JP6964468B2 - How to wash textiles - Google Patents

Description

The present invention relates to a method for washing textile products.

In recent years, an increasing number of consumers are using fabric softeners for the purpose of imparting flexibility and scenting. When a softener is contained in the rinse water after washing, the textile products such as towels and clothes have a soft finish, but also have a feature that the hydrophilicity is lowered and the water absorption is easily lowered.
In Patent Document 1, in order to prevent a decrease in hydrophilicity due to softener treatment, _{a polymer compound having a structural unit represented by −S (= O) 2} − and a structural unit having a cationic group. A method of processing the fabric has been proposed. In the embodiment, a commercially available powder detergent for clothes and the above-mentioned polymer compound are dissolved in tap water supplied to a washing machine, a test cloth is put therein, and the washing machine is washed (washed for 15 minutes, rinsed twice) and rinsed. The method of adding a commercially available soft finishing agent at the beginning of the second time is described.

Japanese Unexamined Patent Publication No. 2008-190091

However, in the conventional method, the flexibility and water absorption of the textile product after the softening treatment are not always sufficient.
The present invention provides a washing method in which a textile product after being washed and dried has an excellent fluffy and voluminous feel and can suppress a decrease in water absorption due to a softener treatment.

The present invention has the following aspects.
[1] A liquid detergent containing the following component (A) and the following component (B) is diluted with water to obtain a cleaning solution, and after performing a cleaning step of cleaning the textile product in the cleaning solution at least once, the following ( E) A method for washing a textile product, which comprises a rinsing step of rinsing the textile product with rinse water containing an ingredient.
Component (A): A polymer having at least one of a structural unit represented by the following formula (a-1) and a structural unit represented by the following formula (a-2).
(B) Ingredient: Surfactant (excluding higher fatty acid salts).
(E) Ingredient: One or more soft bases selected from the group consisting of tertiary amine salt type cationic surfactants and quaternary ammonium type cationic surfactants.

(In the formula, R ¹ and R ² are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and X ⁻ is a counterion.)

(In the formula, R ³ and R ⁴ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and X ⁻ is a counterion.)

[2] The method for washing a textile product according to [1], wherein the mass ratio of the component (B) to the component (A) represented by (B) / (A) is 30 or more.
[3] The method for washing a textile product according to [1] or [2], wherein the component (B) contains at least one of the following component (B-1) and the following (B-2).
(B-1) Ingredient: Nonionic surfactant.
(B-2) Ingredient: Anionic surfactant (excluding higher fatty acid salts).
[4] The (B-2), wherein the component (B) contains the component (B-1) and the component (B-2) and is represented by (B-1) / (B-2). The method for washing a textile product according to [3], wherein the mass ratio of the component (B-1) to the component is 0.9 to 5.
[5] The textile product of [3] or [4], which is represented by (B-1) / (A) and has a mass ratio of the component (B-1) to the component (A) of 10 or more. Washing method.
[6] The method for washing a textile product according to any one of [1] to [5], wherein the component (B) contains the following component (C).
(C) Ingredient: Higher fatty acid or salt thereof.
[7] The method for washing a textile product according to any one of [1] to [6], wherein the liquid detergent contains the following component (D).
Component (D): From the group consisting of an alkyl group or phenyl group having 1 to 6 carbon atoms, an alkylene glycol ether having an alkylene glycol unit having 2 or 3 carbon atoms, and a compound represented by the following formula (d-1). One or more solvents of choice.

(In the formula, R ^{51 to} R ⁵³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ⁵⁴ is a hydrogen atom or acetyl group.)

[8] The method for washing a textile product according to any one of [1] to [7], wherein the content of the component (A) is 0.3 to 15 mass ppm with respect to the total mass of the washing liquid.
[9] The method for washing a textile product according to any one of [1] to [8], wherein the content of the component (E) is 10 to 200 mass ppm with respect to the total mass of the rinse water.

According to the washing method of the present invention, the textile product after washing and drying has an excellent fluffy and voluminous feel (hereinafter, may be simply referred to as "fluffy feeling"), and also absorbs water due to the softener treatment. It is possible to suppress the deterioration of sex.

≪Liquid cleaner≫
The liquid detergent of the present embodiment contains the component (A) and the component (B).
<Ingredient (A)>
The component (A) is a constituent unit represented by the following formula (a-1) (hereinafter, also referred to as a constituent unit (a-1)) and a constituent unit represented by the following formula (a-2) (hereinafter referred to as a constituent unit). , Also referred to as a constituent unit (a-2)).
The structural units (a-1) and (a-2) are structural units derived from the dialkyldialyl ammonium salt monomer represented by the following formula (a-4).
The component (A) is adsorbed on the fiber by forming a complex with the component (B) in a cleaning solution obtained by diluting the liquid detergent with water, exerting a shape-retaining effect and giving the fiber after drying a fluffy feeling. , Contributes to the suppression of decrease in water absorption due to the softener treatment.
As the component (A), one type may be used alone, or two or more types may be used in combination.

In the formula (a-4), R ⁸ and R ⁹ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, respectively.
^{R 1} , R ² in the formula (a-1) ^{, and R 3} and R ⁴ in the formula (a-2) are the same as ^{R 8} and R ^{9 in the} formula (a-4), respectively.
^{X −} in the formulas (a-1), (a-2) and (a-4) is a counterion, for example, halogen ions such as chlorine ion and bromine ion; sulfate ion, nitrate ion, sulfite ion and the like. Inorganic acid ions; organic acid ions such as methyl sulfate ion, acetate ion, and lactate ion; can be mentioned.

In addition to the structural units (a-1) and (a-2), the component (A) has a structural unit derived from another monomer copolymerizable with the monomer represented by the above formula (a-4). You may.
The component (A) has a structural unit represented by the following formula (a-3) (hereinafter, also referred to as a structural unit (a-3)) in terms of imparting a fluffy and voluminous feel and formulation. preferable.
In the formula (a-3), R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁶ and R ⁷ are independently hydrogen atoms and an alkyl group having 1 to 3 carbon atoms. Alternatively, it is a hydroxyalkyl group having 1 to 3 carbon atoms.

