JP2022115502A - liquid detergent composition - Google Patents

Abstract

To provide a liquid detergent composition having excellent low temperature stability.SOLUTION: A liquid detergent composition comprises: a component (A) which is a nonionic surfactant represented by the following general formula (I): R1-C(=O)O-[(EO)s/(PO)t]-(EO)u-R2 (I) (in formula (I), R1 is a C17 alkyl or alkenyl group; R2 is a C1-6 alkyl group; s represents an average repeating number of EO and is a number between 6 and 20; t represents an average repeating number of PO and is a number between 0 and 6; u represents an average repeating number of EO and is a number between 0 and 20; EO represents an oxyethylene group; PO represents an oxypropylene group; and when t is 1 or more, oxyethylene groups and oxypropylene group(s) in [(EO)s/(PO)t] may represent random polymerization or block polymerization); and a component (B) which is an anionic surfactant.

Description

The present invention relates to liquid detergent compositions.

Since polyoxyethylene fatty acid alkyl esters have excellent detergency, they are blended in liquid detergents (for example, liquid detergents containing A-1 (MEE) described in Examples of Patent Document 1).
Surfactants made from natural fats and oils usually have lipophilic groups with 12 to 14 carbon atoms, but they have the problem of competing with edible oils. On the other hand, long-chain fats and oils with 18 carbon atoms, etc., have limited applications. Although it is very significant to effectively utilize the oil and fat raw materials, which have hardly been used from the environmental point of view, the currently used surfactant with 12 to 14 carbon atoms was simply changed to 18. Detergents had a problem of inferior cleaning performance.

JP 2018-188785 A

The present inventors have found that the detergency problem can be solved by appropriately adjusting a polyoxyethylene fatty acid alkyl ester having a specific chain length and an anionic surfactant.
An object of the present invention is to provide a liquid detergent composition that is both environmentally friendly and cleansing performance.

The present invention has the following aspects.
[1]
Component (A): Nonionic surfactant R ¹ —C(═O)O—[(EO) _s /(PO) _t ]—(EO) _u —R ² .・(I)
(In formula (I), R ¹ is an alkyl or alkenyl group having 17 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, s represents the average repeating number of EO, and 6 to 20 is a number, t represents the average number of repetitions of PO and is a number from 0 to 6, u represents the average number of repetitions of EO and is a number from 0 to 20, EO represents an oxyethylene group, and PO is When t is 1 or more, the oxyethylene group and the oxypropylene group in [(EO)s/(PO)t] may be random polymerization or block polymerization. may be used.)
When,
(B) Component: A liquid detergent composition containing an anionic surfactant.

An object of the present invention is to provide a liquid detergent composition that utilizes a polyoxyethylene fatty acid alkyl ester having a specific chain length and has excellent detergency.

The liquid detergent composition of the present invention contains components (A) and (B).

<(A) Component>
Component (A) is a nonionic surfactant represented by the following general formula (I).
In addition, the compound represented by the following general formula (I) is also referred to as compound (I).

R ¹ —C(=O)O—[(EO) _s /(PO) _t ]—(EO) _u —R ² (I)
In formula (I), R ¹ is an alkyl or alkenyl group having 17 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, s represents the average repeating number of EO, and a number of 6 to 20 and t represents the average number of repetitions of PO and is a number from 0 to 6, u represents the average number of repetitions of EO and is a number from 0 to 20, EO represents an oxyethylene group, and PO is an oxy represents a propylene group. When t is 1 or more, the oxyethylene group and the oxypropylene group in [(EO)s/(PO)t] may be random polymerization or block polymerization.
The average repetition number can be measured by gas chromatography or the like.

^R1 in the general formula (I) is derived from the raw material fatty acid alkyl ester.
Examples of fatty acid alkyl esters include saturated or unsaturated fatty acid alkyl esters having 18 carbon atoms such as methyl stearate, methyl oleate, methyl linoleate and methyl linolenate, or mixtures thereof such as palm oil and palm kernel oil. , fatty acid alkyl ester mixtures derived from coconut oil or soybean oil.
Among these, fatty acid methyl ester mixtures derived from 18 carbon fractions such as oleic acid and linoleic acid of palm oil, palm kernel oil or coconut oil, or mixtures of two or more thereof are preferable, and the proportion of 18 carbon fractions is A fatty acid methyl ester mixture derived from a C18 fraction of palm oil is more preferable because it is readily available in large quantities.
The fatty acid methyl ester mixture derived from the 18-carbon fraction contains a large amount of unsaturated components such as methyl oleate and methyl linoleate, and these may be used after being hydrogenated. A large amount is preferable, and unhydrogenated palm oil, palm kernel oil, a mixture of fatty acid methyl esters derived from a fraction having 18 carbon atoms of coconut oil, or a mixture of two or more thereof is preferable.
These fatty acid methyl esters may be those obtained by known production methods, or commercially available products. For example, Pastel M182 (trade name) manufactured by Lion Chemical Co., Ltd. (fatty acid methyl ester mixture derived from palm oil-derived carbon number 18 fraction [methyl stearate (C16): methyl oleate (C18: 1): methyl linoleate (C18:2): Methyl palmitate (C18:0) and other minor components = 10:70:18:2 mixture (mass ratio)] The number after C indicates the number of carbon atoms in the fatty acid residue. "X" in "C18:X" indicates the number of double bonds in the fatty acid residue).

In general formula (I), R ¹ is an alkyl group or alkenyl group having 17 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, s represents the average repeating number of EO, and is a number, t represents the average repeating number of PO and is a number from 0 to 20, u represents the average repeating number of EO and is a number from 0 to 20, EO represents an oxyethylene group, PO is represents an oxypropylene group. When t is 1 or more, the oxyethylene group and the oxypropylene group in [(EO)s/(PO)t] may be random polymerization or block polymerization.
The average repetition number can be measured by gas chromatography or the like.
In general formula (I), R ¹ has 17 carbon atoms. R ¹ may be linear or branched. It may also be an alkyl group or an alkenyl group.
The number of carbon atoms in R ² is preferably 1-6, more preferably 1-3.
s is 3 to 25, preferably 5 to 20, more preferably 7 to 18, even more preferably 7 to 15, and particularly preferably 7 to 12.
t is 0-6, preferably 0-3.
u is 0 to 20, preferably 0 to 15, more preferably 0 to 10.
s + u, that is, the average number of added EO moles of the general formula (I) is 3 to 25, preferably 5 to 20, more preferably 7 to 18, further preferably 7 to 15, particularly 7 to 12. preferable.
When t is not 0, that is, when general formula (I) has EO and PO, the distribution (arrangement order) of EO and PO is not particularly limited, and may be arranged in blocks or randomly. You may have In the case of block polymerization, three or more blocks may be arranged. Alternatively, a combination of random arrangement and block arrangement may be used.
Methods for arranging EO and PO in blocks include, for example, a method of introducing ethylene oxide and then propylene oxide, a method of introducing propylene oxide and then ethylene oxide, and a method of introducing ethylene oxide and then propylene oxide. and a method of introducing ethylene oxide.

The content of component (A) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, still more preferably 2 to 40% by mass, and 2 to 35% by mass, relative to the total mass of the liquid detergent composition. % is particularly preferred. (A) Favorable detergency is obtained because content of a component is in the said range.
The method for producing component (A) is not particularly limited. (see JP-A-2003-200013), at least one selected from the group consisting of alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, alkaline earth metal oxides and alkaline earth metal hydroxides. , a method for producing a fatty acid alkyl ester alkoxylate by subjecting a fatty acid alkyl ester and an alkylene oxide to an addition reaction in the presence of an alkoxylation catalyst formed by reacting sulfuric acid in a liquid dispersion medium (International Publication No. 2013/ 154189)). Depending on the catalyst used and the manufacturing conditions other than the catalyst (temperature, pressure, solvent used, etc.), EO addition by-products are generated during the synthesis of component (A), and the mass of EO addition by-products relative to the mass of component (A) The expressed mass ratio (EO adduct by-product)/(A) component ratio is between 0.01 and 0.3. EO addition by-products are polyalkylene glycols, monoalkoxypolyalkylene glycols having an alkoxy group having 1 to 6 carbon atoms, and dialkoxy polyalkylene glycols having an alkoxy group having 1 to 6 carbon atoms among the component (C) described later. It corresponds to alkylene glycol.

