JP7122909B2 - Liquid detergent composition for clothes - Google Patents

Description

The present invention relates to a liquid detergent composition for clothes.

One of the features of the liquid detergent composition for clothes is that it can be directly applied to the object to be washed (textile products, etc.) to which dirt has adhered. When the liquid detergent composition for clothes is directly applied to an object to be washed, the viscosity of the liquid detergent composition for clothes is an important index of usability. Usability refers to ease of discharge when the liquid detergent composition for clothes is discharged from a container, and the liquid detergent composition for clothes when directly applying the liquid detergent composition for clothes to the object to be washed. It refers to ease of use of the liquid detergent composition for clothes, such as spreadability. When the liquid detergent composition for clothes has a high viscosity (for example, 2000 mPa·s or more), it becomes difficult to discharge from the container. In addition, when the liquid laundry detergent composition is applied directly to the object to be washed, it becomes difficult to spread. will increase.

To address these problems, Patent Document 1 proposes a liquid laundry detergent composition containing an anionic surfactant, a cationic polymer having a specific structure, and a solvent having a specific structure. The liquid detergent composition for clothes of Patent Document 1 is intended to improve usability at low temperatures (for example, 5°C) in winter.

JP 2017-222789 A

A liquid detergent composition for clothes becomes less viscous at high temperatures (e.g., 35°C) in summer, making it difficult to apply the composition to soiled items to be washed as intended, or causing the liquid to drip from the container. .
However, in Patent Document 1, usability at high temperatures is not taken into consideration.
In addition, it is required that the liquid detergent composition for clothes does not precipitate solids and that the liquid does not become cloudy (liquid stability).

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition for clothes that is excellent in liquid stability and can achieve both usability at low temperatures and usability at high temperatures. .

As a result of extensive studies, the present inventors have found that the above problems can be solved by combining a nonionic surfactant, a specific solvent, and a specific polymer.
That is, the present invention has the following aspects.

[1] Component (A): a nonionic surfactant, Component (B): a compound represented by the following general formula (b-1), and Component (C): uncrosslinked alkyl acrylate and alkyl methacrylate. and a copolymer of the type.

［式中、Ｒ^１～Ｒ^３は、それぞれ独立に水素原子又は炭素数１～３のアルキル基であり、Ｒ^４は、水素原子又はアセチル基である。］

[In the formula, R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group. ]

[2] The liquid detergent composition for clothes according to [1], wherein the component (A) is a compound represented by the following general formula (a-1).
R ¹¹ —O—(EO) _m —H (a-1)
[In the formula, R ¹¹ is an alkyl or alkenyl group having 10 to 18 carbon atoms, EO is an oxyethylene group, and m represents the average repeating number of EO and is a number of 2 to 20. ]
[3] The liquid detergent composition for clothes according to [1] or [2], wherein the component (B) is 3-methoxy-3-methylbutanol.
[4] The liquid detergent composition for clothes according to any one of [1] to [3], wherein the content of component (B) is 0.1 to 15% by mass relative to the total mass.
[5] The liquid detergent composition for clothes according to any one of [1] to [4], wherein the content of component (C) is 0.01 to 3% by mass relative to the total mass.
[6] The liquid detergent composition for clothes according to any one of [1] to [5], wherein the weight average molecular weight of component (C) is 100,000 or more.
[7] The liquid detergent composition for clothes according to any one of [1] to [6], wherein the mass ratio represented by component (B)/component (C) is 1 to 300.

ADVANTAGE OF THE INVENTION According to the liquid detergent composition for clothes of this invention, it is excellent in liquid stability, and can aim at compatibility with the usability at the time of low temperature, and the usability at the time of high temperature.

[Liquid detergent composition for clothes]
The liquid detergent composition for clothes of the present invention (hereinafter also simply referred to as "liquid detergent") is a composition containing component (A), component (B) and component (C).

<(A) Component>
(A) Component is a nonionic surfactant. Since the liquid detergent of the present invention contains the component (A), it exhibits detergency against various stains.
Component (A) includes, for example, polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, and polyoxyethylene-polyoxypropylene block copolymers. , fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or alkylene oxide adduct thereof, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, hydrogenated castor oil alkylene oxide adduct, sugar fatty acid ester, N- Alkyl polyhydroxy fatty acid amides, alkyl glycosides and the like can be mentioned.
As the component (A), among the above, a polyoxyalkylene type nonionic surfactant is preferable from the viewpoint of improving the liquid stability while maintaining the appropriate viscosity of the liquid detergent.

Examples of polyoxyalkylene-type nonionic surfactants include compounds represented by the following general formula (a-1) (hereinafter also referred to as "compound (a1)"), and compounds represented by the following general formula (a-2). (hereinafter also referred to as "compound (a2)").
R ¹¹ —O—(EO) _m —H (a-1)
R ¹² —CO—(OR ¹³ ) _n —OR ¹⁴ (a-2)

In formula (a-1), R ¹¹ is an alkyl or alkenyl group having 10 to 18 carbon atoms, EO is an oxyethylene group, and m represents the average number of repeating EO, and is a number of 2 to 20. .
The number of carbon atoms in R ¹¹ is preferably 12-16, more preferably 12-15, from the viewpoint of detergency. R ¹¹ is preferably an alkyl group, more preferably an alkyl group having 12 to 15 carbon atoms.
m is 2 to 20, preferably 2 to 15, more preferably 2 to 7. When m is within the above numerical range, the permeability to the laundry is likely to be improved. In addition, the detergency (lipid detergency) against lipid stains on the object to be washed is likely to be improved.
As the compound (a1), a primary alcohol ethoxylate obtained by adding ethylene oxide to a primary alcohol is particularly preferable.