The mass average molecular weight of the component (A) is usually 1,000 to 5,000,000, preferably 10,000 to 3,000,000, more preferably 100,000 to 2,000,000, and further 500. Thousands to 2,000,000 are more preferred. The mass average molecular weight in the present specification means a value obtained by gel permeation chromatography (GPC) using polyethylene glycol as a standard substance.
The form of polymerization of the component (A) is not particularly limited and may be block polymerization, random polymerization or graft polymerization.

The total of the constituent units (a-1) and the constituent units (a-2) is preferably 10 mol% or more, more preferably 20 mol% or more, based on all the constituent units of the component (A).
(A) When the component has the constituent unit (a-3), [the sum of the constituent unit (a-1) and the constituent unit (a-2)]: the molar ratio of the constituent unit (a-3) is 1: 9 to 7: 3 is preferable, and 2: 8 to 6: 4 is more preferable.

As the component (A), formula (a-4) a structural unit derived from a diallyl dialkyl ammonium salt represented ^{by, R 5, R 6, R} 7 in the structural unit (above (a-3) derived from acrylamide A polymer having (a structural unit in which is a hydrogen atom) is preferable, and a copolymer of diallyldimethylammonium chloride ( ^{a compound in which R 8} and R ⁹ are methyl groups and X ⁻ is a chloride ion in the above (a-4)) and acrylamide are preferable. Is more preferable.

As the component (A), a synthetic product or a commercially available product may be used.
The component (A) can be produced by ordinary radical polymerization. For example, it can be produced by polymerizing the monomer constituting the component (A) by a polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization. Further, in the polymerization, it is preferable to use a polymerization initiator used for ordinary radical polymerization, for example, peroxides such as benzoyl peroxide and potassium persulfate, azobisisobutyronitrile, and azobiscyanovaleric acid. And other azo compounds can be used.

<Ingredient (B)>
The component (B) is a surfactant. The component (B) exerts a cleaning effect and contributes to the adsorption of the component (A) to the fiber by forming a complex with the component (A). As a result, the shape-retaining effect of the component (A) is exhibited, the textile product after washing and drying is given a fluffy feeling, and the decrease in water absorption due to the softener treatment is suppressed.
As the component (B), a known surfactant used as a cleaning agent for textile products can be used. As the component (B), one type may be used alone, or two or more types may be used in combination.

The component (B) is the following component (B-1) and the following (B) in that higher detergency can be obtained and the effect of forming a complex with the component (A) and adsorbing the component (A) to the fiber is excellent. -2) It is preferable to contain at least one of the components.
(B-1) Ingredient: Nonionic surfactant.
(B-2) Ingredient: Anionic surfactant (excluding higher fatty acid salts).

[(B-1) component]
As the nonionic surfactant as the component (B-1), a compound represented by the following formula (b-1-1) or a compound represented by the following formula (b-1-2) is preferable.
R ^11- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ¹² ... (b-1-1)
R ^21- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (b-1-2)
In formula (b-1-1), R ¹¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ¹² is an alkyl group having 1 to 6 carbon atoms, and s represents the average number of repetitions of EO. ~ 20, t represents the average number of repetitions of PO, 0-6, u represents the average number of repetitions of EO, 0-20, and EO represents an oxyethylene group. , PO represents an oxypropylene group. When t is 1 or more, in [(EO) _s / (PO) _t ], the oxyethylene group and the oxypropylene group may be random polymerization or block polymerization.
In formula (b-1-2), R ²¹ is a hydrocarbon having 6 to 22 carbon atoms, v represents the average number of repetitions of EO, 3 to 20, and w represents the average number of repetitions of PO. It is a number from 0 to 6, x represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, and PO represents an oxypropylene group. When w is 1 or more, in [(EO) _v / (PO) _w ], the oxyethylene group and the oxypropylene group may be random polymerization or block polymerization.
The average number of repetitions can be measured by gas chromatography or the like.

In the formula (b-1-1), ^{the carbon number of R 11} is preferably 9 to 21, and more preferably 11 to 21. R ¹¹ is preferably an alkyl group or an alkenyl group. R ¹¹ may be linear or branched. ^{R 11} is preferably an alkyl group having 7 to 22 carbon atoms in a straight chain or a branched chain, or an alkenyl group having 7 to 22 carbon atoms in a straight chain or a branched chain, in terms of being superior in detergency.
R ¹² may be linear or branched. Of these, a methyl group and an ethyl group are preferable.
s + u is preferably 6 to 20, more preferably 6 to 18, even more preferably 11 to 18, and particularly preferably 14 to 18. t is preferably 0 to 3, more preferably 0.

In the formula (b-1-2), ^{the carbon number of R 21} is preferably 10 to 20, and more preferably 10 to 18. In the formula (b-1-2), R ²¹ may be a linear hydrocarbon group, and is a group selected from a primary hydrocarbon group of a branched chain and a secondary hydrocarbon group of a straight chain. There may be.
In the formula (b-1-2), when R ²¹ is a linear hydrocarbon group, v + x is preferably 3 to 20, more preferably 5 to 18, further preferably 6 to 18, and particularly preferably 11 to 18. .. w is a number from 0 to 6, preferably 0 to 3.
In formula (b-1-2), when R ²¹ is a group selected from a primary hydrocarbon group of a branched chain and a secondary hydrocarbon group of a straight chain, v + x is particularly preferably 3 to 8. w is preferably 0.

It is preferable that the component (B-1) contains a compound (that is, a polyoxyethylene fatty acid alkyl ester) in which t in the formula (b-1-1) is 0. It is more preferable to contain a polyoxyethylene fatty acid methyl ester (hereinafter referred to as "MEE") in which t in the formula (b-1-1) is 0 and R ^{12 is a methyl group.}
The component (B-1) is a ^{linear or branched alkyl group or alkenyl group in which R 21} in the formula (b-1-2) has 10 to 18 carbon atoms, w is 0, and (v + x). ) Is 7 to 16 (hereinafter referred to as “AE”), and MEE is preferably contained.
The total of AE and MEE is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass with respect to the total mass of the component (B-1).
When the component (B-1) contains AE and MEE, the mass ratio of MEE / AE is preferably 0.4 to 20, more preferably 0.5 to 10, and even more preferably 0.8 to 5. When the mass ratio of MEE / AE is within the above range, the rinsing property becomes better, the surfactant is less likely to remain after the rinsing step, and the decrease in water absorption is further suppressed. Also, the feeling of plumpness becomes higher.