<(B) Component>
(B) Component is an anionic surfactant.
Examples of anionic surfactants include linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt. Salts, linear or branched alkyl sulfates or salts thereof (AS), polyoxyalkylene alkyl (alkenyl) ether sulfates or salts thereof (AES), alkanesulfonic acids having alkyl groups or salts thereof, α- Sulfofatty acid ester or its salt (MES), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide ether carboxylic acid or its salt, acylaminocarboxylic acid or a carboxylic acid type anionic surfactant such as a salt thereof, an alkyl phosphate ester or a salt thereof, a polyoxyalkylene alkyl phosphate ester or a salt thereof, a polyoxyalkylene alkylphenyl phosphate ester or a salt thereof, a glycerin fatty acid ester monophosphate ester or phosphate ester type anionic surfactants such as salts thereof, higher fatty acids or salts thereof, etc., and from the viewpoint of detergency, linear alkylbenzene sulfonic acid or salts thereof (LAS), polyoxyalkylene alkyl ether sulfate esters or Salts thereof (AES), α-sulfofatty acid esters or salts thereof (MES) are preferred, and LAS, AES, and a combination of LAS and AES are more preferred.
In order to improve rinsability, it is preferable to use a higher fatty acid or a salt thereof as the component (B).
Examples of salts include alkali metal salts with sodium, potassium and the like, alkaline earth metal salts with magnesium and the like, and alkanolamine salts with monoethanolamine, diethanolamine and the like.
The anionic surfactant is preferably 1 to 60% by mass relative to the total mass of the liquid detergent composition. 1 to 50% by mass is more preferable, and 1 to 40% by mass is even more preferable.
Sufficient detergency can be ensured by using both the component (A) and the component (B) anionic surfactant. Combination of component (A) and one or more selected from LAS, AES and MES as component (B) is preferred, and combination of component (A) and LAS is more preferred.
The mass ratio represented by the content of component (B) to the content of component (A) ((B)/(A) ratio) is preferably 0.1 to 10, more preferably 0.15 to 8. 0.15 to 5 are more preferred.

Examples of polyoxyalkylene alkyl (alkenyl) ether sulfate esters or salts thereof include compounds represented by the following formula (III) (hereinafter referred to as "compound (III)").
R ²¹ —O—[(EO) _k /(PO) _n ]—SO ₃ M (III)
In formula (III), R ²¹ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms, and EO is oxyethylene. is a group, PO is an oxypropylene group, k represents the average number of repetitions of EO and is a number of 0 or more, n represents the average number of repetitions of PO and is a number of 0 to 6, M is a hydrogen atom or It is a counter cation.
R ²¹ is preferably a linear or branched alkyl group having 10 to 20 carbon atoms, more preferably a linear or branched alkyl group having 12 to 14 carbon atoms.
The content of the components where k=0 and n=0 in formula (III) is preferably 35 to 55% by mass relative to the total mass.
k is preferably 0 to 5, more preferably 0.1 to 3, still more preferably 0.5 to 3, and particularly preferably 0.5 to 2.5.
n is preferably 0 to 3, more preferably 0.
k+n is preferably a number greater than 0, more preferably 1-5.
When k and n are each different from 0, that is, when compound (III) has both EO and PO, EO and PO may be added blockwise or randomly. good. Examples of the method of adding EO and PO in blocks include a method of introducing ethylene oxide and then propylene oxide, and a method of introducing propylene oxide and then ethylene oxide. The addition mole number distribution of ethylene oxide and propylene oxide is not particularly limited.
Counter cations for M include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, and alkanolamines such as monoethanolamine and diethanolamine. The formula (III) component is preferably 0.1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1 to 20% by mass, relative to the total mass of the liquid detergent composition.

<(C) Component>
Glycols such as propylene glycol (PG), butylene glycol and hexylene glycol, polyalkylene glycols, monoalkoxy polyalkylene glycols in which the alkoxy group has 1 to 6 carbon atoms, and dialkoxy groups in which the alkoxy group has 1 to 6 carbon atoms It is one or more selected from the group consisting of alkoxypolyalkylene glycols.
Component (C) may be a by-product produced during the synthesis of component (A), or may be blended as a separate raw material.
Polyalkylene glycol is specifically an oxyalkylene adduct of a polyhydric alcohol having 2 to 6 carbon atoms. Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol, dipropylene glycol, glycerin, diglycerin, butylene glycol, sorbitol, sorbitan, erythritol, pentaerythritol, trimethylolpropane and other oxy alkylene adducts, and the like.
Oxyalkylene groups include ethylene oxide (EO) and propylene oxide (PO), and EO and PO may be mixed. When the EO and PO groups are mixed, they may be mixed in blocks or randomly.
The average repeating number of the oxyalkylene group is preferably 3-30, more preferably 3-20. The average repeating number of EO is preferably 3-30, more preferably 3-20. The average repeating number of PO is preferably 0-30.

The oxyalkylene group of the monoalkoxypolyalkylene glycol in which the alkoxy group has 1 to 6 carbon atoms and the dialkoxypolyalkylene glycol in which the alkoxy group has 1 to 6 carbon atoms is ethylene oxide (EO ) and propylene oxide (PO), and EO and PO may be mixed. When the EO and PO groups are mixed, they may be mixed in blocks or randomly.
The average repeating number of the oxyalkylene group is preferably 3-30, more preferably 3-20. The average repeating number of EO is preferably 3-30, more preferably 3-20. The average repeating number of PO is preferably 0-30. Specific examples of monoalkoxypolyalkylene glycols and dialkoxypolyalkylene glycols that are separately blended in addition to by-products of component (A) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, Methoxypolyethylene glycol and the like can be mentioned.

In the liquid detergent composition of the present invention, the content of component (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, even more preferably 1 to 8% by mass. 0.5 to 6% by weight is particularly preferred. By being within the above range, the appearance stability of the component (A) at low temperatures can be maintained satisfactorily.

The mass ratio ((A)/(C) ratio) represented by the content of component (A) to the content of component (C) is preferably 1 to 30, more preferably 2 to 25, and 2 to 22. More preferred. By being within the above range, the appearance stability of the component (A) at low temperatures can be maintained satisfactorily.

Other surfactants include nonionic surfactants other than component (A), cationic surfactants, semipolar surfactants, and amphoteric surfactants. Specific examples are given below.