In formula (a-2), R ¹² is a hydrocarbon group having 9 to 13 carbon atoms, R ¹³ is an alkylene group having 2 to 4 carbon atoms, and R ¹⁴ is an alkyl group having 1 to 4 carbon atoms. . n indicates the average number of repetitions of OR ¹³ and is a number from 5 to 25. A plurality of R ¹³ may be the same or different from each other. When a plurality of R ¹² are different, they may be added in blocks or randomly.

As the compound (a2), among those mentioned above, polyoxyethylene fatty acid alkyl esters in which R ¹³ is an ethylene group are preferable, and among them, polyoxyethylene fatty acid methyl esters in which R ¹⁴ is a methyl group (hereinafter referred to as “MEE”) ) is more preferable. Even if they contain a high-concentration surfactant, they hardly cause a significant increase in viscosity (gelation) and tend to have good fluidity.

(A) component may be used individually by 1 type, and may use 2 or more types together.
The content of component (A) is preferably 10 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 30% by mass, relative to the total mass of the liquid detergent. When the content of the component (A) is at least the above lower limit, the detergency increases and the dispersibility of the component (C), which will be described later, is easily improved. (A) It is easy to suppress the increase in the viscosity of a liquid cleaning agent as content of a component is below the said upper limit.

<(B) Component>
Component (B) is a compound represented by the following general formula (b-1). Containing the component (B), the liquid detergent of the present invention tends to improve usability.

In the formula, R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group.

In formula (b-1), all of R ¹ to R ³ are preferably hydrogen atoms, or one is an alkyl group and the other two are hydrogen atoms. That is, two or more of R ¹ to R ³ are preferably hydrogen atoms. When two or more of R ¹ to R ³ are hydrogen atoms, the liquid stability of the liquid detergent can be easily improved. In addition, when two or more of R ¹ to R ³ are hydrogen atoms, the usability of the liquid detergent is likely to be improved.
When any one of R ¹ to R ³ is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 2, more preferably 1. When the number of carbon atoms in R ¹ to R ³ is within the above numerical range, the usability of the liquid detergent is likely to be improved.
R ⁴ is preferably a hydrogen atom from the viewpoint of easily improving the usability of the liquid detergent.

Component (B) includes, for example, 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-3-ethylbutanol, 3-methoxy-3-propylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-2-ethylbutanol, 3-methoxy-2-propylbutanol, 3-methoxy-1-methylbutanol, 3-methoxy-1-ethylbutanol, 3-methoxy-1-propylbutanol, etc., formula (b- 1) wherein R ⁴ is a hydrogen atom; 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, 3-methoxy-3-ethylbutyl acetate, 3-methoxy-3-propylbutyl acetate, 3 -Methoxy-2-methylbutylacetate, 3-Methoxy-2-ethylbutylacetate, 3-Methoxy-2-propylbutylacetate, 3-Methoxy-1-methylbutylacetate, 3-Methoxy-1-ethylbutylacetate, 3 -Methoxy-1-propylbutylacetate and the like, wherein R ⁴ in formula (b-1) is an acetyl group.
Among them, component (B) includes 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, and 3-methoxy-3-methylbutyl acetate. is preferred, and 3-methoxy-3-methylbutanol is more preferred.

(B) component may be used individually by 1 type, and may use 2 or more types together.
The content of component (B) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, relative to the total mass of the liquid detergent. (B) It is easy to improve the usability of a liquid detergent as content of a component is more than the said lower limit. (B) It is easy to make liquid stability of a liquid detergent more favorable as content of a component is below the said upper limit.

<(C) Component>
Component (C) is a non-crosslinked copolymer of alkyl acrylate and alkyl methacrylate. Containing the component (C) makes it easier for the liquid detergent of the present invention to improve usability.
As used herein, the term "non-crosslinked copolymer" refers to a copolymer obtained by polymerizing monomers having only one carbon-carbon double bond in the molecule.

As the component (C), a repeating unit derived from a monomer represented by the following general formula (c-1) (hereinafter also referred to as "monomer (c1)"), and the following general formula (c -2) (hereinafter also referred to as "monomer (c2)").

In formula (c-1), R ⁵¹ is a hydrogen atom or a methyl group, and R ⁵² is a hydrogen atom.
In formula (c-2), R ⁵³ is a hydrogen atom or a methyl group, and R ⁵⁴ is an alkyl group having 1 to 40 carbon atoms.

Monomer (c1) includes acrylic acid and methacrylic acid.
The monomer (c1) may be used alone or in combination of two or more.

In monomer (c2), the alkyl group of R ⁵⁴ may be linear or branched. The alkyl group of ^R54 may contain a cyclic structure.
The number of carbon atoms in the alkyl group of R ⁵⁴ is 1-40, preferably 1-20, more preferably 1-10.

Examples of the monomer (c2) include acrylic acids such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, and icosyl acrylate. Ester; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, decyl methacrylate, dodecyl methacrylate and icosyl methacrylate.
Acrylic acid esters are preferred as the monomer (c2).
Monomer (c2) may be used alone or in combination of two or more.

(C) As a component, you may use a commercial item. (C) As a commercial item of a component, the brand name "Novethix HC200" by Lubrizol is mentioned, for example.

The weight average molecular weight of component (C) is preferably 100,000 or more. (C) It is easy to adjust to the viscosity which is easy to use a liquid cleaning agent as the mass average molecular weight of a component is more than the said lower limit.
The mass average molecular weight of component (C) can be determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

(C) component may be used individually by 1 type, and may use 2 or more types together.
The content of component (C) is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass, relative to the total mass of the liquid detergent. . (C) It is easy to increase the viscosity of a liquid detergent as content of a component is more than the said lower limit. (C) When the content of the component is equal to or less than the above upper limit, thickening is suppressed, and the liquid stability of the liquid detergent is likely to be improved.

