are preferred, and hydrogen atoms are particularly preferred. Examples of alkanolamines include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. In the present invention, as component (5), an alkanolamine selected from monoethanolamine and triethanolamine is preferred, and monoethanolamine is more preferred. Furthermore, the alkaline agent, which is component (5) above, can also be used to adjust the pH of the liquid detergent composition of the present invention to a predetermined value. In the liquid detergent composition of the present invention, component (5) may be added in an amount such that the pH described later is achieved. The amount of component (5) added is preferably 0.01 to 10% by mass, and more preferably 0.5 to 8% by mass, based on 100% by mass of the composition. In this invention, the amount of the alkaline agent of component (5), especially the alkanolamine, includes the amount added to the composition due to other components, such as the counterions of anionic surfactants.

[0117] (6) Chelating agents Specific examples of the chelating agents mentioned above include, for example, aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), alkali metals thereof, or lower amine salts thereof. (6) The content of the chelating agent in the component, when considered as an acid type, is 0.1% by mass or more and 5% by mass or less, preferably 0.1% by mass or more and 4% by mass or less, and more preferably 0.1% by mass or more and 3% by mass or less, based on 100% by mass of the composition.

[0118] (7) Anti-redeposition agents and / or polymer-based dispersants Examples of anti-redeposition agents and / or polymer-based dispersants include polyacrylic acid, polymaleic acid, and carboxymethylcellulose. The content of the anti-redeposition agent and / or polymer-based dispersant is preferably 0.01% to 10% by mass per 100% by mass of the composition.

[0119] (8) Bleach Examples of bleaching agents include hydrogen peroxide, sodium percarbonate, and sodium perborate. The bleaching agent content is preferably 0.01% to 10% by mass, based on 100% by mass of the composition.

[0120] (9) Bleach activator Examples of bleaching activators include tetraacetylethylenediamine and bleaching activators represented by general formulas (I-2) to (I-7) of Japanese Patent Publication No. 6-316700. The bleaching activator content is preferably 0.01% to 10% by mass per 100% by mass of the composition.

[0121] (10) Enzymes The liquid detergent composition of the present invention preferably contains an enzyme, from the viewpoint of its cleaning power against various types of stains attached to clothing. The enzymes themselves are not particularly limited as long as they break down dirt components, but examples include carbohydrate-digesting enzymes, protein-digesting enzymes, and fat-digesting enzymes. Examples of carbohydrate-digesting enzymes include amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase, and cellulase. From the viewpoint of improving washing performance and maintaining washing performance after storage, amylase is preferred as the carbohydrate-degrading enzyme, and α-amylase is more preferred. Specifically, commercially available enzymes that can be used include the brand name Rapidase (manufactured by Gist Brokers), the brand names Termamyl, Duramyl, Stainzyme, and Amplify Prime 100L (manufactured by Novozyme Japan Co., Ltd.), the brand names Plaster ST and Plaster OxAm (manufactured by Jeunesse Cor International), and the brand name Preferred S210 (manufactured by DuPont Co., Ltd.).

[0122] The above-mentioned proteolytic enzymes are not particularly limited, but examples include proteases such as pepsin, trypsin, and peptidases. Examples of the above-mentioned fat-degrading enzymes include lipase. The enzyme content is preferably 0.001% to 2% by mass per 100% by mass of the composition. The enzyme is preferably a protease, as it provides superior cleaning performance against food stains such as meat sauce on clothing that has accumulated sebum. From the viewpoint of further enhancing soil release properties, the composition is preferably composed of both protease and amylase.

[0123] (11) Fluorescent dyes Examples of fluorescent dyes include commercially available fluorescent dyes such as Chinopearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.). The fluorescent dye content is preferably 0.001% by mass or more and 1% by mass or less per 100% by mass of the composition.