(Nonionic surfactant other than component (A))
Nonionic surfactants other than component (A) include polyoxyalkylene type nonionic surfactants, alkylphenols, alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, Examples include polyhydric alcohol fatty acid esters or alkylene oxide adducts thereof, polyhydric alcohol fatty acid ethers, alkylene oxide adducts of hardened castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, and the like.
Among the above, polyoxyalkylene-type nonionic surfactants represented by the following general formula (II)-1 and the following general formula (II)-2 (hereinafter, compound (II) -1, also referred to as compound (II)-2).
R ³ —O—[(EO) _v /(AO) _w ]—(EO) _x —H (II)-1
R ⁴ —C(═O)O—[(EO) _e /(AO) _f ]—(EO) _g —R ⁵ (II)-2

In formula (II)-1, R ³ is an alkyl group having 8 to 22 carbon atoms, v represents the average repeating number of EO, is a number of 3 to 20, w represents the average repeating number of AO, A number of 0 to 20, x represents the average number of repetitions of EO, a number of 0 to 20, EO represents an oxyethylene group, AO is a PO (oxypropylene group) or an oxybutylene group (hereinafter referred to as BO Also called.) represents at least one of When w is 1 or more, in [(EO)v/(AO)w], an oxyethylene group and an oxypropylene group or an oxyethylene group and an oxybutylene group may be random polymerization or block polymerization. may be
The average repetition number can be measured by gas chromatography or the like.
In general formula (II)-1, R ³ preferably has 10 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms.
In general formula (II)-1, R ³ may be a straight-chain alkyl group, or a group selected from a branched-chain primary alkyl group and a straight-chain secondary alkyl group. .
In general formula (II)-1, when R ³ is a linear alkyl group, v+x is preferably 3 to 30, more preferably 5 to 18, still more preferably 6 to 18, and particularly preferably 10 to 18. w is a number from 0 to 6, preferably from 0 to 3.
In general formula (II)-1, when R ³ is a group selected from a branched primary alkyl group and a linear secondary alkyl group, v+x is particularly preferably 3 to 10, and w is 0. is preferred.
In general formula (II)-1, v+w+x is preferably 3 to 40, more preferably 10 to 25, even more preferably 10 to 20, and particularly preferably 10 to 18.
In formula (II)-2, R ⁴ is an alkyl or alkenyl group having 7 to 21 carbon atoms (excluding 17), R ⁵ is an alkyl group having 1 to 6 carbon atoms, and e is the average of EO represents the number of repetitions, a number from 3 to 20, f represents the average number of repetitions of AO, a number from 0 to 20, g represents the average number of repetitions of EO, a number from 0 to 20, EO represents an oxyethylene group, and AO represents at least one of PO (oxypropylene group) or oxybutylene group (hereinafter also referred to as BO). When e is 1 or more, in [(EO) e/(AO) f], the oxyethylene group and the oxypropylene group or the oxyethylene group and the oxybutylene group may be random polymerization or block polymerization. may be
The average repetition number can be measured by gas chromatography or the like.
In general formula (II)-2, R ⁴ preferably has 9 to 21 carbon atoms (excluding 17), more preferably 9 to 19 (excluding 17), and still more preferably 10 to 15 carbon atoms. ^R4 may be a linear alkyl group or a branched alkyl group.
In general formula (II)-2, R ⁵ preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.
In general formula (II)-2, e+g is preferably 3 to 25, more preferably 5 to 18, even more preferably 6 to 18, and particularly preferably 10 to 18. f is a number from 0 to 6, preferably from 0 to 3.

Nonionic surfactants other than component (A) are preferably 0 to 60% by mass relative to the total mass of the liquid detergent composition. 0 to 50% by mass is more preferable, and 1 to 40% by mass is even more preferable.
The mass ratio ((A)/total nonionic ratio) represented by the content of component (A) to the total content of nonionic surfactant containing component (A) is preferably 0.2 to 1, and 0.3. ~1 is preferred, and 0.4 to 1 is more preferred.
When nonionic surfactants other than component (A) are included, the mass ratio represented by the total content of nonionic surfactants other than component (A) with respect to the content of component (A) (nonionic other than (A) / (A) ratio) is preferably 0 to 0.95, preferably 0 to 0.9, and more preferably 0.6 to 1.

(cationic surfactant)
Examples of cationic surfactants include alkylamidoamines. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

(Amphoteric surfactant)
Examples of amphoteric surfactants include alkylbetaine type, alkylamidobetaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type, and phosphoric acid type. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

(semi-polar surfactant)
Semipolar surfactants include, for example, lauryldimethylamine oxide, lauramidopropyldimethylamine oxide, and the like. It is preferably 0.1 to 20% by mass, more preferably 1 to 10% by mass, based on the total mass of the liquid detergent composition.

The total surfactant content is preferably 10 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 10 to 60% by mass, relative to the total mass of the liquid detergent composition.

The mass ratio of component (A) to total surfactant (component (A)/total active agent) is preferably 0.01 to 0.8, more preferably 0.1 to 0.8, and 0.3 to 0. .8 is more preferred.
The mass ratio of the total content of the nonionic surfactant containing the component (A) to the total surfactant (total nonionic surfactant/total surfactant) is preferably 0.01 to 0.9, and 0.1 to 0.8 is more preferred, and 03 to 0.7 is even more preferred.

The mass ratio of the total content of the anionic surfactant to the total surfactant (total anionic surfactant/total surfactant) is preferably 0.01 to 0.9, more preferably 0.05 to 0.8. , 0.1 to 0.8 are more preferred.

The mass ratio represented by the total content of anionic surfactants to the total content of nonionic surfactants (total anionic surfactants/total nonionic surfactants) is preferably 0.1 to 8, and 0.2 to 7 is more preferred, and 0.2 to 5 is even more preferred.

<Water>
The liquid detergent composition can contain water. The water content is preferably 1 to 90% by mass, more preferably 5 to 90% by mass, even more preferably 20 to 90% by mass, relative to the total mass of the liquid detergent composition.

<Other optional ingredients>
In addition to the above components, the liquid detergent composition may contain optional components known in liquid detergent compositions for textiles, as long as they do not impair the effects of the present invention.
Optional components include, for example, organic solvents, stabilizers, bleaching agents, fluorescent brighteners, soil release agents, polymers (P) such as alkylene oxide adducts of polyalkyleneamines, dispersants, antifoaming agents, and pH adjusters. agents, enzymes, enzyme stabilizers, chelating agents, alkaline agents, texture improvers, antibacterial agents, preservatives, antioxidants, fragrances, dyes, pigments, plant extracts, plant extract oils, and the like.

Examples of organic solvents (other than component (C)) include ethanol, glycerin, 1-propanol, 2-propanol, 1-butanol, 3-methoxy-3-methyl-1-butanol (Solfit, trade name). , sorbitol, phenoxyethanol, and phenoxyisopropanol.
These solvents may be used singly or in combination of two or more.
1 to 30% by weight is preferred relative to the total weight of the liquid detergent composition.

Stabilizers include aromatic sulfonic acids or salts thereof. Aromatic sulfonic acids include benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, and the like. Examples of the salt form of the aromatic sulfonic acid include alkali metal salts (sodium salt, potassium salt, etc.), alkaline earth metal salts (magnesium salt, etc.), alkanolamine salts (monoethanolammonium salt, diethanolammonium salt, etc.), and the like. are mentioned. These aromatic sulfonic acids or salts thereof may be used singly or in combination of two or more. 0.01 to 10% by weight is preferred with respect to the total weight of the liquid detergent composition.

Bleaching agents include oxygen-based bleaching agents. Examples of oxygen-based bleaching agents include sodium percarbonate, sodium perborate, sodium monopersulfate, and hydrogen peroxide. These bleaching agents may be used singly or in combination of two or more. 0.01 to 10% by weight is preferred with respect to the total weight of the liquid detergent composition.

Examples of fluorescent brightening agents include biphenyl type fluorescent brightening agents such as 4,4′-bis(2-sulfostyryl)biphenyl disodium salt, 4,4′-bis((4-amino-6-morpholino-1 ,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonate and other stilbene-type optical brighteners. These fluorescent brightening agents may be used singly or in combination of two or more. 0.01 to 10% by weight is preferred with respect to the total weight of the liquid detergent composition.