The mass ratio represented by (B) component / (C) component (hereinafter also referred to as (B) / (C) ratio) is preferably 1 to 300, more preferably 10 to 100, and further 20 to 80 preferable. When the (B)/(C) ratio is within the above numerical range, the usability of the liquid detergent is likely to be improved.

<Optional component>
The liquid detergent of the present invention may contain optional components other than the components (A), (B) and (C) as long as they do not impair the effects of the present invention. As optional ingredients, ingredients that are commonly used in liquid detergents can be blended.
Optional components include, for example, surfactants other than component (A), water-miscible organic solvents other than component (B), enzymes, water, solubilizers, viscosity reducers, alkaline agents, metal ion scavengers (chelate agents), antioxidants, preservatives, enzyme stabilizers, texture improvers, fluorescent brighteners, anti-soil agents, pearlescent agents, soil release agents, flavoring agents, coloring agents, emulsifying agents, natural products and other extracts, pH adjusters, and the like.

Examples of surfactants other than component (A) (hereinafter also referred to as other surfactants) include anionic surfactants, cationic surfactants, amphoteric surfactants, and semipolar surfactants.

The anionic surfactant can be appropriately selected from known anionic surfactants and used.
Examples of anionic surfactants include linear alkylbenzenesulfonic acids or salts thereof; α-olefin sulfonates; linear or branched alkyl sulfates; alkyl ether sulfates or alkenyl ether sulfates; alkanesulfonate; α-sulfo fatty acid ester salt and the like. Salts of these anionic surfactants include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
From the viewpoint of easily increasing the detergency of the liquid detergent, the straight-chain alkylbenzenesulfonic acid or salt thereof preferably has a straight-chain alkyl group with 8 to 16 carbon atoms, more preferably 10 to 14 carbon atoms. .
The α-olefin sulfonate preferably has 10 to 20 carbon atoms from the viewpoint of easily increasing the detergency of the liquid detergent.
From the viewpoint of easily increasing the detergency of the liquid detergent, the alkyl sulfate salt preferably has an alkyl group with 10 to 20 carbon atoms.
From the viewpoint of easily increasing the detergency of the liquid detergent, the alkyl ether sulfate salt or alkenyl ether sulfate salt has a linear or branched alkyl or alkenyl group having 10 to 20 carbon atoms, and has an average of 1 Additions of ˜10 moles of ethylene oxide (ie, polyoxyethylene alkyl ether sulfates or polyoxyethylene alkenyl ether sulfates) are preferred.
The alkanesulfonate preferably has an alkyl group with 10 to 20 carbon atoms, more preferably 14 to 17 carbon atoms, from the viewpoint of easily increasing the detergency of the liquid detergent. Among them, those in which the alkyl group is a secondary alkyl group (that is, secondary alkanesulfonate) are particularly preferred.
Examples of α-sulfo fatty acid ester salts include α-sulfo fatty acid esters of R ^a CH(SO ₃ M)COOR ^b (wherein R ^a and R ^b are each independently a hydrocarbon group, and M is a counterion is.). From the viewpoint of easily increasing the detergency of the liquid detergent, the compound represented by R ^a CH(SO ₃ M)COOR ^b is a fatty acid residue (that is, a group represented by R ^a —C(H)—COO). ) having 10 to 20 carbon atoms is preferable.
Among these, at least one anionic surfactant selected from linear alkylbenzenesulfonic acids or salts thereof, alkanesulfonates, polyoxyethylene alkyl ether sulfates, and α-olefinsulfonates is more preferable, and poly Oxyethylene alkyl ether sulfate ester salts are particularly preferred.

Examples of anionic surfactants other than the above include fatty acids having 8 to 22 carbon atoms (higher fatty acids) or salts thereof, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, Carboxylic acid type anionic surfactants such as acid salts and acylaminocarboxylates; phosphate type anionic surfactants such as
Commercially available products may be used as these anionic surfactants.

When the liquid detergent contains an anionic surfactant, the content of the anionic surfactant is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, based on the total mass of the liquid detergent. ~15% by mass is more preferred. When the content of the anionic surfactant is at least the above lower limit, the detergency against sebum stains (sebum detergency) is enhanced. When the content of the anionic surfactant is equal to or less than the above upper limit value, the fluidity of the liquid detergent is further increased, and the liquid stability is likely to be improved.

Cationic surfactants include, for example, tetrashort-chain (alkyl having 1 to 4 carbon atoms) ammonium salts such as tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts; octyltrimethylammonium salts, decyl Trimethylammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, lauryltrimethylammonium salt, cetyltrimethylammonium salt, palmityltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt, dodecyldimethyl ethylammonium salt, tetradecyldimethylethylammonium salt, lauryldimethylethylammonium salt, cetyldimethylethylammonium salt, stearyldimethylethylammonium salt, octyldiethylmethylammonium salt, decyldiethylmethylammonium salt, dodecyldiethylmethylammonium salt, tetradecyldiethyl Long-chain (alkyl having 8 to 18 carbon atoms) trishort-chain (alkyl having 1 or 2 carbon atoms) ammonium salts such as methylammonium salts, cetyldiethylmethylammonium salts, stearyldiethylmethylammonium salts; dioctyldimethylammonium salts, didecyl dimethylammonium salt, didodecyldimethylammonium salt, ditetradecyldimethylammonium salt, dicetyldimethylammonium salt, distearyldimethylammonium salt, dioctylmethylethylammonium salt, didecylmethylethylammonium salt, didodecylmethylethylammonium salt, di Di-long chain (alkyl having 8 to 18 carbon atoms) di-short chain (alkyl having 1 or 2 carbon atoms) ammonium salts such as tetradecylmethylethylammonium salt, dicetylmethylethylammonium salt, distearylmethylethylammonium salt; stearyl Long-chain (alkyl having 8 to 18 carbon atoms) dishort-chain (alkyl having 1 or 2 carbon atoms) hydroxyalkyl (1 or 2 carbon atoms) ammonium salts such as dimethylhydroxyethylammonium; [3(trimethoxysilyl)]propyl (Dimethyl)octadecylammonium salts and other di-short-chain (alkyl having 1 or 2 carbon atoms) long-chain (alkyl having 8 to 18 carbon atoms) ammonium salts having a trialkoxysilylalkyl group (4 to 10 carbon atoms); rate; benzylate trimethylammonium salt; benzalkonium salt; benzethonium salt and the like.
Salts include halides such as chlorine, bromine and iodine; hydroxides; sulfonate, sulfate and nitrate having 1 to 5 carbon atoms.