[0124] (12) Antioxidants Examples of antioxidants include butylhydroxytoluene, distyrenated cresol, sodium sulfite, and sodium bisulfite. The antioxidant content is preferably 0.01% to 2% by mass, based on 100% by mass of the composition.

[0125] (13) It is preferable to contain appropriate amounts of pigments, fragrances, antimicrobial preservatives such as dichrosan, and antifoaming agents such as silicone.

[0126] (14) Organic solvents having a hydroxyl group As the organic solvent having a hydroxyl group, one or more compounds selected from the following components (14-1) to (14-6) are used. (14-1) Components: Monohydric alcohol having an aliphatic hydrocarbon group with 2 to 6 carbon atoms. (14-1) Examples of components include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0127] (14-2) Components: Divalent to Hexavalent alcohols with 2 to 6 carbon atoms. (14-2) Examples of components include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-methyl-2,4-pentanediol is also known as hexylene glycol.

[0128] (14-3) Components: Polyalkylene glycol containing alkylene glycol units with 2 to 4 carbon atoms. (14-3) Examples of components include polyalkylene glycol selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol with a weight-average molecular weight of 400 to 4000, and polypropylene glycol with a weight-average molecular weight of 400 to 4000.

[0129] (14-4) Components: Monoalkyl ether of (mono or poly)alkylene glycol having alkylene glycol units with 2 to 4 carbon atoms and alkyl groups with 1 to 4 carbon atoms. (14-4) Examples of components include compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0130] (14-5) Components: Alkyl glyceryl ether having an alkyl group with 1 to 8 carbon atoms. (14-5) Examples of components include alkyl glyceryl ethers selected from 1-methylglyceryl ether, 2-methylglyceryl ether, 1,3-dimethylglyceryl ether, 1-ethylglyceryl ether, 1,3-diethylglyceryl ether, triethylglyceryl ether, 1-pentylglyceryl ether, 2-pentylglyceryl ether, 1-octylglyceryl ether, and 2-ethylhexylglyceryl ether.

[0131] (14-6) Components: Aromatic alkyl ether of (mono or poly)alkylene glycol having alkylene glycol units with 2 or 3 carbon atoms. (14-6) Examples of components include 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether with an average molecular weight of approximately 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

[0132] In the above components (14-4) and (14-6), the term "(mono or poly)alkylene glycol" means monoalkylene glycol or polyalkylene glycol. Furthermore, "polyalkylene glycol" means containing two to nine alkylene glycol units.

[0133] (14) Component is preferably one or more compounds selected from components (14-1), (14-2), (14-4), and (14-6) in order to further improve storage stability at low temperatures. More specifically, the liquid detergent composition of the present invention preferably contains one or more compounds selected from ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, diethylene glycol monophenyl ether, and triethylene glycol monophenyl ether. The liquid detergent composition of the present invention preferably contains one or more organic solvents selected from ethanol, propylene glycol, diethylene glycol monobutyl ether, 2-phenoxyethanol, and polyethylene glycol phenyl ether as organic solvents having hydroxyl groups. (14) The content of the component is preferably 1 to 40% by mass, more preferably 4 to 20% by mass, and even more preferably 5 to 10% by mass, based on 100% by mass of the composition.

[0134] (15) Hydrotrope A hydrotrope agent may be added to the liquid detergent composition for stability. The hydrotrope agent of the present invention is an organic compound having an anionic group, and further includes alkylbenzene carboxylic acid or alkylbenzene sulfonic acid or salts thereof, which contain one or two alkyl groups selected from methyl, ethyl, or propyl groups and have one sulfonic acid group or carboxylic acid group, as well as benzoic acid or salts thereof. More specifically, these are p-toluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, and benzoic acid, and alkali metal salts are preferred. In the present invention, p-toluenesulfonic acid or its alkali metal salt is preferred and may be added as an acid and neutralized with an alkaline agent in the composition. The liquid detergent composition of the present invention may contain the hydrotrope agent in an amount equivalent to an acidic compound, preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and even more preferably 1 to 3% by mass.