Examples of soil release agents include polymers having at least one repeating unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and oxyalkylene units. Such polymers include, for example, those described in WO2017/142012. Commercially available SR agents include, for example, the trade name "TexCare SRN-170" manufactured by Clariant.
Polymers (P) such as alkylene oxide adducts of polyalkyleneamines are also included. Examples of the alkylene oxide adduct of polyalkyleneamine include those in which a side chain represented by the following formula (p) is bonded to the alkyleneamine main chain and the nitrogen atom of the alkyleneamine main chain.
-(EO)a(PO)b Formula (p)
In formula (p), EO is an oxyethylene group, PO is an oxypropylene group, a is a number from 3 to 60 representing the average number of repetitions of EO, and b is 0 to 0 representing the average number of repetitions of PO. Sixty numbers. As such a polymer (P), for example, International Publication No. 2017/142012 and
Examples thereof include those described in JP 2017-514967. Examples of the polymer (P) include trade name "Sokalan HP20" manufactured by BASF.
Further, cationized cellulose described in JP-A-2019-90057 can be mentioned.
Examples of dye transfer inhibitors include polyvinylpyrrolidone, carboxymethylcellulose, and polyalkyleneamine.
The dye transfer inhibitor may be used singly or in combination of two or more.
These are preferably 0.1 to 10% by mass relative to the total mass of the liquid detergent composition.

Examples of dispersants include polyacrylic acid and its salts, polymethacrylic acid and its salts, polymeric polycarboxylic acids and their salts.
These are preferably 0.01 to 5% by mass relative to the total mass of the liquid detergent composition.

Antifoaming agents include, for example, alcohol propylene oxide adducts (excluding component (C)), fatty acid esters (excluding component (A) and nonionic surfactants other than component (A)), antifoaming silicone and the like.
Examples of propylene oxide adducts of alcohols include those obtained by adding propylene oxide to monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol. The weight average molecular weight of the propylene oxide adduct of alcohol is preferably 2,500 to 5,500, more preferably 3,000 to 5,000. In this specification, the weight average molecular weight is obtained from the molecular weight distribution obtained by GPC (gel permeation chromatography) using polypropylene glycol (weight average molecular weight: 800, 1,200, 2,000, 4,000) as a standard. 0.1 to 10% by weight is preferred with respect to the total weight of the liquid detergent composition.
Examples of fatty acid esters include those represented by the following formula (IV).
X ²¹ -COO-Y ²¹ (IV)
In the formula, X ²¹ is a branched alkyl group having 5 to 21 carbon atoms or a linear alkyl group having 5 to 21 carbon atoms. When X ²¹ is a linear alkyl group, the carbon atom bonded to the carbon atom of the carbonyl group in formula (IV) is a secondary carbon atom. Y ²¹ is an alkyl group having 3 to 16 carbon atoms. Specific examples of fatty acid esters include 2-ethylhexyl 2-ethylhexanoate (also known as 2-ethylhexyl isooctyl acid, 2H08). 0.01 to 5% by weight is preferred relative to the total weight of the liquid detergent composition.

Examples of pH adjusters include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamine (monoethanolamine, diethanolamine, triethanolamine, etc.), ammonia, and the like. These pH adjusters may be used singly or in combination of two or more.

Examples of enzymes include protease, amylase, lipase, cellulase, mannanase and the like. Here, "enzyme" means an enzyme preparation.
Examples of proteases include Progress Uno (registered trademark) 100L, Medley (registered trademark) Core 210L, Savinase (registered trademark) 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Savinase Evity 16L, Everlase (available from Novozymes as protease preparations). Registered trademarks) 16L TypeEX, Everlase 16L, Everlase Ultra 16L, Esperase® 8L, Alcalase® 2.5L, Alcalase Ultra 2.5L, Liquanase® 2.5L, Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase (registered trademark) 48L (all trade names), Purafect (registered trademark) L, Purafect OX, and Properase L (all trade names) available from Genencor Inc., and the like.
Amylases include Termamyl® 300L, Termamyl Ultra 300L, Duramyl® 300L, Stainzyme® 12L, Stainzyme Plus 12L, Amplify 12L®, Amplify, available from Novozymes as amylase preparations. Prime 100L, Medley (registered trademark) Core210L (all trade names), Maxamyl (trade name) available from Genencore, Pullulanase Amano (trade name) available from Amano Pharmaceutical Co., Ltd., Available from Seikagaku Corporation Examples include DB-250 (trade name).
Examples of lipases include Lipex (registered trademark) 100L, Lipex Evity 100L, and Lipolase (registered trademark) 100L (all trade names) available from Novozymes as lipase preparations.
Examples of cellulase include Endolase (registered trademark) 5000L, Celluzyme (registered trademark) 0.4L, and Carzyme (registered trademark) 4500L (all trade names) available from Novozymes as cellulase preparations.
Examples of mannanase include Mannaway (registered trademark) 4L (trade name) available from Novozymes as a mannanase preparation.
プロテアーゼとしては、上記の中でも、Ｓａｖｉｎａｓｅ １６Ｌ、Ｓａｖｉｎａｓｅ Ｕｌｔｒａ １６Ｌ、Ｓａｖｉｎａｓｅ Ｕｌｔｒａ １６ＸＬ、Ｓａｖｉｎａｓｅ Ｅｖｉｔｙ １６Ｌ、Ｅｖｅｒｌａｓｅ １６Ｌ、Ｅｖｅｒｌａｓｅ Ｕｌｔｒａ １６Ｌ、Ａｌｃａｌａｓｅ ２．５Ｌ、Ａｌｃａｌａｓｅ Ｕｌｔｒａ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ ２．５Ｌ、Ｌｉｑｕａｎａｓｅ Ｕｌｔｒａ ２． 5L, Liquanase Ultra 2.5XL, Coronase 48L and Progress Uno are preferred, and Alcalase 2.5L, Everlase 16L, Savinase 16L, Savinase Evity 16L, Coronase 48L and Progress Uno are particularly preferred. These enzymes may be used singly or in combination of two or more.
These enzymes are preferably 0.1 to 10% by mass relative to the total mass of the liquid detergent composition.
Enzyme stabilizers include, for example, boric acid, borax, formic acid or salts thereof, lactic acid or salts thereof, calcium salts such as calcium chloride and calcium sulfate.
An enzyme stabilizer may be used individually by 1 type, and may be used in combination of 2 or more types.
The content of the enzyme stabilizer is preferably 2% by mass or less with respect to the total mass of the liquid detergent.

Examples of thickeners include acrylic polymers, xanthan gum, galrageenan, fine cellulose, hydrogenated castor oil, hydrogenated palm oil and the like.
Examples of commercially available acrylic polymers include the Carbopol (registered trademark) series manufactured by Lubrizol. The Carbopol series includes, for example, Carbopol ETD 2623, Carbopol EZ3, Carbopol EZ4, Carbopol Ultrez20, Carbopol Ultrez21, Carbopol Aqua 30 and the like.
Fine cellulose includes bacterial cellulose, non-bacterial cellulose, available from CPKelco U.S.A.; S. company's trade name "CELLULON (registered trademark)", FMC's trade name "Avicel (registered trademark)", Fiberstar's trade name "Citri-Fi", and Cosun's trade name "Betafib". be done.
A thickener may be used individually by 1 type, and may be used in combination of 2 or more type.
The content of the thickener is preferably 6% by mass or less, more preferably 0.2 to 4% by mass, relative to the total mass of the liquid detergent.
By blending a thickener, it is possible to impart appropriate viscosity and structural viscosity to the liquid detergent composition, and to disperse and stabilize insoluble substances such as capsule fragrances.

Examples of the texture improver include silicones such as dimethylsilicone, polyether-modified silicone and amino-modified silicone. Examples of these silicones include oil-type, oil-compound-type, solution-type, emulsion-type, and self-emulsifying-type silicones. These texture improvers may be used singly or in combination of two or more. 0.1 to 10% by weight is preferred with respect to the total weight of the liquid detergent composition.

Chelating agents include, for example, acetic acid, adipic acid, glycolic acid, diglycolic acid, monochloroacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, gluconic acid, and carboxymethylsuccinic acid. , Carboxylic acids of acids or salts thereof such as carboxymethyltartaric acid; ), hydroxyethylethylenediaminetriacetic acid (HEDTA), hydroxyethyliminodiacetic acid (HIDA), hydroxyiminodisuccinic acid (HIDS), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), propylenediaminetetraacetic acid, triethylenetetra Acids or their Salts of aminocarboxylic acids; 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), N,N,N',N'-tetrakis(phosphonomethyl)ethylenediamine (EDTMP) and other acids or organic phosphonic acids of salts thereof, etc. is mentioned. Salt forms of the chelating agent include, for example, sodium, potassium, calcium, magnesium and the like. These chelating agents may be used singly or in combination of two or more.
0.001 to 10% by mass is preferred relative to the total mass of the liquid detergent composition.