Amphoteric surfactants include, for example, betaine octaamidopropyldimethylaminoacetate, betaine decanoamidopropyldimethylaminoacetate, betaine lauramidopropyldimethylaminoacetate, betaine myristateamidopropyldimethylaminoacetate, and amidopropyldimethyl stearate. betaine amino acetate, betaine oleic acid amidopropyldimethylaminoacetate, betaine coconut fatty acid amidopropyldimethylaminoacetate, betaine palm oil fatty acid amidopropyldimethylaminoacetate, betaine palm kernel fatty acid amidopropyldimethylaminoacetate, betaine octyldimethylaminoacetate, Betaine Decyldimethylaminoacetate, Betaine Lauryldimethylaminoacetate, Betaine Myristyldimethylaminoacetate, Betaine Stearyldimethylaminoacetate, Betaine Oleyldimethylaminoacetate, Betaine Octanoamidopropyl Hydroxysulfobetaine, Decanoamidopropyl Hydroxysulfobetaine, Lauramidopropyl Hydroxysulfobetaine, myristate amidopropyl hydroxysulfobetaine, stearamide propyl hydroxysulfobetaine, oleic acid amidopropyl hydroxysulfobetaine, coconut fatty acid amidopropyl hydroxysulfobetaine, palm oil fatty acid amidopropyl hydroxysulfobetaine, palm kernel fatty acid amidopropylhydroxysulfobetaine, octylhydroxysulfobetaine, decylhydroxysulfobetaine, laurylhydroxysulfobetaine, myristylhydroxysulfobetaine, stearylhydroxysulfobetaine, oleylhydroxysulfobetaine and the like.

Examples of semipolar surfactants include amine oxide type surfactants such as lauryldimethylamine oxide and lauramidopropyldimethylamine oxide.

When the liquid detergent contains another surfactant, the content of the other surfactant is preferably 5 to 40% by mass, more preferably 5 to 35% by mass, based on the total mass of the liquid detergent. , 5 to 30 mass % is more preferable.

The total mass of the surfactant is preferably 5-70% by mass, more preferably 10-60% by mass, and even more preferably 15-40% by mass, relative to the total mass of the liquid detergent. When the total mass of the surfactant is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the total mass of the surfactant is equal to or less than the above upper limit, the liquid stability of the liquid cleaning agent can be easily improved.
The content of component (A) relative to the total weight of the surfactant is preferably 50-100% by mass, more preferably 75-100% by mass. When the content of component (A) with respect to the total mass of the surfactant is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the content of component (A) with respect to the total mass of the surfactant is equal to or less than the above upper limit, the liquid stability of the liquid detergent can be easily improved.

By containing a water-miscible organic solvent excluding the component (B), the liquid detergent of the present invention can improve the liquid stability and tend to improve the fluidity of the liquid detergent. As used herein, a water-miscible organic solvent refers to an organic solvent that dissolves in 1 L of deionized water at 25° C. in an amount of 50 g or more.

Examples of water-miscible organic solvents other than component (B) include monohydric alcohols having 2 to 4 carbon atoms, polyhydric alcohols having 2 to 4 carbon atoms, and glycol ether solvents represented by the following general formula (I). etc.

R ³¹ —(OR ³² ) _w OH (I)
(I) In the formula, R ³¹ is hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ³² is an alkylene group having 2 to 4 carbon atoms, w represents the average number of added moles, and 1 to 30,000 numbers.

Examples of monohydric alcohols having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol and 1-butanol.
Examples of polyhydric alcohols having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol and glycerin.
Examples of glycol ether solvents represented by formula (I) include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and the like. be done.

Compounds of formula (I) in which R ³¹ is hydrogen include polyethylene glycol. As the polyethylene glycol, those in which w in formula (I) is 5 or more are preferable. Further, the weight average molecular weight of polyethylene glycol is preferably 200 to 1,320,000, more preferably 200 to 5,000, even more preferably 200 to 2,000, and particularly preferably 200 to 1,000. Among these, polyethylene glycol having a mass average molecular weight of 1000 (w is 22 to 24) is particularly preferred. In addition, the mass average molecular weight of polyethylene glycol shows the value calculated based on the calibration curve in polyethylene glycol from the value measured by GPC using methanol as a solvent.
Water-miscible organic solvents other than component (B) include ethanol, propylene glycol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, Polyethylene glycol is preferred, and ethanol and polyethylene glycol are more preferred.

The water-miscible organic solvents other than component (B) may be used singly or in combination of two or more.
When the liquid detergent contains a water-miscible organic solvent excluding the component (B), the content of the water-miscible organic solvent excluding the component (B) is 2.5 to 2.5% of the total mass of the liquid detergent. 25% by weight is preferred. When the content of the water-miscible organic solvent excluding the component (B) is within the above numerical range, it is easy to improve the liquid stability.