[0135] The liquid detergent composition of the present invention contains water. The water can be deionized water, distilled water, tap water, or water containing 1 mg / kg to 5 mg / kg of sodium hypochlorite. From the viewpoint of physical properties such as viscosity of the composition and workability when washing clothes, the water content of the liquid detergent composition of the present invention is preferably 50 to 90% by mass or more, more preferably 60 to 85% by mass, based on 100% by mass of the composition.

[0136] The liquid detergent composition of the present invention has a pH at 25°C that is preferably 6.5 to 11, more preferably 7 to 10.5, and even more preferably 8 to 10, from the viewpoint of improving cleaning performance and composition stability. The pH is the value measured at 25°C using a glass electrode. Specifically, it was measured by the following method. (Method for measuring pH) The pH electrode (model 6367) of the Horiba D-52 pH meter is calibrated beforehand using phthalate buffer (pH 4.01), phosphate standard solution (pH 6.84), and borate standard solution (pH 9.18), and then thoroughly rinsed with deionized water. The pH electrode, which has been calibrated and rinsed as described above, is placed in a liquid cleaning agent composition adjusted to a temperature of 25°C, and measurements are taken using the AUTO HOLD mode of the pH meter until the measured value becomes constant.

[0137] [Washing method, pretreatment method] The liquid detergent composition of the present invention is suitably used for washing clothing, towels, bedding, and textile products for bedding (sheets, pillowcases, etc.). Other washable textile products can also be treated as clothing and washed according to the present invention. A cleaning method comprising the step of bringing the liquid cleaning agent composition of the present invention into contact with an object is also one of the present inventions. A pretreatment method comprising the step of bringing the liquid detergent composition of the present invention into contact with an object is also one of the present inventions.

[0138] The above-described cleaning method and the contact step in the cleaning method are not particularly limited as long as the liquid cleaning agent composition of the present invention is brought into contact with the object. However, it is preferable to bring a cleaning solution containing the liquid cleaning agent composition and water into contact with the object, and then apply an external force to the object to which the liquid cleaning agent composition has been brought into contact to perform the cleaning.

[0139] In the cleaning method and pretreatment method of the present invention, the value of the bath ratio, which is expressed as the ratio of the mass (kg) of the object to the amount (liters) of the cleaning solution, i.e., the value of the amount (liters) of the cleaning solution / the mass (kg) of the object (hereinafter, this ratio may also be referred to as the bath ratio), is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, even more preferably 5 or more, and preferably 400 or less, and more preferably 300 or less, from the viewpoint of ensuring cleaning performance.

[0140] In the garment washing method and pretreatment method of the present invention, the time for washing or pretreatment of the object is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 3 minutes or more, and preferably 12 hours or less, more preferably 8 hours or less, even more preferably 6 hours or less, even more preferably 3 hours or less, and even more preferably 1 hour or less, from the viewpoint of ensuring washability.

[0141] In the cleaning and pretreatment methods of the present invention, after cleaning or pretreatment an object, the object is rinsed with water. In rinsing, the rinsing water can be used on the object in the same ratio as the bath ratio of the cleaning solution described above. The rinsing time can also be within the same range as the cleaning time described above.

[0142] The cleaning method of the present invention is also suitable for rotary cleaning methods. A rotary cleaning method refers to a cleaning method in which an object that is not fixed to a rotating machine rotates around a rotating shaft together with the cleaning solution. A rotary cleaning method can be carried out using a rotary washing machine. Specifically, rotary washing machines include drum-type washing machines, pulsator-type washing machines, and agitator-type washing machines. Commercially available rotary washing machines for household use can be used. Drum-type washing machines have become rapidly popular in recent years because they can reduce the amount of water used in one wash cycle. Drum-type washing machines, in particular, can reduce the amount of water used during washing. [Examples]

[0143] 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 "mass%".