[(B-2) component]
Examples of the anionic surfactant as the component (B-2) include linear alkylbenzene sulfonic acid or a salt thereof (LAS); α-olefin sulfonic acid salt (AOS); linear or branched alkyl sulfate ester salt (AS). Examples thereof include alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt (AES); alkane sulfonate having an alkyl group; α-sulfo fatty acid ester salt (MES) and the like.
Examples of the salt in the anionic surfactant include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

The component (B-2) preferably contains LAS or AES.
As the LAS, a linear alkyl group having 8 to 16 carbon atoms is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
As the AES, a compound represented by the following formula (b-2-1) is preferable.
R ^31- O- (EO) _j- SO ₃ M ... (b-2-1)
(In the formula, R ³¹ is a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, j represents the average number of repetitions of EO, is a number of 1 to 10, and M is a counterion. be.)

The content of LAS is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, based on the total mass of the component (B-2). When the LAS content is at least the lower limit of the above range, the recontamination prevention performance is excellent and the handling property of the liquid detergent is also excellent.

In the liquid detergent, the mass ratio of (B) / (A) is preferably 30 or more, more preferably 40 or more, further preferably 70 or more, and particularly preferably 80 or more. The upper limit is preferably 1000 or less, more preferably 400 or less, and even more preferably 200 or less.
When it is at least the lower limit of the above range, the dispersibility of the component (A) in the liquid detergent is more excellent. When it is less than the upper limit, a complex of the component (A) and the component (B) is sufficiently formed to give a fluffy feeling to the textile product after washing and drying, and a decrease in water absorption due to the softener treatment. It is superior in the effect of suppressing.

When the liquid detergent contains the component (B-1), the mass ratio of (B-1) / (A) is preferably 10 or more. The larger this value is, the more excellent the effect of giving a fluffy feeling to the textile products after washing and drying.

When the component (B) contains the component (B-1) and the component (B-2), the mass ratio of (B-1) / (B-2) is preferably 0.9 to 5, and 1 to 2.5. Is more preferable, and 1.2 to 2 is even more preferable.
When the component (B-1) / component (B-2) is at least the lower limit of the above range, it is more excellent in the effect of giving a fluffy feeling to the textile product, and when it is at least the upper limit, (A) in the liquid detergent. ) The dispersibility of the components is better.

The total content of the component (B-1) and the component (B-2) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and 90 to 90 to the total mass of the component (B). 100% by mass is more preferable. When the total content of the component (B-1) and the component (B-2) is at least the lower limit of the above range, the effect of giving a fluffy feeling to the textile product after washing and drying is more excellent.

<Ingredient (C)>
The liquid detergent preferably contains a higher fatty acid or a salt thereof, which is the component (C). By containing the component (C), foaming due to the component (B) is reduced and the rinsing property is improved, the surfactant is less likely to remain after the rinsing step, and the decrease in water absorption is further suppressed.
"Higher fatty acid" means a fatty acid having 8 to 22 carbon atoms. As the higher fatty acid, a chain monocarboxylic acid having 8 to 18 carbon atoms is preferable. Specific examples thereof include compounds represented by the general formula: R ^41- COOH (in the formula, R ⁴¹ is an aliphatic hydrocarbon group having 7 to 21 carbon atoms). In the formula, ^{the aliphatic hydrocarbon group of R 41} may be linear or branched chain, a linear or branched alkyl group, or a linear or branched alkenyl. Groups are preferred. The number of carbon atoms in the aliphatic hydrocarbon group of ^{R 41 is preferably 10 to 20.}

Examples of the salt form in the component (C) include alkali metal salts, alkaline earth metal salts, amine salts, ammonium salts and the like. Examples of the alkali metal salt include sodium salt, potassium salt and the like. Examples of the alkaline earth metal salt include calcium salts and magnesium salts. Examples of the amine salt include alkanolamine salts (monoethanolamine salt, diethanolamine salt, triethanolamine salt, etc.) and the like.
The component (C) may be used alone or in combination of two or more.
Further, the component (C) may be a mixture having a single chain length or a mixture having two or more chain lengths.
When the liquid detergent contains the component (C), the mass ratio of (B) / (C) is preferably 1 to 35, more preferably 4 to 35, and even more preferably 6 to 35. When it is not more than the upper limit value, the rinsing property is more excellent. When it is at least the lower limit value, the stability of the liquid detergent is more excellent.
In particular, it is preferable that the component (C) contains a coconut fatty acid or a salt thereof from the viewpoint of rinsability and formulation. The total ratio of the coconut fatty acid and the coconut fatty acid salt to the total mass of the component (C) is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. ..

<Ingredient (D)>
The liquid detergent preferably contains the following component (D).
Component (D): An alkylene glycol ether having an alkyl group or phenyl group having 1 to 6 carbon atoms and an alkylene glycol unit having 2 or 3 carbon atoms (hereinafter referred to as "specific alkylene glycol"), and the following formula (d-). One or more solvents selected from the group consisting of the compounds represented by 1).
By including the component (D) in the liquid detergent, it becomes easy to mix the component (A), the component (B) and the optional component when preparing the liquid detergent.
The component (D) may be used alone or in combination of two or more.

In the formula (d-1), R ^{51 to} R ⁵³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ⁵⁴ is a hydrogen atom or acetyl group.
Of R ^{51 to} R ⁵³ , it is preferable that two or more are hydrogen atoms. When ^{any one of R 51 to} R ⁵³ is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 2, and more preferably 1. R ⁵⁴ is preferably a hydrogen atom.