Antibacterial agents include diphenyl ether antibacterial agents such as diclosan (4,4′-dichloro-2-hydroxydiphenyl ether) and triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol), quaternary ammonium salts. (benzalkonium chloride, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts), bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene guanidine hydrochloride, 8-oxyquinoline, polylysine and the like. These antibacterial agents may be used singly or in combination of two or more. 0.001 to 10% by mass is preferred relative to the total mass of the liquid detergent composition.

Examples of antiseptics include "Cason CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan, "NIPACIDE BIT 20" (trade name) manufactured by Clariant, and the like. . The preservatives may be used singly or in combination of two or more. 0.001 to 1% by weight is preferred relative to the total weight of the liquid detergent composition.

Antioxidants include BHT (dibutylhydroxytoluene), BHA (butylhydroxyanisole), vitamin E (tocopherol), sodium erythorbate, methoxyphenol, sulfur dioxide, coffee bean extract (chlorogenic acid), green tea extract (catechin ), rosemary extract and the like. Antioxidants may be used alone or in combination of two or more. 0.01 to 3% by weight is preferred relative to the total weight of the liquid detergent composition.
If the liquid detergent contains an inorganic reducing agent, fading and discoloration due to light or heat can be suppressed.
Examples of the inorganic reducing agent include sulfites such as sodium sulfite and potassium sulfite; pyrosulfites such as sodium pyrosulfite and potassium pyrosulfite; and bisulfites such as sodium hydrogensulfite and potassium hydrogensulfite. Among these, sodium sulfite is preferable from the viewpoint of excellent storage stability.
An inorganic reducing agent may be used individually by 1 type, and may be used in combination of 2 or more types.
The content of the inorganic reducing agent is preferably 0.01 to 3% by mass, more preferably 0.02 to 1% by mass, and even more preferably 0.05 to 0.5% by mass, relative to the total mass of the liquid detergent. .

Examples of the perfume include those containing a perfume raw material alone, or a perfume composition comprising a perfume raw material, a solvent for perfume, a perfume stabilizer, and the like. can. For example, 1996 Kagaku Kogyo Nippousha, Genichi Indo, "Synthetic Perfume Chemistry and Product Knowledge"; 1969 Montclair, N.; J. published by STEFFEN ARCTANDER, "Perfume and Flavor Chemicals". More specific examples include synthetic fragrances, natural fragrances derived from animals or plants, mixed fragrances containing natural and/or synthetic fragrances, and fragrance ingredients described in, for example, JP-A-2002-146399. Moreover, you may mix|blend a capsule fragrance. 0.01 to 5% by weight is preferred relative to the total weight of the liquid detergent composition.
Plant extracts and plant oils include γ-oryzanol, scutellaria root extract, horsetail extract, hop extract, pine extract, lemon extract, rosemary extract, aspalathus lineari extract, oolong tea extract, hypericum perforatum extract, button extract, eucalyptus extract, Sage extract, cotton seed oil, jojoba oil, lavender oil, orange oil, lemon oil, rose extract oil, lime oil, cypress extract oil, herb extract oil and the like. These components may be blended as perfume components, or may be blended separately from perfumes as plant extracts or plant extract oils. Plant extracts and plant extract oils may be used singly or in combination of two or more.
The content of the plant extract or plant extract oil is preferably 0.00001 to 3% by mass, more preferably 0.0001 to 1% by mass, and 0.001 to 0.5% by mass relative to the total mass of the liquid detergent. % is more preferred.

Examples of coloring agents include quinone-based dyes, triphenylmethane-based dyes, xanthene-based dyes, quinoline-based dyes, and pyrene-based dyes. As used herein, "C.I." is an abbreviation for Color Index.
The structure of each dye is described in "Legal Dyes Handbook" (edited by Japan Cosmetic Industry Association) and Dye Handbook (edited by Synthetic Organic Chemistry Society).
Examples of quinone dyes include C.I. I. Solvent Blue 63 (C.I. Solvent Blue 63, Blue No. 403), C.I. I. Solvent Violet 13 (C.I. Solvent Violet 13, Murasaki No. 201), C.I. I. Acid Green 25 (C.I. Acid Green 25, Green No. 201), C.I. I. Acid Blue 112, C.I. I. Solvent Green 3 (Green No. 202), C.I. I. Vat Blue 6 (C.I. Bat Blue 6, Blue No. 204), C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 36, C.I. I. Acid Violet 43 (Purple No. 401), C.I. I. Acid Blue 41, C.I. I. Acid Blue 62, C.I. I. Acid Blue 78, C.I. I. Direct Green 28 (C.I. Direct Green 28), C.I. I. Acid Violet 34, C.I. I. Acid Vioret 41, C.I. I. Acid Vioret 51, C.I. I. Acid Blue 23, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 40, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 80, C.I. I. Acid Blue 126, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 138, C.I. I. Acid Blue 143, C.I. I. Acid Blue 182, C.I. I. Acid Blue 183, C.I. I. Acid Blue 203, C.I. I. Acid Blue 204, C.I. I. Acid Blue 205, C.I. I. Acid Green 36, C.I. I. Acid Green 40, C.I. I. Acid Green 41, C.I. I. Acid Green 44, C.I. I. Acid Brown 27 (C.I. Acid Brown 27), C.I. I. Acid Black 48 (C.I. Acid Black 48), C.I. I. Acid Black 50, C.I. I. Disperse Red 9 (C.I. Disperse Red 9), C.I. I. Solvent Violet 14, C.I. I. Disperse Violet 1, C.I. I. Acid Green 27 and the like. In addition, among the above solvent-based (oil-soluble) dyes, the end of the chromophore structure is chemically modified with a water-soluble polymer such as polyethylene glycol or polypropylene glycol to increase water solubility. It's okay. Specifically, trade names such as Liquitint Blue HP, Liquitint Blue BL, and Liquitint Blue MC manufactured by Milliken Co., Ltd. can be mentioned.
Examples of triphenylmethane dyes include Green No. 3 (C.I. 42053).
Examples of xanthene dyes include Red No. 106 (CI Acid Red 52), Red No. 3 (CI Acid Red 51), Red No. 214 (CI Solvent Red 49), Red No. 215 ( CI Solvent Red 49), Red No. 218 (CI Solvent Red 48), Red No. 223 (CI Solvent Red 43), Orange No. 201 (CI Solvent Red 72), Orange Color No. 206 (C.I. Solvent Red 73), Red No. 104 (1) (C.I. Acid Red 92), Red No. 105 (1) (C.I. Acid Red 94), Red No. 213 (C.I. Basic Violet 10), (1) of Red No. 230 (C.I. Acid Red 87), (2) of Red No. 230 (C.I. Acid Red 87), Red No. 231 (C.I. Acid Red 87) Acid Red 92), Red No. 232 (CI Acid Red 94), Orange No. 207 (CI Acid Red 95), Yellow No. 201 (CI Acid Yellow 73), Yellow No. 202 No. (1) (CI Acid Yellow 73), Yellow No. 202 (2) (CI Acid Yellow 73), and Red No. 401 (CI Acid Violet 9). Here, "C.I." is an abbreviation for "color index."
Examples of quinoline dyes include Yellow No. 203 (CI Acid Yellow 3) and Yellow No. 204 (CI Solvent Yellow 33).
Pyrene dyes include, for example, C.I. Solvent Green 7. 0.1 to 100 mass ppm is preferred relative to the total mass of the liquid detergent composition.