[0144] <Ingredients> [Component 1] • Synthesis example (1-1): Amino group-containing copolymer 1 In a glass separable flask equipped with a thermometer, reflux condenser, and stirrer, 47.9 g of ethanol(i) was charged, and under stirring, nitrogen was flowed at 200 ml / min for 10 minutes, after which the temperature was raised to 70°C. After reducing the nitrogen flow to 50 ml / min, under stirring, in a polymerization reaction system maintained at a constant temperature of 70°C, a monomer solution consisting of 49.7 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereafter referred to as PGM25E), 4.3 g of methacrylic acid (hereafter referred to as MAA), 60.8 g of dimethylaminoethyl methacrylate (hereafter referred to as DAM), 39.6 g of ethanol(ii), 22.0 g of acetic acid, and 20.3 g of benzyl methacrylate (hereafter referred to as BzMA); and an initiator aqueous solution consisting of 41.7 g of a 6% ethanol solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (hereafter referred to as V-65) were added dropwise from separate dropping nozzles. Regarding the dropwise addition time, the monomer solution and the initiator aqueous solution were added simultaneously. The monomer solution was added for 180 minutes, and the initiator aqueous solution for 240 minutes. After all addition was complete, the reaction solution was maintained at 70°C for another 60 minutes to mature and complete the polymerization, yielding amino group-containing copolymer 1.

[0145] • Synthesis example (1-2): Amino group-containing copolymer 2 In synthesis example (1-1), the following steps were taken: ethanol(i) was changed to 52.5 g, PGM25E to 59.7 g, MAA to 5.1 g, DAM to 50.0 g, ethanol(ii) to 38.7 g, acetic acid to 18.1 g, BzMA to 20.3 g, and the initiator aqueous solution to 39.2 g of 6% V-65 ethanol solution. The synthesis was carried out in the same manner as in synthesis example (1-1) to obtain amino group-containing copolymer 2.

[0146] • Synthesis example (1-3): Amino group-containing copolymer 3 In synthesis example (1-1), the mixture was prepared in the same manner as in synthesis example (1-1), except that ethanol(i) was changed to 50.3 g, PGM25E to 68.4 g, MAA to 5.8 g, DAM to 40.5 g, ethanol(ii) to 37.9 g, acetic acid to 14.7 g, BzMA to 20.3 g, and the initiator aqueous solution to 43.2 g of 6% V-65 ethanol solution. Amino group-containing copolymer 3 was obtained.

[0147] • Synthesis example (1-4): Amino group-containing copolymer 4 In synthesis example (1-1), the mixture was synthesized in the same manner as in synthesis example (1-1), except that ethanol(i) was changed to 50.7 g, PGM25E to 56.0 g, MAA to 4.8 g, DAM to 60.8 g, ethanol(ii) to 39.7 g, acetic acid to 22.0 g, BzMA to 13.5 g, and the initiator aqueous solution to 37.1 g of 7% V-65 ethanol solution. Amino group-containing copolymer 4 was obtained.

[0148] • Synthesis example (1-5): Amino group-containing copolymer 5 In synthesis example (1-1), the synthesis was carried out in the same manner as in synthesis example (1-1), except that ethanol(i) was changed to 51.6 g, PGM25E to 65.9 g, MAA to 5.6 g, DAM to 50.0 g, ethanol(ii) to 38.8 g, acetic acid to 18.1 g, BzMA to 13.5 g, and the initiator aqueous solution to 38.3 g of 7% V-65 ethanol solution, to obtain amino group-containing copolymer 5.

[0149] • Synthesis example (1-6): Amino group-containing copolymer 6 In synthesis example (1-1), the synthesis was carried out in the same manner as in synthesis example (1-1), except that ethanol(i) was changed to 47.9 g, PGM25E to 74.6 g, MAA to 6.4 g, DAM to 40.5 g, ethanol(ii) to 38.0 g, acetic acid to 14.7 g, BzMA to 13.5 g, and the initiator aqueous solution to 43.8 g of 6% V-65 ethanol solution, to obtain amino group-containing copolymer 6.