Examples of the compound represented by the formula (d-1) include 3-methoxybutanol, 3-methoxy-3-methylbutanol, 3-methoxy-2-methylbutanol, 3-methoxy-1-methylbutanol, and 3-methoxy-. 3-Methylbutyl acetate is preferable, and 3-methoxy-3-methylbutanol is more preferable.
As the "specific alkylene glycol", (poly) alkylene glycol (mono or di) alkyl ether is preferable, and diethylene glycol monobutyl ether (also known as butyl carbitol) is more preferable.

When the liquid detergent contains the component (D), the mass ratio of (D) / (B) is preferably 0.03 to 0.8, more preferably 0.05 to 0.5, and 0. 1 to 0.3 is more preferable.

<Arbitrary ingredient>
In addition to the above components, the liquid detergent may contain components known in the liquid detergent for textile products as long as the effects of the present invention are not impaired.
For example, water, enzymes, chelating agents, hydrotropes, detergency builders, stabilizers, alkaline agents (eg, alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, etc.), texture improvers such as silicone, antiseptic. Examples of agents, fluorescent agents, dye transfer inhibitors, pearl agents, antioxidants, colorants include general-purpose pigments or pigments, emulsifying agents, fragrances, pH adjusters and the like.
The liquid detergent is obtained by mixing the component (A), the component (B), and the components to be blended if necessary. That is, in the liquid detergent, the component (A) and the component (B) are contained in a mixed state.
≪Softener composition≫
<Ingredient (E)>
The softener composition of the present embodiment contains the following component (E).
(E) Ingredient: One or more soft bases selected from the group consisting of tertiary amine salt type cationic surfactants and quaternary ammonium type cationic surfactants.
As the component (E), a tertiary amine salt type cationic surfactant and a quaternary ammonium type cationic surfactant known as a base material of the softener can be used.

By adsorbing to the textile product, the component (E) gives the textile product after drying a soft touch and contributes to the improvement of the plumpness.

As the component (E), for example, 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms (hereinafter, also referred to as “long-chain hydrocarbon groups”) which may be separated by an ester group or an amide group are preferable. Can be used with one or more compounds selected from the group consisting of 2-3 tertiary amine compounds, salts thereof and quaternized products thereof.
The long-chain hydrocarbon group preferably has 17 to 26 carbon atoms, more preferably 19 to 24 carbon atoms. The long-chain hydrocarbon group may be saturated or unsaturated. The long-chain hydrocarbon group may be chain-like (linear or branched-chain) or may have a ring structure. Chained hydrocarbon groups are preferred. The chain hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.
A long-chain hydrocarbon group has at least one fragmenting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is partitioned by the fragmenting group. good. When the carbon chain has a dividing group, the carbon atom of the dividing group shall be counted as the number of carbon atoms of the long-chain hydrocarbon group.
Long-chain hydrocarbon groups are usually industrially used unhydrogenated beef fat-derived fatty acids, fatty acids obtained by hydrogenating or partially hydrogenating unsaturated portions, and plant-derived unhydrogenated fatty acids such as palm palms and oil palms. It is preferably a monovalent group introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated portion.

The salt of the tertiary amine compound is obtained by neutralizing the tertiary amine compound with an acid. The acid used for neutralizing the tertiary amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid.
A quaternized product of an amine compound is obtained by reacting this amine compound with a quaternizing agent. Examples of the quaternizing agent used for quaternizing the amine compound include alkyl halides such as methyl chloride and dialkyl sulfuric acid such as dimethyl sulfate. When these quaternary agents are reacted with an amine compound, the alkyl group of the quaternary agent is introduced into the nitrogen atom of the amine compound, and a salt of the quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion is formed. .. The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

<Other ingredients>
Softener compositions are known in softener compositions such as water, water-soluble solvents, nonionic surfactants, cyclic dextrins, enzyme stabilizers, chelating agents, fragrances, dyes, pigments, preservatives, UV absorbers, antibacterial agents, etc. May contain the components of.
Cyclic dextrin contributes to the anti-recontamination effect. The cyclic dextrin may be any dextrin having one or more cyclic structures in the molecule, and examples thereof include cyclodextrin and highly branched cyclic dextrin. Of these, highly branched cyclic dextrins are preferred.

≪Washing method≫
In the washing method of the present embodiment, the liquid detergent is diluted with water to obtain a washing liquid, and after performing a washing step of washing the textile product in the washing liquid at least once, the textile product is washed with rinse water containing the component (E). It has a rinsing step for rinsing.
The method of diluting the liquid detergent with water is not particularly limited, and any method may be used as long as the liquid detergent can be dispersed in water before the start of the cleaning step or during the cleaning step.
Examples of textile products include clothing, fabrics, sheets, curtains, carpets and the like.
The material of the textile product is not particularly limited, and examples thereof include natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.

In the cleaning step, an external force is applied to the textile product in the cleaning liquid to transfer dirt into the cleaning liquid, and then dehydration or the like is performed to separate the textile product from the cleaning liquid.
In the rinsing step, after the cleaning step, no liquid detergent is added, and the liquid detergent remaining in the textile product is preferably applied with an external force in the rinse water containing the component (E). After transferring the components of the above into the rinse water, dehydration or the like is performed to separate the textile product from the rinse water.
The cleaning step is usually performed once. It may be repeated twice or more. The rinsing step may be performed once or repeated twice or more.
When the rinsing step is performed twice or more, the component (E) is contained in the rinsing water at least once. Preferably, in the final rinsing step, the component (E) is contained in the rinsing water. The rinsing step is preferably performed once because the shape-retaining effect of the component (A) is more likely to be exhibited.
The method of applying an external force to the textile product may be, for example, a method of applying a mechanical force by a washing machine or a method of hand washing.

The content of the component (A) is preferably 0.3 to 15 mass ppm, more preferably 0.5 to 10 mass ppm, still more preferably 0.9 to 3 mass ppm, based on the total mass of the cleaning liquid.
When the content of the component (A) is within the above range, the fibers after drying are given a fluffy feeling, and the effect of suppressing a decrease in water absorption due to the softener treatment is more excellent.
The content of the component (E) is preferably 10 to 200 mass ppm, more preferably 20 to 150 mass ppm, still more preferably 30 to 100 mass ppm, based on the total mass of the rinse water.
When the content of the component (E) is within the above range, the effect of giving a fluffy feeling to the dried fibers is more excellent.