The total weight of the water-miscible organic solvent is preferably 2.5-40% by weight, more preferably 3-35% by weight, even more preferably 3.5-30% by weight, relative to the total weight of the liquid detergent. When the total mass of the water-miscible organic solvent is at least the above lower limit, the usability of the liquid cleaning agent is likely to be improved. When the total mass of the water-miscible organic solvent is equal to or less than the above upper limit, the liquid stability of the liquid cleaning agent is likely to be improved.
The content of component (B) with respect to the total mass of the water-miscible organic solvent is preferably 4-60% by mass, more preferably 10-45% by mass. When the content of the component (B) with respect to the total mass of the water-miscible organic solvent is at least the above lower limit, the usability of the liquid cleaning agent is likely to be improved. When the content of the component (B) relative to the total mass of the water-miscible organic solvent is equal to or less than the above upper limit, the liquid stability of the liquid detergent tends to be improved.

Examples of enzymes include protease, amylase, lipase, cellulase, mannanase and the like. As used herein, the term "enzyme" means an enzyme preparation.
As the protease, Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everlase 16L TypeEX, Everlase Ultra 16L, Esperase 8L, Alcalase 2.5L, Alcalase 2.5L, 2.5L, Ultraq. , Liquanase Ultra 2.5L, Liquanase Ultra 2.5XL, Coronase 48L, Purafect L, Purafect OX, Properase L available from Genencor, and the like.
Amylases include Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L and Stainzyme Plus 12L available from Novozymes as amylase preparations, Maxamyl available from Genencor, and Pullulanase available from Amano Enzyme. Amano, trade name DB-250 available from Seikagaku Corporation, and the like.
Examples of lipase include trade names Lipex 100L and Lipolase 100L available from Novozymes as lipase preparations.
Examples of cellulase include Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L and the like available from Novozymes as cellulase preparations.
Examples of mannanase include Mannaway 4L (trade name) available from Novozymes as a mannanase preparation.

An enzyme may be used individually by 1 type, and may use 2 or more types together.
When the liquid detergent contains an enzyme, the enzyme content is preferably 0.01 to 1.0% by mass, more preferably 0.03 to 0.9% by mass, relative to the total mass of the liquid detergent. , 0.05 to 0.8 mass % is more preferable. When the enzyme content is at least the above lower limit, the detergency of the liquid detergent can be easily increased. When the content of the enzyme is equal to or less than the above upper limit, it is easy to improve the liquid stability.

The liquid detergent of the present invention preferably contains water. The water content is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 40 to 90% by mass, relative to the total mass of the liquid detergent. When the water content is at least the above lower limit, the easiness of handling during production and the solubility in water during use are more excellent. When the content of water is equal to or less than the above upper limit, the detergency of the liquid detergent can be easily increased.

Solubilizers or viscosity reducers include aromatic sulfonic acids or salts thereof. Examples of aromatic sulfonic acids or salts thereof include toluenesulfonic acid, xylenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted naphthalenesulfonic acid, toluenesulfonate, xylenesulfonate, cumenesulfonate, substituted or non-substituted Substituted naphthalene sulfonates may be mentioned.
Salts include sodium salts, potassium salts, calcium salts, magnesium salts, ammonium salts, alkanolamine salts, and the like.
The solubilizers may be used singly or in combination of two or more.
When the liquid detergent contains a solubilizer or a viscosity reducer, the content of the solubilizer or viscosity reducer is preferably 3 to 7% by mass based on the total weight of the liquid detergent.

Examples of alkaline agents include monoethanolamine, diethanolamine, and triethanolamine.
Alkaline agents may be used alone or in combination of two or more.
When the liquid detergent contains an alkaline agent, the content of the alkaline agent is preferably 0.5 to 5% by mass with respect to the total mass of the liquid detergent.

Metal ion scavengers (chelating agents) include, for example, malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, HEDP (hydroxyethadisulfonic acid), or salts thereof, MGDA (methylglycine diacetic acid 3 sodium) and the like.
When the liquid detergent contains a chelating agent, the content of the chelating agent is preferably 0.01 to 20% by mass with respect to the total mass of the liquid detergent composition.

The antioxidant is not particularly limited, but is preferably a phenolic antioxidant because of its good detergency and liquid stability. Monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole , 2'-methylenebis(4-methyl-6-t-butylphenol and other bisphenol antioxidants, dl-α-tocopherol and other polymer-type phenol antioxidants are more preferred, monophenol antioxidants, high Molecular antioxidants are more preferred.
Among monophenolic antioxidants, dibutylhydroxytoluene is particularly preferred. Among polymeric phenolic antioxidants, dl-α-tocopherol is particularly preferred.
Antioxidants may be used alone or in combination of two or more.
When the liquid detergent contains an antioxidant, the content of the antioxidant is preferably 0.01 to 2 mass % with respect to the total mass of the liquid detergent composition.

Examples of antiseptic agents include Dow's trade name "Cason CG", Lonza's trade name "AN-1000", Thaw's trade name "MBS", and Clariant's trade name "NIPACIDE BIT 20." ” and the like.
When the liquid detergent contains an antiseptic, the content of the antiseptic is preferably 0.001 to 1 mass % with respect to the total mass of the liquid detergent.

Enzyme stabilizers include, for example, boric acid, borax, formic acid or salts thereof, benzoic acid, lactic acid or salts thereof, calcium salts such as calcium chloride and calcium sulfate.
The content of the enzyme stabilizer is preferably 0 to 2% by mass with respect to the total mass of the liquid detergent.