[0150] [Comparative compound of component 1] • Synthesis example (1'-1): Amino group-containing copolymer 7 In synthesis example (1-1), the amount of ethanol (i) was changed to 53.1 g, PGM25E to 55.7 g, MAA to 4.8 g, DAM to 27.0 g, ethanol (ii) to 36.6 g, acetic acid to 9.8 g, BzMA to 47.3 g, and the initiator aqueous solution to 50.4 g of 4% V-65 ethanol solution. The synthesis was carried out in the same manner as in synthesis example (1-1) to obtain amino group-containing copolymer 7.

[0151] Table 1 shows the monomer composition and weight-average molecular weight of amino group-containing copolymers 1 to 7 obtained in the above synthesis examples (1-1) to (1-6) and (1'-1).

[0152] [Table 1]

[0153] [Second component] (2-1): Nonionic surfactant 1 (in the above general formula (6-1), R 13 It is a mixed alkyl group containing a lauryl group and a myristyl group in a mass ratio of 70 / 30, and q1 is 0, -(A 2 O) q2 -but, -[(EO)] q2’ (PO) q2’’ ]-, where q2' is the number 17, and q2'' is the number 4, R 13 4 moles of propyleneoxy groups are added to O, followed by 17 moles of ethyleneoxy groups, R 14 (This is a hydrogen atom.)

[0154] • (2-2): Nonionic surfactant 2 (in the above general formula (6-1), R 13 It is a mixed alkyl group containing a lauryl group and a myristyl group in a mass ratio of 70 / 30, and q1 is 0, A 2 O is an oxyethylene group, q2 is the number 10, and R 14 (This is a hydrogen atom.)

[0155] (2-3): Nonionic surfactant 3 (in the above general formula (6-1), R 13 It is a mixed alkyl group containing a lauryl group and a myristyl group in a mass ratio of 70 / 30, and q1 is 0, -(A 2 O) q2 -but, -[(EO)] q2’ (PO) q2’’ ]-, where q2' is the number 18, and q2'' is the number 2, R 13 Nine moles of ethyleneoxy groups are added to O, then two moles of propyleneoxy groups are added, and then nine moles of ethyleneoxy groups are added to R14 (A compound containing a hydrogen atom.)

[0156] [Any surfactant] [Nonionic surfactants other than the second component] (2-4): Nonionic surfactant 4 (in the above general formula (6-2), R 15 A is a linear secondary alkyl group having 9 to 16 carbon atoms, 3 O is an oxyethylene oxy group, q3 is the number 3, and R 16 (This is a hydrogen atom.)

[0157] • Cationic surfactant 1: In general formula (8), R 18 The myristyl group is R 19 , R 20 R is a methyl group, 21 The compound is an ethyl group, and X- is an ethyl sulfate ion. • Cationic surfactant 2: In general formula (8), R 18 , R 19 is a decyl group, and R 20 R is a methyl group, 21 is an ethyl group, X - A compound in which the ethyl sulfate ion is present.

[0158] • Fatty Acid 1: Mixed fatty acids (compounds in which the mixed ratio of decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid / oleic acid / linoleic acid is 1 / 57 / 22 / 10 / 3 / 6 / 1 by mass).