The dilution ratio when the softener composition is dispersed in water to obtain rinse water is not particularly limited, but for example, the amount of the softener composition added to 1 L of water is designed to be 0.3 to 0.5 g. Is preferable.
When the dilution ratio of the softener composition is in the above range, for example, a softener composition having the following composition is preferable.
A softener composition in which the component (E) is 5 to 15% by mass, water is 70 to 95% by mass, and the total is 100% by mass with respect to the total mass of the softener composition.
When the component (E) is at least the lower limit of the above range, the effect of imparting a fluffy feeling to the textile product after washing and drying is more excellent, and when it is at least the above upper limit, freeze-restorability can be maintained.

<Mechanism of action>
According to the washing method of the present embodiment, the textile product after washing and drying is excellent in a fluffy and voluminous feel, and can suppress a decrease in water absorption due to the softener treatment.
The reason is considered as follows. After the complex of the component (A) and the component (B) is formed in the process of diluting the liquid detergent containing the component (A) and the component (B) with water, and the complex is adsorbed on the fiber in the cleaning step. By further adsorbing the component (E) in the rinsing step, the dried fibers are given a fluffy and voluminous feel, and the effect of suppressing the decrease in water absorption due to the softener treatment can be obtained.
Further, the component (B) contributes to the dispersibility of the component (A) in the liquid detergent, and when the liquid detergent contains the component (A) and the component (B) in a mixed state, it is a liquid. It is believed that the complex is formed more efficiently in the process of diluting the cleaning agent with water.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description.

(Raw materials used)
<Ingredient (A)>
A-1: Dimethyldialylammonium-acrylamide copolymer (manufactured by Lubrizol, trade name "Neverite 300").
A-2: Dimethyldialylammonium-acrylamide copolymer (manufactured by Lubrizol, trade name "Neverite 302").
A-3: Dimethyldialylammonium / acrylamide / acrylic acid polymer (manufactured by Lubrizol, trade name "Marcoat 3330PR").
a-4: Dimethyldialylammonium / acrylamide / acrylic acid polymer (manufactured by Lubrizol, trade name "Marcoat 3331PR").

<Comparative component (A')>
A'-5: Made by Lubrizol, trade name "Marcourt 2003".
A'-6: POE-modified silicone (manufactured by Toray Dow Silicone Co., Ltd., trade name "CF1188N", silicone compound into which a polyoxyethylene group has been introduced).

<Ingredient (B)>
[(B-1) component]
B-1-1 (MEE): Fatty acid methyl ester ethoxylate (12 to 14 carbon atoms of fatty acid, 15 average addition moles of EO), in the general formula (b-1-1), R ¹¹ = 11 carbon atoms. Alkyl group and alkyl group having 13 carbon atoms, R ¹² = methyl group, s = 15, t = 0, u = 0. Synthesized according to the following synthesis example 1.
B-1-2 (AE (EO15)): Natural alcohol with 15 moles of ethylene oxide added. In the above formula (b-1-2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 15, w = 0, x = 0. Synthesized according to Synthesis Example 2 below.
B-1-3 (AE (EO12)): Natural alcohol with 12 moles of ethylene oxide added. In the above formula (b-1-2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 12, w = 0, x = 0.
B-1-4 (EO / PO nonion): Natural alcohol (12 carbons by mass ratio / 14 carbons = 7/3), ethylene oxide equivalent to 8 mol, propylene oxide equivalent to 2 mol, equivalent to 8 mol Ethylene oxide blocks are added in this order. In the above formula (b-1-2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, x = 8.
B-1-5: A secondary alcohol having 12 carbon atoms and a secondary alcohol having 14 carbon atoms to which ethylene oxide equivalent to 7 mol is added. Product name "Softanol 70", manufactured by Nippon Shokubai Co., Ltd. In the above formula (b-1-2), R ²¹ = a secondary alkyl group having 12 carbon atoms and a secondary alkyl group having 14 carbon atoms, v = 7, w = 0, x = 0.

[(B-2) component]
B2-11: Sodium linear alkylbenzene sulfonate (LAS), manufactured by Lion Corporation, trade name "Rypon LH-200", linear alkyl group has 10 to 14 carbon atoms.
B-2-2: Polyoxyethylene alkyl ether sodium sulfate (AES), represented by the above formula (b-2-1), R ³¹ = linear alkyl group having 12 to 14 carbon atoms, j = 1.0, A compound in which M = sodium.
[(C) component]
C-1: Palm fatty acid: Defoamer, trade name "Palm fatty acid", NOF CORPORATION.

<Ingredient (D)>
D-1: Diethylene glycol monobutyl ether, trade name "butyl diglycol", manufactured by Nippon Emulsifier.
D-2: 3-Methoxy-3-methylbutanol, trade name "Solfit", manufactured by Kuraray Co., Ltd.

<Arbitrary component (X)>
-BHT: Dibutylhydroxytoluene (antioxidant), trade name "SUMILZER BHT-R", manufactured by Sumitomo Chemical Co., Ltd. The blending amount is 0.05% by mass with respect to the total mass of the liquid detergent.
-Ethanol: Water-miscible organic solvent, "fermented alcohol water-containing first grade", manufactured by Japan Alcohol Trading Co., Ltd. The blending amount is 2% by mass with respect to the total mass of the liquid detergent.
-Metal ion supplement (chelating agent): Citric acid (manufactured by Yushi Kogyo Co., Ltd.). The blending amount is 0.3% by mass with respect to the total mass of the liquid detergent.
-Cleaning aid: A water-soluble polymer containing an alkylene terephthalate unit and / or an alkylene isophthalate unit and having a (poly) oxyalkylene unit, trade name "TexCare SRN-170C", manufactured by Clariant Japan. The blending amount is 0.5% by mass with respect to the total mass of the liquid detergent.
-Storage stability improver: Sodium benzoate, manufactured by Toagosei Co., Ltd. The blending amount is 0.2% by mass with respect to the total mass of the liquid detergent.
-Storage stability improver: p-toluenesulfonic acid, trade name "paratoluenesulfonic acid", manufactured by Kyowa Hakko Kogyo Co., Ltd. The blending amount is 0.2 mass with respect to the total mass of the liquid detergent.
-Enzyme: Product name "Coronase (registered trademark) 48L", manufactured by Novozymes. The blending amount is 0.5% by mass with respect to the total mass of the liquid detergent.
Perfume: Perfume, perfume composition A shown in Tables 11 to 18 of JP-A-2002-146399, the blending amount is 0.8% with respect to the total mass of the liquid detergent.
-Dye: Colorant, trade name "Yellow No. 203", manufactured by Ami Kasei Co., Ltd., the blending amount is 1 ppm with respect to the total mass of the liquid detergent.
-Dye: Colorant, trade name "Red No. 106", manufactured by Ami Kasei Co., Ltd., the blending amount is 1.5 ppm with respect to the total mass of the liquid detergent.