Examples of the texture improver include silicones such as dimethyl silicone, polyether-modified silicone, and amino-modified silicone.
The content of the texture improver is preferably 0 to 5% by mass with respect to the total mass of the liquid detergent.

A fluorescent whitening agent is an agent added for the purpose of improving the whiteness of white clothing. Examples of fluorescent brightening agents include distyrylbiphenyl-type fluorescent brightening agents.
The content of the fluorescent whitening agent is preferably 0 to 1% by mass with respect to the total mass of the liquid detergent.

Anti-soil redeposition agents include, for example, polyvinylpyrrolidone and carboxymethylcellulose.
The content of the anti-soil redeposition agent is preferably 0 to 2% by mass with respect to the total mass of the liquid detergent.

Examples of the pearl agent include the product name "SRN-100" manufactured by Clariant Co., Ltd., and the like. Examples of the soil release agent include BASF's product name "HP20".

The liquid detergent may contain a flavoring agent, a coloring agent, an emulsifying agent, an extract of a natural product, or the like, for the purpose of improving the added value of the product.
Examples of flavoring agents include fragrance compositions A, B, C and D described in Tables 11 to 18 of JP-A-2002-146399.
When the liquid detergent contains a flavoring agent, the content of the flavoring agent is preferably 0.1 to 1% by mass relative to the total weight of the liquid detergent.

Coloring agents include general-purpose dyes such as Acid Red 138, Polar Red RLS, Acid Yellow 203, Acid Blue 9, Blue No. 1, Blue No. 205, Green No. 3, and Turquoise P-GR. and pigments.
When the liquid detergent contains a coloring agent, the content of the coloring agent is preferably 0.00005 to 0.005% by mass (0.5 to 50 ppm by mass) relative to the total mass of the liquid detergent.

Examples of emulsifying agents include polystyrene emulsions and polyvinyl acetate emulsions, and usually emulsions having a solid content of 30 to 50% by mass are preferably used. Commercially available products include polystyrene emulsion (manufactured by Saiden Chemical Co., Ltd., trade name “Cybinol RPX-196 PE-3”, solid content 40% by mass).
When the liquid detergent contains an emulsifying agent, the content of the emulsifying agent is preferably 0.01 to 0.5% by mass based on the total weight of the liquid detergent.

Extracts of natural products include, for example, dog pagoda, barnacle, echinacea, scutellaria baicalensis, yellowfin tuna, Japanese coptis, allspice, oregano, pagoda, chamomile, honeysuckle, clara, key mussel, kay, bay bay, magnolia, burdock, comfrey, jassho, Burnt, Peony, Ginger, Goldenrod, Sambucus nigra, Sage, Mistletoe, Hosoba okera, Thyme, Hanagusuge, Clove, Unshu mandarin, Tea tree, Barberry, Houttuynia cordata, Nandina, Nigweed, Iron rush, Shirogaya, Boletus, Hollanda goat, Hop, Honshitan, Mountain grape, purple tagaya, sycamore, black leopard, wild rose, eucalyptus, lavender, rose, rosemary, balan, cedar, gilead balsam, hollyhock, broom, honey willow, jingyo lily, lily lily, bonito ginseng, yamabishi, thicket mustard, licorice, St. John's wort and other plant extracts.
The content of extracts such as natural products is preferably 0 to 0.5% by mass with respect to the total mass of the liquid detergent.

Examples of pH adjusters include sulfuric acid, hydrochloric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, ammonia and the like. Among these, sulfuric acid, sodium hydroxide, and potassium hydroxide are preferable, and sulfuric acid and sodium hydroxide are more preferable, from the viewpoint of making it easier to improve the liquid stability of the liquid detergent.
One of the pH adjusters may be used alone, or two or more of them may be used in combination.

In addition, the total amount of the components constituting the liquid detergent of the present invention does not exceed 100% by mass.

[Method for producing liquid detergent]
The liquid detergent of the present invention is produced by mixing components (A), (B), (C), and optionally optional components by a conventionally known method.
The pH of the liquid detergent of the present invention at 25°C is preferably 4-12, more preferably 6-10. When the pH is within the above numerical range, the sebum detergency and liquid stability of the liquid cleanser are likely to be improved. In addition, when the liquid detergent is used for coating and cleaning, it is easy to keep the liquid detergent at a viscosity that facilitates application.
The pH can be adjusted by adding an appropriate amount of pH adjuster.
The pH in the present specification indicates a value measured with a pH meter (for example, product name "HM-30G" manufactured by Toa DKK Co., Ltd.) at 25°C.

The viscosity of the liquid detergent at 25° C. is preferably 20 to 500 mPa·s, more preferably 50 to 300 mPa·s. When the viscosity of the liquid detergent at 25° C. is at least the above lower limit value, it becomes easier to apply the liquid detergent to stains on textile products and the like as intended when used for coating and cleaning. In addition, it is easy to suppress dripping from the container. When the viscosity of the liquid detergent at 25° C. is equal to or less than the above upper limit, the liquid detergent can be easily measured with a measuring cap or the like. In addition, when using for coating cleaning, it becomes easy to apply a liquid cleaning agent over a wide range of textile products and the like.
Viscosity in the present specification is a value measured with a Brookfield viscometer (manufactured by TOKIMEC) at 5°C, 25°C or 35°C. The viscosity measurement conditions are as follows.
<Measurement conditions>
[rotor]
The rotor numbers corresponding to the viscosities to be measured are as follows.
・When the viscosity of the object to be measured is less than 500 mPa·s: Rotor No. No. 2.
・When the viscosity of the object to be measured is 500 mPa·s or more and 2000 mPa·s: Rotor No. No. 3.
・When the viscosity of the object to be measured is 2000 mPa·s or more: Rotor No. No. 4.
[Rotor speed]
60 rpm.
[Read Number]
60 seconds after the start of rotation of the rotor.