[0159] [Other ingredients] • Protease: Manufactured by Kao Corporation • Amylase: Manufactured by Novozyme Calcium chloride Butylcarbitol • Citric acid • Monoethanolamine • Ion-exchanged water

[0160] <Preparation of test fabric> (1) Test cloth The following synthetic fabrics or garments containing synthetic fibers were used as SR test cloths: (i) Polyester fabric (Polyester faille, manufactured by Dyeing Test Materials Co., Ltd., 100% polyester), (ii) Dress shirt (sun-ml-sbu-1788, plain white, manufactured by Atelier 365 Co., Ltd., 100% polyester), (iii) Innerwear (TV158SA3202C, SilkyFACT Short-Sleeve Crew Neck Men's Topvalu PEACE FIT, white, manufactured by AEON Co., Ltd., 90% polyester, 10% polyurethane), (iv) Innerwear (451899 or 441620, Heattech Crew Neck T (9 / 10 sleeve), 00WHITE, manufactured by Uniqlo Co., Ltd. and Toray Industries, Inc., 39% polyester, 32% acrylic, 21% rayon, 8% polyurethane)

[0161] (2) Preparation of the test cloth The garment described in (1) was washed five times cumulatively using the standard course (48L water, 12 minutes wash, 2 rinses, 3 minutes spin) in a fully automatic washing machine (NA-F70PB1, Panasonic Corporation). 4.8g of Emulgen 108 (Kao Corporation) was added during the wash cycle. After that, it was washed once with water only (48L water, 12 minutes wash, 2 rinses, 3 minutes spin), and then rinsed again in a twin-tub washing machine (PS-H45L, Hitachi Global Life Solutions, Ltd.) with running water until all the foam was gone, and then air-dried at room temperature. After that, it was cut into 6cm x 6cm pieces and used as test fabric.

[0162] (3) Pretreatment of the test cloth In a screw-top tube (No. 8, 40mm x 120mm, manufactured by Maruemu Co., Ltd.), 50 mL of tap water (20°C) and 0.05 mL of each detergent composition shown in Tables 2, 3, and 4 were mixed to obtain a washing solution. Then, six synthetic fiber test cloths (2.5 g) pre-treated using the method described above were placed in the tube, and the cloths were shaken horizontally back and forth at 300 rpm for 10 minutes using a shaker (SA300, manufactured by Yamato Scientific Co., Ltd.) to perform the washing solution treatment. After treatment, the cloths were dewatered for 1 minute using the aforementioned two-tub washing machine. Next, 50 mL of tap water and the dewatered synthetic fiber test cloths were placed in the screw-top tube, and the cloths were shaken horizontally back and forth for 3 minutes using the shaker to perform a rinsing treatment. Then, the same dewatering treatment was performed for 1 minute using the two-tub washing machine. After performing this treatment a total of five times, the cloths were allowed to air dry at room temperature.

[0163] (4) Preparation of model sebum-stained cloth A 0.06 mL artificial contamination solution of model sebum, prepared by mixing 0.02% Sudan III (manufactured by Tokyo Chemical Industry Co., Ltd.) as a pigment with model sebum having the composition described below, was applied in a 4 cm diameter circle to the center of a synthetic fiber test cloth treated by the method described in (3) above, and left to stand for 1 hour in a forced-air constant-temperature dryer (DRM420DA, manufactured by ADVANTEC Corporation) at 60°C. After that, it was dried for 24 hours at 20°C and 70% RH. *Composition of model sebum: Lauric acid 0.54% by mass, myristic acid 1.78% by mass, pentadecanoic acid 0.91% by mass, palmitic acid 3.53% by mass, heptadecanoic acid 0.30% by mass, linoleic acid 1.40% by mass, oleic acid 19.74% by mass, triolein 46.00% by mass, squalene 13.80% by mass, cholesterol 2.90% by mass, sterol ester 3.00% by mass, n-hexadecyl palmitate 6.10% by mass (total 100% by mass)

[0164] (5) Washing test The cleaning operation was performed using a Turgotometer (MS-8212, manufactured by Ueshima Seisakusho Co., Ltd.). In the stainless steel beaker attached to the Turgotometer, 0.6 mL of each cleaning agent composition shown in Tables 2-4 was mixed with 599.4 mL of tap water to obtain a cleaning solution. Then, five model sebum-stained cloths obtained in (4) above were placed in the solution and washed at 85 rpm for 10 minutes. After washing, the cloths were dewatered for 1 minute using the aforementioned twin-tub washing machine. Next, 600 mL of the aforementioned tap water and the dewatered synthetic fiber test cloths were placed in the stainless steel beaker and rinsed in the Turgotometer for 3 minutes. After rinsing, the cloths were dewatered for 1 minute using the twin-tub washing machine and then air-dried at room temperature.