<pH adjuster>
-MEA: Monoethanolamine (alkaline agent), trade name "monoethanolamine", manufactured by Nippon Shokubai Co., Ltd. The blending amount is an amount (appropriate amount) at which the pH (25 ° C.) of the liquid detergent becomes the value shown in the table.

<Ingredient (E)>
E-1 (TES): Quaternary ammonium type soft base (cationic surfactant described in Example 4 of JP-A-2003-12471. Obtained in Synthesis Example 4 below).
E-2 (DES): Quaternary ammonium type soft base, N, N-di (taro oil oxyethyl) -N, N-dimethylammonium chloride.

<Arbitrary component (Y)>
Nonion EO60: A compound in which ethylene oxide is added to a nonionic surfactant, an adduct of 60 mol of ethylene oxide of a primary isotridecyl alcohol, and lutenzole TO3 manufactured by BASF.
Nonion EO21: A compound obtained by adding an average of 21 mol of ethylene oxide to a nonionic surfactant and lauryl alcohol.
-Glycerin: Made by Kanto Chemical Co., Inc., trade name "glycerin".
-Calcium chloride: (enzyme stabilizer), manufactured by Kanto Chemical Co., Inc., trade name "calcium chloride (special grade)".
Perfume: Fragrance, Perfume Composition A according to Tables 11 to 18 of JP-A-2002-146399.
-EDTA: Ethylenediaminetetraacetic acid, manufactured by Kanto Chemical Co., Inc., trade name "ethylenediaminetetraacetic acid".
HEDP: (chelating agent), 1-hydroxyethane-1,1-diphosphonic acid (manufactured by Rhodia, trade name "BRICUEST ADPA-60A").
-Cluster dextrin (registered trademark, manufactured by Glico Foods Co., Ltd.). The main component has a molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and has a weight average degree of polymerization of about 2,500 in which a large number of glucan chains are bonded to the cyclic portion. dextrin. The cyclic structure portion is composed of about 16 to 100 glucoses, and a large number of acyclic branched glucan chains are bonded to this cyclic structure.

<Synthesis Example 1: Synthesis of B-1-1 (MEE)>
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Alumina hydroxide / magnesium (Kyoward 300 (trade name), manufactured by Kyowa Chemical Industry Co., Ltd.) having a composition of 2.5 MgO / Al2O3 / zH2O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere, and then fired hydroxide. An alumina-magnesium (unmodified) catalyst was obtained. 2.2 g of calcined alumina-magnesium hydroxide (unmodified) catalyst, 2.9 mL of 0.5N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester, and 70 g of myristic acid methyl ester were charged into a 4 L autoclave. The catalyst was modified in. Then, after replacing the inside of the autoclave with nitrogen, 1052 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, and the reaction was carried out with stirring.
The obtained reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filtration aids were added and mixed, and then the catalyst was filtered off to obtain B-1-1 (MEE). ..

<Synthesis Example 2: Synthesis of B-1-2 (AE (EO15))>
224.4 g of CO-1214 (trade name) manufactured by Procter & Gamble Co., Ltd. and 2.0 g of a 30 mass% NaOH aqueous solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. Next, after dehydration at a temperature of 100 ° C. and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160 ° C. Then, while stirring the reaction solution, 760.6 g of ethylene oxide (gaseous) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blow tube while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C.
After the addition of ethylene oxide was completed, the mixture was aged at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes.
Next, after cooling the temperature to 100 ° C. or lower, 70% by mass p-toluenesulfonic acid was added to neutralize the reaction product so that the pH of the 1% by mass aqueous solution of the reaction product became about 7, and B-1-2 (AE (EO15)) was obtained.

<Synthesis Example 3: Synthesis of B-2-2 (AES)>
In an autoclave with a capacity of 4 L, 400 g of CO1270 alcohol (mass ratio of 12 carbon atoms / 14 carbon atoms mass ratio = 75/25) manufactured by P & G Co., Ltd. as a raw material alcohol and hydroxylation as a reaction catalyst. 0.8 g of potassium was charged, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised while stirring. Subsequently, 91 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, and the reaction was carried out to obtain alcohol ethoxylate.
Gas chromatograph mass spectrometer: GC-5890 manufactured by Hewlett-Packard, detector: hydrogen flame ionization detector (FID), column: Ultra-1 (manufactured by HP, L25m x φ0.2mm x T0.11μm) As a result of analysis using), the obtained alcohol ethoxylate had an average number of moles of ethylene oxide added of 1.0. The amount of the compound to which ethylene oxide was not added was 43% by mass with respect to the total mass of the obtained alcohol ethoxylate.
Next, 237 g of the alcohol ethoxylate obtained above was taken in a 500 mL flask equipped with a stirrer, replaced with nitrogen, and then 96 g of liquid anhydrous sulfuric acid (sulfur) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of the dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Then, this was neutralized with an aqueous sodium hydroxide solution to obtain B-2-2 (AES).