<How to use textile products>

The method of use in the washing process is to bring the textiles coated with the liquid detergent into contact with at least water, and remove the dirt adhering to the textiles and the liquid detergent by transferring them into the water. There is no particular limitation. A typical laundry process includes a wash process and a rinse process. The rinsing process is a process for removing residual liquid detergent after the cleaning process. After the rinsing treatment, drying or the like is carried out to remove water from the objects to be washed (textile products).
In the cleaning process, in a cleaning solution containing water and a liquid detergent, preferably, an external force is applied to the object to be washed to transfer dirt into the cleaning solution, and then dehydration or the like is performed to separate the object to be washed from the cleaning solution. .
In the rinsing treatment, after the washing treatment, in rinsing water containing no liquid detergent, an external force is preferably applied to the objects to be washed to transfer the remaining liquid detergent into the rinsing water, followed by dehydration, etc. to separate the items to be washed from the rinse water.
Washing treatment is usually performed once. The rinsing treatment may be performed once, or may be repeated twice or more. If the rinsing treatment is performed only once, the use of rinsing water can be saved and the washing time can be shortened, which is preferable.
The method of applying an external force to the article to be washed may be, for example, a method of applying a mechanical force using a washing machine, or a hand-washing method such as rubbing, pressing, beating, grasping, pinching, or shaking.

At the beginning of the laundering process (washing process), the textiles may be contacted with water alone or with a cleaning liquid comprising water and liquid detergent. When only water is brought into contact, the liquid cleaning agent applied to the textile product is dispersed in the water and becomes a cleaning liquid. When the cleaning liquid containing water and the liquid cleaning agent is contacted, the liquid cleaning agent applied to the textile is dispersed in the cleaning liquid and the concentration of the liquid cleaning agent in the cleaning liquid increases.

The items to be washed in the washing process may include not only textile products to which the liquid detergent has been applied, but also other textile products to which the liquid detergent has not been applied.
Regarding the amount of the liquid detergent used in the cleaning process, the ratio of the total mass of the object to be washed (the amount of cloth)/the total mass of the liquid detergent is preferably 10 to 500, more preferably 10 to 300, and 10 to 100. is more preferred. When it is at least the lower limit, the rinsability is excellent when applied for a long period of time, and when it is at most the upper limit, it is more excellent in detergency for other textile products to which the liquid detergent is not applied.
All of the liquid detergent used in the laundry process may be used for application to the textile soil, or a portion may be applied to the textile soil and the remainder added during the laundry process.
The amount of water used in the cleaning treatment is preferably 30 times or more, preferably 30 to 5000 times, more preferably 30 to 3500 times the amount of the liquid detergent used in the cleaning treatment. Rinsability is more excellent in it being more than a lower limit. Washing performance is more excellent in it being below an upper limit.

As in the method of use described above, excellent detergency can be exhibited by carrying out the washing treatment after bringing the stain adhering to the textile product into contact with the specific liquid detergent for a long period of time.
Textile products include, for example, clothes, cloths, sheets, and curtains. The material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide. In particular, it is preferably applied to stains that are difficult to remove by conventional washing methods. For example, it is suitable for removing stains caused by ink, foundation, lipstick, sebum, solid fat, food spills (curry, ketchup, sauce), blood, yellowing, and the like.

<pH>
The pH of the liquid detergent at 25° C. is preferably 4-10, more preferably 5-9, even more preferably 6-9.

<Viscosity>
The viscosity of the liquid detergent at 25° C. is preferably 5-1700 mPa·s, more preferably 10-500 mPa·s.
Viscosity is a value measured using a B-type (Brookfield type) viscometer.

The raw materials for the liquid detergent were as follows.
With the composition shown in Table 1, each component was added to water and mixed to prepare a liquid detergent for each example.
The compounding amount in the table is a pure content conversion value.
Ingredients whose blending amounts are not listed in the table are not blended.
The "appropriate amount" of the pH adjuster is the amount required to adjust the pH of the liquid composition of each example to 7 at 25°C.
The water content “balance” means the balance added so that the total of all components contained in the liquid composition (α) is 100% by mass.

<(A) Component>
· A-1: Fatty acid methyl ester ethoxylate synthesized by the following synthesis method.
A compound represented by the above formula (I), wherein R ¹ is an alkyl group having 17 carbon atoms, R ² is an alkyl group having 1 carbon atom, s=9, t=0, and u=0.
(Method for synthesizing component (A-1))
[Production of catalyst]
150 g of calcium acetate monohydrate (Calfresh (trade name), manufactured by Daito Kagaku Co., Ltd.) and 450 g of isopropyl alcohol (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) are placed in an acid-resistant container, and stirred at 45° C. for 20 minutes with a stirrer. A dispersion was prepared by dispersing calcium acetate monohydrate in isopropyl alcohol with mixing for a minute.
<Reaction process>
While stirring the dispersion liquid, 81.6 g of sulfuric acid (special grade reagent, manufactured by Kanto Kagaku Co., Ltd., concentration 95% by mass) was added dropwise by a pump over about 80 minutes to allow calcium acetate monohydrate and sulfuric acid to react. to generate these reactants.
<Aging process>
After the dropwise addition of sulfuric acid to the dispersion liquid was completed, the dispersion liquid was further stirred with a stirrer for 12 hours while maintaining the temperature at 45° C. to obtain a slurry.
<Separation process>
The resulting slurry was subjected to pressure filtration at 0.1 MPa using a filter and filter cloth to remove sulfuric acid from the slurry to obtain a filter cake.
<Washing process>
After that, 20 parts by mass of isopropyl alcohol was poured from the top of the filter cake with respect to 100 parts by mass of the filter cake, and the filter cake was filtered again to obtain a washed cake.
<Drying process>
The washed cake separated from the isopropyl alcohol was dried by heating under reduced pressure to obtain a catalyst. In the drying step, for example, using a rotary evaporator, the pressure was reduced to 0.005 MPa at 70° C., and heat drying was performed while rotating.
[EO addition reaction]
Thereafter, C18 fatty acid methyl ester (mass ratio methyl stearate: methyl oleate: methyl linoleate: methyl palmitate and other minor components = 10:70:18:2 mixture) was added to a 4 L autoclave equipped with a Maxblend blade. 648 g, 2.13 g of catalyst, and 63.8 g of propylene glycol (guaranteed reagent, manufactured by Kanto Kagaku Co., Ltd.) as a reaction accelerator were added.
These were stirred with a Maxblend impeller at a rotation speed of 420 rpm, and after nitrogen substitution, the temperature was raised to 160°C. Ethylene oxide was introduced into the autoclave while controlling the pressure in the system to be 0.5 MPa or less, and addition reaction was carried out at 160° C. to obtain about 2500 g of a reaction crude product. At this time, ethylene oxide was initially introduced at a constant feed rate (2 g/min). After the addition reaction started and the pressure in the system was observed to drop, the EO was fed at a constant acceleration while increasing the EO feed rate, and the maximum EO feed rate was set at 9 g/min.
[Step of flocculation and separation of crude reaction product]
550 g of the reaction crude product was placed in a 1 L separable flask, 9% by mass of water (100% by mass relative to the reaction crude product) was added thereto, and the mixture was mixed at 70° C. for 30 minutes at 470 rpm using a paddle stirring blade. Thereafter, 0.1% by mass of aluminum sulfate 14-18 hydrate (100% by mass relative to the reaction crude product) was added and mixed at 70° C. for 45 minutes to form aggregates to obtain a mixed solution. The resulting mixture was then cooled to 50° C. and 0.07% by weight of 30% sodium hydroxide solution (100% by weight of reaction crude) was added to neutralize the mixture. Thereafter, the component (A) and aggregates were separated using a centrifuge (AS ONE AS185) to obtain a purified product of the component (A).
· A-2: Fatty acid methyl ester ethoxylate synthesized by a conventional synthesis method (manufacturing method of JP-A-2016-124972). A compound represented by the above formula (I), wherein R ¹ is an alkyl group having 17 carbon atoms, R ² is an alkyl group having 1 carbon atom, s=7, t=0, and u=0.