The viscosity of the liquid detergent at 5° C. is preferably 30 to 1000 mPa·s, more preferably 60 to 500 mPa·s. When the viscosity of the liquid detergent at 5°C is within the above numerical range, the liquid detergent can be easily measured with a measuring cap or the like. Moreover, when using for coating cleaning, it becomes easy to apply a liquid cleaning agent over a wide range, such as a textile product.

The viscosity of the liquid detergent at 35° C. is preferably 10 to 300 mPa·s, more preferably 40 to 200 mPa·s. When the viscosity of the liquid detergent at 35° C. is within the above numerical range, it becomes easier to apply the liquid detergent to stains such as textile products as intended when using for coating cleaning. In addition, when the viscosity of the liquid detergent at 35°C is within the above numerical range, it is easy to suppress dripping from the container.

The viscosity difference between the viscosity of the liquid detergent at 5° C. and the viscosity at 35° C. (hereinafter also simply referred to as “viscosity difference”) is preferably less than 50 mPa·s, more preferably less than 40 mPa·s. When the viscosity difference is less than the above upper limit, it is easy to achieve both usability at low temperatures and usability at high temperatures.

[How to use the liquid detergent]
Methods of using the liquid detergent include, for example, a method of putting the liquid detergent into water together with the object to be washed during washing, and a method of immersing the object to be washed in an aqueous detergent solution prepared by previously dissolving the liquid detergent in water. and the like. Alternatively, the liquid detergent may be applied directly to the article to be washed, left for, for example, 3 minutes to 24 hours, and then normal washing may be performed (application washing).
The content of the liquid detergent in the aqueous detergent solution is not particularly limited. The amount of liquid detergent added to water is preferably 2 to 30 mL per 10 L of water, for example.
Items to be washed (textile products, etc.) include, for example, clothes, cloths, sheets, curtains, pillow covers, and the like. Materials such as textiles are not particularly limited, and may be natural fibers such as cotton, silk, or wool, or chemical fibers such as polyester or polyamide.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.
Raw materials used in this example are as shown in [Raw materials used] below.

[raw materials used]
<(A) Component>
a-1: A mixture of a higher alcohol having 12 carbon atoms and a higher alcohol having 13 carbon atoms (Safol 23, manufactured by Sasol Co.) with an average of 5 moles of ethylene oxide added thereto. (C12/13-EO5) synthesized together with a-3 described later by the following synthesis method.

<<Synthesis method of a-1>>
Put 137 g of 2-ethylhexanol (first grade reagent, manufactured by Kanto Chemical Co., Ltd.) and 41.7 g of calcium acetate monohydrate (special grade reagent, manufactured by Kanto Chemical Co., Ltd.) in a 500 mL beaker, and stir at room temperature (25 °C) to obtain a dispersion. While stirring the dispersion, 20.9 g of sulfuric acid (special grade reagent, manufactured by Kanto Kagaku Co., Ltd.) was added and mixed over 10 minutes using a dropping funnel (mixing step). Since heat is generated by the addition of sulfuric acid in the mixing step, the beaker was cooled in a water bath to control the reaction temperature at 30 to 50°C. After adding sulfuric acid, the mixture was stirred for 2 hours while maintaining the temperature at 50° C. to obtain an alkoxylation catalyst (α).
12.5 g of the above alkoxylation catalyst (α) and 1170 g of Safol 23 were placed in an autoclave and stirred. While stirring, the inside of the autoclave was replaced with nitrogen, the temperature was raised to 100° C., and dehydration was performed for 30 minutes under reduced pressure conditions of 1.3 kPa or less. Next, the temperature was raised to 160°C, and 1330 g of ethylene oxide (equivalent to 5 mol per 1 mol of Safol 23) was introduced under conditions of 0.1 to 0.5 MPa, stirred for 0.5 hours, and then heated to 80°C. After cooling, 2513 g of a mixture of crude a-1 (5 mol EO adduct of Safol 23) and a-3 (5 mol EO adduct of 2-ethylhexanol) was obtained as a reaction crude product. . After that, 1000 g of the mixture was collected in a 2 L beaker and heated to 80° C., then 10 g of KC floc and 5 g of Hyflo Supercel were added and stirred for 10 minutes. After that, it was filtered with a pressure filter to obtain a purified product.
The resulting purified product contained 98% by mass of component a-1 and 2% by mass of component a-3.

a-2: A mixture of a branched chain-containing higher alcohol having 12 carbon atoms and a branched chain-containing higher alcohol having 13 carbon atoms (manufactured by Sasol, Safol 23) added with an average of 7.5 moles of ethylene oxide, Lion Chemical Co., Ltd., trade name "NNAH-90".
a-3: 2-ethylhexanol (primary reagent, manufactured by Kanto Kagaku Co., Ltd.) added with an average of 5 moles of ethylene oxide. (2EH-EO5) obtained by the above <<synthesis method of a-1>>.

<(B) Component>
b-1: 3-Methoxy-3-methyl-1-butanol, manufactured by Kuraray Co., Ltd., trade name "Solfit".
<(B)' component (Comparative component of (B) component)>
b'-1: Ethanol, manufactured by Nippon Alcohol Sales Co., Ltd., trade name "Specific Alcohol 95 Degree Synthesis".
b'-2: Butyl carbitol, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "butyl carbitol".

<(C) Component>
c-1: Non-crosslinked copolymer of alkyl acrylate and alkyl methacrylate, trade name "Novethix HC200" manufactured by Lubrizol.
<(C)' component (comparative component of (C) component)>
c′-1: A crosslinked copolymer of alkyl acrylate and alkyl methacrylate, trade name “Carbopol Aqua 30” manufactured by Lubrizol.