<Synthesis Example 4: Synthesis of E-1 (TES)>
A mixture of fatty acid lower alkyl esters containing 45% by mass of methyl stearate derived from palm oil, 35% by mass of methyl oleate and 20% by mass of methyl palmitate (Lion Co., Ltd., trade names "Pastel M180", "Pastel M181", 785 g (2.68 mol) of "pastel M16" mixture, 250 g (1.68 mol) of triethanolamine, 0.52 g of magnesium oxide, and 3.71 g of 14% sodium hydroxide aqueous solution (ester exchange catalyst; molar ratio). (Sodium compound / magnesium compound) = 1.01 / 1, the amount of the catalyst used with respect to the total mass of the fatty acid lower alkyl ester and triethanolamine: 0.10 mass%), the stirrer, the splitter, the cooler, and the temperature. It was charged into a meter and a 2 L four-necked flask equipped with an ester introduction tube. After the nitrogen substitution, nitrogen was allowed to flow at a flow rate of 0.52 L / min. The temperature was raised to 190 ° C. at a rate of 1.5 ° C./min, and the reaction was carried out for 6 hours. It was confirmed that the unreacted methyl ester was 1% by mass or less, and the reaction was stopped. The fatty acid salt derived from the catalyst was filtered off from the obtained product to obtain an intermediate alkanolamine ester.
The amine value was measured and the molecular weight was determined to be 582.
270 g (0.464 mol) of the obtained alkanolamine ester (molecular weight 582) was placed in a four-necked flask equipped with a thermometer, a dropping funnel and a condenser and replaced with nitrogen. Then, the mixture was heated to 85 ° C., and 57.4 g (0.455 mol) of dimethyl sulfate was added dropwise over 1 hour. After the addition of dimethyl sulfate was completed, the mixture was kept at 95 ° C. and stirred for 1 hour. After completion of the reaction, about 62 g of isopropanol was added dropwise and cooled to prepare an isopropanol solution to obtain TES. All operations were performed under a trace amount of nitrogen.

[Examples 1 to 19, Comparative Examples 1 to 4]
Examples 6 to 8 and 16 to 19 are reference examples.
Each component of the liquid detergent shown in Tables 1 to 3 was mixed to prepare a liquid detergent. Moreover, each component of the softener composition shown in Table 4 was mixed to obtain a softener composition.
The blending amount shown in the table is a net conversion value. In addition, the ingredients whose blending amount is not listed in the table are not blended.
Using the liquid detergent and fabric softener compositions shown in Tables 1 to 3, the textile products were washed by the following methods. As the textile product, a bath towel pretreated by the following method was used. The textile products after washing were evaluated for "puffy and voluminous tactile sensation" and "water absorption" by the following methods. The results are shown in Tables 1-3.
[Comparative Examples 5 and 6]
Each component of the softener composition shown in Table 4 was mixed to obtain a softener composition.
Of the components of the liquid detergent shown in Table 3, components other than the component (A) and the component (B) were mixed to prepare a mixture (1).
Using the obtained mixture (1), the component (A), the component (B), and the softener composition, the textile product was washed by the following method. However, when the liquid detergent was applied to the water used, the mixture (1), the component (A), and the component (B) were added separately. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

(Pretreatment method of the object to be washed)
Using the index detergent described in JIS K 3362: 1998, 6 cotton bath towels (100% cotton, approx. 140 cm x 70 cm, approx. 250 g / per sheet) were washed 5 times with the Hitachi fully automatic washing machine NW-6CY. A cotton bath towel was prepared by removing excess chemicals and pretreated by indoor drying (detergent concentration 0.0667 mass%, tap water 47 L used, water temperature 20 ° C., washing 10 minutes, rinsing twice). ..

(Washing method)
In the washing tub of a fully automatic electric washing machine (JW-Z23A manufactured by Haier), 30 L of water used according to JIS K3362: 1998 and pretreated textile products (6 cotton bath towels, 1500 g) were placed.
The liquid detergent shown in the table was added to the water used in the amount shown in the table (the amount of the liquid detergent added per 1 L of water, unit: g / L), and the mixture was washed in the standard mode for 10 minutes. Then, in order to separate the cleaning liquid from the textile product, it was dehydrated for 1 minute [cleaning step].
Subsequently, 30 L of tap water was put into the washing tub containing the textile product. The softener composition shown in the table was added to the tap water in the amount used in the table (addition amount of the softener composition per 1 L of water, unit: g / L) in rinse water for 5 minutes in standard mode. After stirring and rinsing, dehydration treatment was performed to separate the rinse water from the textile product [rinse step]. The dehydrated textile product was naturally dried for one day in a constant temperature and humidity chamber at 20 ° C. and a humidity of 65% RH, and this was used as a test cloth.

(Preparation method of control cloth (1))
In the washing method, the same applies except that a standard liquid detergent (a 20% by mass aqueous solution of alcohol ethoxylate added with an average of 15 mol of ethylene oxide per mol of lauryl alcohol) was used instead of the liquid detergent. Six washed cotton bath towels were used as the control cloth (1).

(Preparation method of control cloth (2))
In the washing method, 6 cotton bath towels treated in the same manner were used as the control cloth (2) except that the washing step was not performed and only the rinsing step under the same conditions as in Example 1 was performed.

<Evaluation method>
[Puffy and voluminous touch]
A method in which 10 specialized panelists compare a test cloth arbitrarily extracted from the 6 test cloths and a control cloth arbitrarily extracted from the control cloth (1) in 8 folds. The "fluffy and voluminous feel" of the test cloth was scored according to the following scoring criteria. The tactile sensation was evaluated in the above-mentioned constant temperature and humidity chamber (closed space of ^{20 m 3).}
The tactile sensation was evaluated according to the following evaluation criteria based on the average value of the scoring results of 10 specialized panelists. Those with evaluation results of ○, ◎, and ◎◎ were considered as acceptable.
≪Scoring criteria≫
-1 point: There is no fluffy volume compared to the control cloth.
0 points: Equivalent to the control cloth.
1 point: Slightly voluminous and plump compared to the control cloth.
2 points: It is voluminous and plump compared to the control cloth.
3 points: Very voluminous and plump compared to the control cloth.
≪Evaluation criteria≫
◎ ◎: 2.5 points or more.
⊚: 2 points or more and less than 2.5 points.
◯: 1.5 points or more and less than 2 points.
Δ: 1 point or more and less than 1.5 points.
X: Less than 1 point.