· A-3: Fatty acid methyl ester ethoxylate synthesized by a conventional synthesis method (manufacturing method of JP-A-2016-124972). A compound represented by the above formula (I), wherein R ¹ is an alkyl group having 17 carbon atoms, R ² is an alkyl group having 1 carbon atom, s=12, t=0 and u=0.
· A-4: Fatty acid methyl ester ethoxylate synthesized by a conventional synthesis method (manufacturing method of JP-A-2016-124972). A compound of formula (I) wherein R1 is an alkyl group having 17 carbon atoms, R2 is an alkyl group having 1 carbon atom, s=15, t=0, and u=0.
・A-5: Product name “LEOFAT OA-100M-95” (Lion Specialty Chemicals Co., Ltd.), in the formula (I), R1 is an alkyl group having 17 carbon atoms and R2 is an alkyl group having 1 carbon atom , s=10, t=0, u=0.

<(B) Component>
· B-1: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name “Lipon LH-200”).
· B-2: Polyoxyethylene alkyl ether sulfate. In general formula (III), R ²¹ is a straight-chain alkyl group with 12 carbon atoms and a straight-chain alkyl group with 14 carbon atoms, k is 1, n is 0, and M is sodium. A compound (AES (1)) in which the ratio of compounds in which m is 0 and n is 0 to the entire AES is 43% by mass.
· B-3: Polyoxyethylene alkyl ether sulfate. In general formula (III), R ²¹ is a straight-chain alkyl group with 12 carbon atoms and a straight-chain alkyl group with 14 carbon atoms, k is 2, n is 0, and M is sodium. A compound (AES (2)) in which the ratio of compounds in which m is 0 and n is 0 to the entire AES is 43% by mass.
· B-4: sodium salt of α-sulfo fatty acid ester (MES), Lion Eco Chemicals Sdn. Bhd. Company product name: “MIZULAN (registered trademark) FL-80”
· B-5: Monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate (AEPS). Synthesized according to the synthesis example below.
(Synthesis of AEPS)
In an autoclave equipped with a stirring device, a temperature control device and an automatic introduction device, a linear primary alcohol having 12 carbon atoms (manufactured by Tokyo Chemical Industry Co., Ltd., trade name “1-dodecanol”, molecular weight 186.33, purity >99%) and 1.0 g of KOH were charged and dehydrated at 110° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120° C., and 199 g of propane-1,2-diyl oxide was charged. Then, after addition reaction and aging were carried out at 120° C., the temperature was raised to 145° C., and 303 g of ethylene oxide was charged. After addition reaction and aging were then carried out at 145° C., the mixture was cooled to 80° C. and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added to the autoclave, stirred at 80° C. for 30 minutes, and then extracted. An alkoxylate having an average number of added moles of EO of 2.0 was obtained. The resulting alkoxylate was sulfated in a falling film reactor with SO3 gas. The obtained sulfate was neutralized with monoethanolamine to obtain a composition containing polyoxyethylene polyoxypropane-1,2-diylalkyl ether sulfate monoethanolamine salt (AEPS).
· B-6: Sodium α-olefin sulfonate (AOS), manufactured by Lion Corporation, trade name "Liporan LB-840".
· B-7: manufactured by NOF Corporation, trade name "coconut fatty acid".
<(C) Component>
・C-1:

The ratio of component (B) in component (A) obtained when component (A) is synthesized can be determined using liquid chromatography (LC method). Specifically, the component (A) is measured by the LC method, and the peak intensity ratio between the peak corresponding to (B) and the polyethylene glycol standard (manufactured by Nippon Emulsion, equivalent to 15 mol) separately measured is calculated. asked. The measurement conditions were as follows.
The concentration of component (B) in the reaction crude product of component (A) can be determined using liquid chromatography (LC method). For example, the component (A) is measured by the LC method, and calculated from the peak intensity ratio between the peak corresponding to (B) and the separately measured polyethylene glycol standard (equivalent to 15 moles manufactured by Nippon Emulsion Co., Ltd.). The measurement method by the LC method is shown below. [Measurement condition]
・Column: ODS guard column + Shodex Asahipak GF-510HQ (7.5 x 300 mm)
・Column temperature: 30°C
・ Detector: Differential refractive index detector (RI)
- Mobile phase: distilled water, 0.6 mL / min
・Sample injection volume: 200 μL
・Measurement equipment: Shimadzu Corporation LC-20AD
· C-2: polyethylene glycol (manufactured by Lion Corporation, trade name "PEG # 1000-L60",
Mass average molecular weight 1000)
・C-3: Product name “CARBOWAX Methylpolyethylene
Glycol 750”, (manufactured by Dow Chemical Japan)

<Other surfactants>

<Nonionic surfactant>
• AE (15EO): polyoxyethylene alkyl ether (15EO), a product obtained by adding 15 moles of ethylene oxide to a natural alcohol. A compound represented by the above formula (II)-1, wherein R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=15, w=0, and x=0.
AE (12EO): Polyoxyethylene alkyl ether (12EO), a product obtained by adding 12 moles of ethylene oxide to a natural alcohol. A compound represented by the above formula (II)-1, wherein R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=12, w=0, and x=0.
AE (9EO): Polyoxyethylene alkyl ether (9EO), a product obtained by adding 9 moles of ethylene oxide to a natural alcohol. A compound represented by the above formula (II)-1, wherein R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=9, w=0, and x=0.
• AE (7EO): Polyoxyethylene alkyl ether (7EO), a product obtained by adding 7 moles of ethylene oxide to a natural alcohol. A compound represented by the above formula (II)-1, wherein R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=7, w=0, and x=0.
• AE (5EO): polyoxyethylene alkyl ether (5EO), a product obtained by adding 7 moles of ethylene oxide to a natural alcohol. A compound represented by the above formula (II)-1, wherein R ³ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v=5, w=0, and x=0.

<Semi-polar surfactant>
AX: Dodecyldimethylamine oxide, manufactured by Lion Corporation, trade name "Cadenax DM12D-W".

<Optional component>
・ Soil release agent: Clariant Japan Co., Ltd., trade name “TexCare SRN-170C”, weight average molecular weight = 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C.) = 4, viscosity (20 ° C.) = 300 mPa s. TexCare SRN-170C is a 70% by weight aqueous solution of trade name: TexCare SRN-100 (manufactured by Clariant Japan, weight average molecular weight: 2000 to 3000).
- Polymer compound (1): BASF Corporation, trade name "Sokalan HP20", ethylene adduct of polyethyleneimine.
- Polymeric compound (2): Copolymer sodium salt of olefin and maleic acid, manufactured by BASF, trade name "Sokalan CP9".
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
・ Capsule fragrance: INTERATIONAL FLAVORS & FRAGRANC
ES Company, trade name: "Mysterious Fly M2"
- Enzyme (1): Trade name "Medley (registered trademark) Core210L", manufactured by Novozymes.
・ Enzyme (2): manufactured by Novozymes, trade name: "Amplify Prime 100L"
・Enzyme (3): Novozymes, trade name: "Savinase Evity 16L"
・ Enzyme (4): Novozymes, trade name: "Carzyme (registered trademark) 4500L"
・ Enzyme (5): Novozymes, trade name: “Mannaway (registered trademark) 200L”
- Sodium lactate: manufactured by Kanto Chemical Co., Ltd., trade name "sodium lactate".
- Solvent (1): Ethanol, manufactured by Japan Alcohol Sales Co., Ltd., trade name "Specified Alcohol 95 Degree Synthesis".
Solvent (2): 3-methoxy-3-methylbutanol, trade name “Solfit”, manufactured by Kuraray Co., Ltd.
・Sodium benzoate Manufactured by Toagosei Co., Ltd., trade name “Sodium benzoate”.
- MEA: manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
- NaOH: trade name "sodium hydroxide" manufactured by Tsurumi Soda Co., Ltd.
・Citric acid: "Anhydrous citric acid" manufactured by Fuso Chemical Industry.
・Acrylic acid-based polymer: manufactured by Lubrizol, trade name “Carbopol EZ4”
- Fluorescent agent: Zhejiang HongDa Chemicals CO.; , Ltd., trade name "CBS-X"
・Anti-transfer agent: INTERNATIONAL SPECIALITY PRODUCTS INC. Product name: Chromabond S-100
・ Antifoaming agent: Mitsui Bussan Chemicals Co., Ltd., trade name “Actocol T-4000”
Antibacterial agent: Diclosan (4,4′-dichloro-2-hydroxydiphenyl ether) (manufactured by BASF, trade name “TINOSAN HP100”).
Pigment (1): Blue No. 3: manufactured by Kisumi Kasei Co., Ltd., trade name "Green No. 3".
・ Pigment (2): manufactured by Milliken, trade name “LIQUITINT VIOLET CT”
・Cotton seed oil (plant extract oil): manufactured by Simrise, trade name “Dragacotton N”