[0165] (6) Evaluation of cleaning efficiency The cleaning rate of the model sebum-stained cloth obtained in the cleaning test described in (5) above was calculated using the following method and is shown in Tables 2 to 4. The reflectance at 460 nm of the raw fabric before contamination and before and after washing was measured using a colorimeter (SE-2000, manufactured by Nippon Denshoku Co., Ltd.), and the washing rate (%) was calculated using the following formula. The colorimeter was calibrated with a standard reflector (white, X=94.03, Y=95.96, Z=113.16). The average cleaning rate of five test cloths was calculated and used as the cleaning rate of the detergent composition. A higher cleaning rate indicates superior cleaning performance. Cleaning rate (%) = 100 × [(Reflectance after cleaning - Reflectance before cleaning) / (Reflectance of the original fabric - Reflectance before cleaning)]

[0166] [Table 2]

[0167] [Table 3]

[0168] [Table 4]

Claims

1. A liquid laundry detergent composition containing the following first and second components. Component 1: The following formula (1) or (1'); 【Chemistry 1】 (R １ , R ２ , R ３ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. ４ , R ５ X represents a hydrogen atom or an organic group having 1 to 12 carbon atoms, either identical or different. Y represents a direct bond or a divalent linking group. － represents an anion. However, an asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by formula (1) or (1') is bonded. ) Structural unit (a) derived from the amino group-containing monomer (A) represented by ), A structural unit (b) derived from a monomer (B) having a polyalkylene glycol chain, and It has a structural unit (c) derived from an unsaturated carboxylic acid monomer (C), Furthermore, it may have a structural unit (d) derived from an aromatic group-containing monomer (D), The content ratios of structural unit (a) and structural unit (d) relative to 100% by mass of all structural units are 25-50% by mass and 0-20% by mass, respectively, and An amino group-containing copolymer in which the total content ratio of structural units (a), (b), (c), and (d) relative to 100% by mass of all structural units is 97% by mass or more. Second component: Nonionic surfactant represented by the following formula (6-1) R １３ -(CO) ｑ１ O- (A) ２ O) ｑ2 -R １４ (6-1) (In the formula, R １３ R represents an aliphatic hydrocarbon group with 8 to 24 carbon atoms. １４ This represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ２ O represents an oxyalkylene group having 2 to 4 carbon atoms, either identical or different. q1 represents the number of 0s or 1s. q2 is A ２ (This represents the average number of moles of oxyalkylene groups represented by O, and is a number between 7 and 50.)

2. The liquid laundry detergent composition according to claim 1, wherein the weight-average molecular weight of the first component is 4,000 or more and 500,000 or less.

3. The liquid laundry detergent composition according to claim 1 or 2, wherein the content of structural unit (b) of the first component is 25 to 70% by mass with respect to 100% by mass of all structural units.

4. The liquid laundry detergent composition according to claim 1 or 2, wherein the content of the structural unit (c) is 1 to 10% by mass relative to 100% by mass of all structural units.

5. The liquid laundry detergent composition according to claim 1 or 2, wherein the content of the nonionic surfactant is 5% by mass or more and 70% by mass or less based on 100% by mass of the liquid laundry detergent composition.

6. A cleaning method comprising the step of bringing the liquid laundry detergent composition described in claim 1 or 2 into contact with an object.

7. A pretreatment method comprising the step of bringing the liquid laundry detergent composition according to claim 1 or 2 into contact with an object.

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