<Optional component>
Enzyme 1: Protease, manufactured by Novozymes, trade name "Evalase 16L".
Water-miscible organic solvent: Polyethylene glycol, manufactured by Lion Corporation, trade name "PEG#1000-L60".
Solubilizer: p-toluenesulfonic acid, manufactured by Kyowa Hakko Kirin Co., Ltd., trade name "p-toluenesulfonic acid".
Alkaline agent: monoethanolamine, manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
Perfume: Perfume composition A described in Tables 11 to 18 of JP-A-2002-146399.
Antioxidant: dibutylhydroxytoluene, manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R".
pH adjuster: sulfuric acid, manufactured by Wako Pure Chemical Industries, Ltd., trade name "sulfuric acid"; or sodium hydroxide, manufactured by Kanto Chemical Co., Ltd., trade name "48% sodium hydroxide solution".
Water: Purified water, manufactured by Kanto Kagaku Co., Ltd., trade name "purified water".

[Examples 1 to 5, Comparative Examples 1 to 3]
According to the composition shown in Table 1, components (A) to (C) and optional components were added to water and mixed to obtain a mixed solution. The temperature of the mixed liquid was 25° C., and an appropriate amount of pH adjuster was added to the mixed liquid so that the pH of the mixed liquid was 9.8 to obtain a liquid detergent.
The obtained liquid detergent was evaluated for liquid stability and usability by the following evaluation methods. Table 1 shows the results. However, Examples 1 and 4 are reference examples.
The unit of the blending amount of each component in the table is "% by mass", which indicates the amount converted to pure content. The "appropriate amount" in the table is the amount of pH adjuster required to bring the pH of the liquid detergent of each example to the value in the table.
"Balance" in the table means that water is blended so that the total amount (% by mass) of all compounding components contained in the composition of each example is 100% by mass. "-" in the table indicates that the component was not blended.

<Evaluation of liquid stability>
A transparent glass bottle (standard wide mouth bottle, PS-No. 11) was filled with 100 mL of the liquid detergent of each example, and the lid was closed and sealed. In this state, it was stored in a constant temperature bath at 5° C. for 7 days.
After such storage, the appearance of the liquid was visually observed, and the liquid stability of the liquid detergent was evaluated according to the following evaluation criteria. "○" was set as a pass.
"Evaluation criteria"
◯: No sediment was observed at the bottom of the glass bottle, and the liquid had fluidity.
Δ: A precipitate is observed at the bottom of the glass bottle, but the precipitate disappears (dissolves) when the glass bottle is lightly shaken.
x: A precipitated substance is observed at the bottom of the glass bottle, and the precipitated substance does not disappear even if the glass bottle is gently shaken, or gelation or cloudiness occurs immediately after the preparation of the liquid detergent.

<Usability evaluation>
The liquid detergent of each example was placed in a 300 mL tall beaker and adjusted to each temperature (5° C. or 35° C.). After that, at each temperature, the viscosity was measured with a Brookfield viscometer (manufactured by TOKIMEC) 1 minute after the rotor started to rotate. The difference between the viscosity at 5°C and the viscosity at 35°C was defined as the "viscosity difference", and usability of the liquid detergent was evaluated according to the following evaluation criteria. "O" or "△" was regarded as a pass.
"Evaluation criteria"
○: Viscosity difference is less than 40 mPa·s.
Δ: Viscosity difference is 40 mPa·s or more and less than 50 mPa·s.
x: Viscosity difference is 50 mPa·s or more.

As shown in Table 1, it was found that Examples 1 to 5 to which the present invention was applied were excellent in liquid stability, with the liquid stability being "○". In addition, it was found that Examples 1 to 5 to which the present invention was applied had usability of “◯” or “Δ”, and could achieve both usability at low temperature and usability at high temperature.
On the other hand, Comparative Examples 1 and 2 in which the component (B)′ was used instead of the component (B) were rated “Poor” in usability. Comparative Example 3, in which the component (C)′ was used instead of the component (C), was evaluated as “Δ” in liquid stability and “×” in usability.

It was found that the liquid detergent composition for clothes of the present invention is excellent in liquid stability and can achieve both usability at low temperatures and usability at high temperatures.

Claims (2)

(A) component: a nonionic surfactant;
(B) component: a compound represented by the following general formula (b-1);
Component (C): From a repeating unit derived from a monomer represented by the following general formula (c-1) and a repeating unit derived from a monomer represented by the following general formula (c-2) and a non-crosslinked copolymer having one or more selected repeating units ,
The content of the component (B) is 1 to 5% by mass with respect to the total mass,
The content of the component (C) is 0.05 to 0.1% by mass with respect to the total mass,
A liquid detergent composition for clothes , wherein the mass ratio of component (B)/component (C) is 20-80 .

[In the formula, R ¹ to R ³ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁴ is a hydrogen atom or an acetyl group. ]

[In the formula (c-1), R ⁵¹ is a hydrogen atom or a methyl group, R ⁵² is a hydrogen atom, and in the formula (c-2), R ⁵³ is a hydrogen atom or a methyl group, and R ⁵⁴ is It is an alkyl group having 1 to 40 carbon atoms. ] The liquid detergent composition for clothes according to claim 1, wherein the component (A) is a compound represented by the following general formula (a-1).
R ¹¹ —O—(EO) _m —H (a-1)
[In the formula, R ¹¹ is an alkyl or alkenyl group having 10 to 18 carbon atoms, EO is an oxyethylene group, and m represents the average repeating number of EO and is a number of 2 to 20. ]