[Water absorption]
From the above test cloth, 10 test pieces of 2 cm × 2 cm were arbitrarily cut out and left in a constant temperature and humidity chamber at 20 ° C. and a humidity of 65% RH for 1 day.
1 L of tap water was put in a 1 L beaker, and the temperature was adjusted to 25 ° C. One of the test pieces was floated on the surface of the water, and the time until the test piece was soaked with water or sank to the bottom of the beaker was measured. The shorter the time, the higher the water absorption. The average time for the 10 test pieces to be submerged in water was calculated and evaluated according to the following evaluation criteria.
The average time measured in the same manner was obtained by appropriately cutting 10 test pieces of 2 cm × 2 cm from the control cloth (2) and leaving them in a constant temperature and humidity chamber at 20 ° C. and a humidity of 65% RH for 1 day. It was 50 seconds. Therefore, according to the following evaluation criteria, a grade of D or higher was considered acceptable.
≪Evaluation criteria≫
A: The average time is less than 5 seconds.
B: The average time is 5 seconds or more and less than 15 seconds.
C: The average time is 15 seconds or more and less than 30 seconds.
D: The average time is 30 seconds or more and less than 45 seconds.
E: 45 seconds or more.

As shown in Tables 1 to 3, Examples 1 to 19 in which a liquid detergent containing the components (A) and (B) was used and the textile products were washed in a cleaning liquid obtained by diluting the liquid detergent with water are shown in Examples 1 to 19. After washing and drying, the textile products had a fluffy, voluminous feel. In addition, the decrease in water absorption due to the softener treatment was suppressed.
On the other hand, the test cloth obtained in Comparative Example 1 in which the liquid detergent does not contain the component (A) has the same water absorption as the control cloth (2) obtained only by the softener treatment without the cleaning treatment and is flexible. The effect of suppressing the decrease in water absorption due to the agent treatment could not be obtained. In addition, the textile products after washing and drying were inferior in the fluffy and voluminous feel.
Further, in Comparative Example 2 in which a polymer having neither a constituent unit (a-1) nor a constituent unit (a-2) was used instead of the component (A), and a silicone-based component instead of the component (A). In Comparative Example 3 using a polymer, the textile product after washing and drying was inferior in the fluffy and voluminous feel. In addition, the effect of suppressing the decrease in water absorption due to the softener treatment was insufficient.
In Comparative Example 5 in which the component (A) and the component (B) were separately added to the washing liquid, the textile product after washing and drying was inferior in the fluffy and voluminous feel. In addition, the effect of suppressing the decrease in water absorption due to the softener treatment was insufficient.

Claims (7)

A liquid detergent containing the following component (A) and the following component (B) is diluted with water to obtain a cleaning solution, and after performing a cleaning step of cleaning the textile product in the cleaning solution at least once, the following component (E) have a rinsing step to process rinsing the textile in the rinse water containing,
The component (B) contains the following component (B-1) and the following component (B-2), and is represented by (B-1) / (B-2). (B-1) A method for washing a textile product, wherein the mass ratio of the components is 1.2 to 5.
Component (A): A polymer having at least one of a structural unit represented by the following formula (a-1) and a structural unit represented by the following formula (a-2).
(B) Ingredient: Surfactant (excluding higher fatty acid salts).
(B-1) Ingredient: Nonionic surfactant.
(B-2) Ingredient: Anionic surfactant (excluding higher fatty acid salts).
(E) Ingredient: One or more soft bases selected from the group consisting of tertiary amine salt type cationic surfactants and quaternary ammonium type cationic surfactants.

(In the formula, R ¹ and R ² are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and X ⁻ is a counterion.)

(In the formula, R ³ and R ⁴ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms, and X ⁻ is a counterion.) The method for washing a textile product according to claim 1, wherein the mass ratio of the component (B) to the component (A) represented by (B) / (A) is 30 or more. The method for washing a textile product according to claim 1 or 2 , wherein the mass ratio of the component (B-1) to the component (A) represented by (B-1) / (A) is 10 or more. The method for washing a textile product according to any one of claims 1 to 3 , wherein the component (B) contains the following component (C).
(C) Ingredient: Higher fatty acid or salt thereof. The method for washing a textile product according to any one of claims 1 to 4 , wherein the liquid detergent contains the following component (D).
Component (D): From the group consisting of an alkyl group or phenyl group having 1 to 6 carbon atoms, an alkylene glycol ether having an alkylene glycol unit having 2 or 3 carbon atoms, and a compound represented by the following formula (d-1). One or more solvents of choice.

(In the formula, R ^{51 to} R ⁵³ are independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and R ⁵⁴ is a hydrogen atom or acetyl group.) The method for washing a textile product according to any one of claims 1 to 5, wherein the component (B-1) contains a compound represented by the following formula (b-1-1-MEE).
R ¹¹ -C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u -R ¹² ... (B-1-1-MEE)
In formula (b-1-1-MEE), R ¹¹ Is a hydrocarbon group having 7 to 22 carbon atoms, and R ¹² Is a methyl group, s represents the average number of repetitions of EO, a number of 6 to 20, t represents the average number of repetitions of PO, 0, u represents the average number of repetitions of EO, 0 It is a number of 20, where EO represents an oxyethylene group and PO represents an oxypropylene group. The component (B-1) further contains a compound represented by the following formula (b-1--2-AE), and the above formula (b-1-AE) is compared with the compound represented by the formula (b-1--2-AE). The method for washing a textile product according to claim 6, wherein the MEE / AE represents the mass ratio of the compound represented by b-1-1-MEE) and is 0.4 to 20.
R ²¹ -O-[(EO) _v / (PO) _w ]-(EO) _x −H ・ ・ ・ (b-1--2-AE)
In formula (b-1--2-AE), R ²¹ Is a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, v represents the average number of repetitions of EO, 3 to 20, and w represents the average number of repetitions of PO. , 0, x represents the average number of repetitions of EO, is a number from 0 to 20, and (v + x) is 7 to 16, EO represents an oxyethylene group, and PO represents an oxypropylene group.