<Evaluation of low temperature stability>
100 mL of the liquid detergent composition of each example was added to a transparent glass bottle (wide mouth standard bottle PS-No. 11), and the lid was closed and sealed. After standing in this state in a constant temperature bath at 5° C. for 1 month, the appearance of the liquid was visually observed and evaluated according to the following criteria. ◎ and 〇 were regarded as passed.
(double-circle): It has fluidity and the whole liquid detergent is transparent.
◯: Fluidity is present, and the entire liquid detergent becomes slightly turbid, but the turbidity disappears within 6 hours when the temperature is returned to room temperature of 25°C.
x: There is no fluidity, and the entire liquid detergent becomes turbid, and the turbidity is not eliminated even when the room temperature is returned to 25°C.
<Evaluation 2: Sebum detergency>
In this method, the reflectance of the cloth is measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name: SE-2000), and the reflectance R is calculated from the Hunter whiteness Z according to the following formula (1). .
R=Z/100 (1)
First, the reflectance of ten sheets of WFK20D (manufactured by WFK (Germany), hereinafter also referred to as "stained cloth") before washing was measured. A Terg-O-Tometer (manufactured by US Testing) was used as a cleaning tester. The washing liquid was prepared by dissolving the liquid detergent composition for clothes in 900 mL of tap water at 25° C. so as to have a concentration of 333, 833 or 1800 ppm. (Examples 1 to 31, Comparative Example 1: 333 ppm, Examples 32 to 41: 1800 ppm, Examples 42, 43: 833 ppm)
Into the washing tank, 10 contaminated cloths and a charge cloth (knitted cloth cut into small pieces, sufficiently washed, rinsed and dried) were put, and a washing liquid was added. The amount of charge cloth was set so that the bath ratio was 30 times.
After washing for 10 minutes at a rotation speed of 120 rpm and a temperature of 25° C., rinsing was performed twice with 900 mL of tap water at 25° C. for 3 minutes. dried. The reflectance R of the contaminated cloth after drying (hereinafter also referred to as washing cloth) is measured using a 460 nm filter, and the washing rate (unit: %, rounded to the nearest whole number) is calculated by the following formula (2). did. In the formula, K is the extinction coefficient, S is the scattering coefficient, and R is the reflectance. The standard white cloth is the original white cloth (original cloth) that is not soiled, and the reflectance R of the standard white cloth is calculated as 87. A larger detergency value obtained by the following formula (2) indicates a higher detergency. In the following evaluation criteria, ⊚ and ◯ were regarded as acceptable.

Cleaning rate (%) = (soiled cloth K/S-washed cloth K/S)/(stained cloth K/S-unstained cloth K/S) x 100 (2)
K/S=(1-R/100)2/(2R/100)
"Evaluation criteria"
The average cleaning rate of 10 contaminated cloths is below.
◎: 65% or more ○: 60% or more and less than 65% ×: less than 60%

表１～３の評価結果に示すように、本発明を適用した実施例では、優れた低温安定性を確認した。

As shown in the evaluation results in Tables 1 to 3, the examples to which the present invention was applied were confirmed to have excellent low-temperature stability.

Claims (14)

Component (A): Nonionic surfactant R ¹ —C(═O)O—[(EO) _s /(PO) _t ]—(EO) _u —R ² .・(I)
(In formula (I), R ¹ is an alkyl or alkenyl group having 17 carbon atoms, R ² is an alkyl group having 1 to 6 carbon atoms, s represents the average repeating number of EO, and 6 to 20 is a number, t represents the average number of repetitions of PO and is a number from 0 to 6, u represents the average number of repetitions of EO and is a number from 0 to 20, EO represents an oxyethylene group, and PO is When t is 1 or more, the oxyethylene group and the oxypropylene group in [(EO)s/(PO)t] may be random polymerization or block polymerization. may be used.)
When,
(B) component: anionic surfactant
A liquid detergent composition containing Component (C): Glycols such as propylene glycol (PG), butylene glycol and hexylene glycol, polyalkylene glycol, monoalkoxypolyalkylene glycol having an alkoxy group having 1 to 6 carbon atoms, and alkoxy group having 1 carbon atom. 2. The liquid detergent composition according to claim 1, which contains one or more selected from the group consisting of dialkoxypolyalkylene glycols of 1 to 6. Component (B) is linear alkylbenzenesulfonic acid or its salt (LAS), linear or branched alkyl sulfate or its salt (AS), polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt ( AES), α-sulfo fatty acid esters or salts thereof (MES), higher fatty acids or salts thereof. The content of component (A) is 1 to 60% by mass with respect to the total mass of the liquid detergent,
The content of component (B) is 1 to 60% by mass with respect to the total mass of the liquid detergent,
The liquid detergent composition according to any one of claims 1 to 3, which is The liquid detergent composition according to any one of Claims 1 to 4, wherein the content of component (C) is 0.1 to 15% by mass relative to the total mass of the liquid detergent. The mass ratio ((B)/(A) ratio) represented by the content of component (B) to the content of component (A) is 0.01 to 10. A liquid cleaning composition as described. The mass ratio ((A)/(C) ratio) represented by the content of component (A) to the content of component (C) is 1 to 30, according to any one of claims 2 to 6. Liquid detergent composition. Furthermore, the mass ratio ((A) / total The liquid detergent composition according to any one of claims 1 to 7, wherein the nonionic ratio) is 0.2 to 1. The liquid detergent composition according to any one of claims 1 to 8, wherein the total amount of surfactant is 10 to 80% by mass based on the total weight of the liquid detergent composition. The liquid detergent composition according to any one of claims 1 to 9, further comprising one or more selected from the group consisting of cationic surfactants, amphoteric surfactants and semipolar surfactants. The liquid detergent composition according to any one of claims 1 to 10, further comprising 1 to 30% by mass of an organic solvent (other than component (C)) relative to the total mass of the liquid detergent composition. . The liquid detergent composition according to any one of Claims 1 to 11, further comprising 0.01 to 10% by mass of an aromatic sulfonic acid or a salt thereof relative to the total mass of the liquid detergent composition. 13. The liquid detergent composition according to any one of claims 1 to 12, further comprising 0.001 to 3% by mass of a plant extract and/or a plant extract oil relative to the total mass of the liquid detergent composition. . In addition, bleaching agents, fluorescent brightening agents, soil release agents, polymers (P) such as alkylene oxide adducts of polyalkyleneamines, dispersants, antifoaming agents, pH adjusters, enzymes, enzyme stabilizers, chelating agents , an alkali agent, a texture improver, an antibacterial agent, a preservative, an antioxidant, a fragrance, a dye, and a pigment according to any one of claims 1 to 13. Liquid detergent composition.