JP6832181B2 - Textile washing methods and textile processing kits - Google Patents

Description

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

In some cases, the washed textile products are treated with a treatment agent such as a softener for the purpose of imparting flexibility and aroma to the textile products.
For example, Patent Document 1 states that after washing a textile product in a cleaning liquid containing a specific amount of a nonionic surfactant and an anionic surfactant, the textile product is washed with rinse water containing a softening agent and a nonionic surfactant. A method of washing the textile product to be processed is disclosed. According to the washing method described in Patent Document 1, the softening effect is improved.

Japanese Unexamined Patent Publication No. 2011-47065

In recent years, it has been required to bring out the performance of softeners more remarkably and to impart more excellent flexibility to textile products.
In addition, from the viewpoint of energy saving and resource saving, water-saving washing that uses a small amount of water is also required. In addition, drum-type washing machines have become widespread, and as a result, the bath ratio (ratio of washing water to textile products) in washing tends to decrease. However, in general, when washing is performed at a low bath ratio, there is a problem that the stains removed during washing tend to adhere (recontaminate) to the textile product again.

The present invention has been made in view of the above circumstances, and provides a method for washing textile products and a treatment kit for textile products, which can impart more excellent flexibility to textile products while exhibiting cleaning performance and recontamination prevention performance. The purpose is to do.

The present invention has the following aspects.
[1] A method for washing textile products, wherein the following steps (1) and the following steps (2) are performed one or more times each, and after the final step (1), one or more steps (2) are performed.
Step (1): A cleaning step of cleaning a textile product in a cleaning liquid containing the following component (a1) and the following component (a2).
Step (2): After the step (1), the textile product is separated from the cleaning liquid, and the textile product separated from the cleaning liquid is rinsed in rinsing water containing the following component (b1).
(A1) Ingredient: Surfactant.
(A2) Component: An alkylene oxide adduct of polyalkyleneamine.
(B1) Component: Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be partitioned by an ester group or an amide group, a salt thereof, and a quaternized product thereof. At least one compound.
[2] The component (a1) contains the following component (a1-1) and the following component (a1-2), and the mass ratio represented by the component (a1-1) / component (a1-2) is 0.1. The method for washing a textile product according to [1], which is ~ 50.
(A1-1) Ingredient: Nonionic surfactant.
(A1-2) Ingredient: Anionic surfactant.
[3] The method for washing a textile product according to [1] or [2], wherein the rinse water further contains the following component (b2).
(B2) Ingredient: Cyclic dextrin.
[4] The method for washing a textile product according to any one of [1] to [3], wherein the step (2) is performed once.
[5] The method for washing textile products according to [2], wherein the content of the component (a1-1) in the washing liquid is 30 to 270 mass ppm with respect to the total mass of the washing liquid.
[6] The method for washing a textile product according to [2] or [5], wherein the content of the component (a1-2) in the washing liquid is 15 to 165 mass ppm with respect to the total mass of the washing liquid.
[7] Any of [2], [5], and [6], wherein the mass ratio represented by {(a1-2) component / (a1) component} / (a2) component is 0.01 to 5. The method for washing textile products according to one.
[8] The content of the component (b1) in the rinse water is higher than the content of the component (a1-2) in any one of [2], [5], [6], and [7]. The method of washing textile products described.
[9] The fiber according to any one of [1] to [8], wherein the content of the component (a2) in the washing liquid is 0.03 to 20 mass ppm with respect to the total mass of the washing liquid. How to wash the product.
[10] The method for washing a textile product according to any one of [1] to [9], wherein the component (a2) is an alkylene oxide adduct of polyalkyleneimine.
[11] The textile product according to any one of [1] to [10], wherein the content of the component (b1) in the rinse water is 1 to 100 mass ppm with respect to the total mass of the rinse water. Washing method.
[12] The method for washing a textile product according to [3], wherein the content of the component (b2) in the rinse water is 0.1 to 10 mass ppm with respect to the total mass of the rinse water.

[13] A treatment for textile products, comprising a first treatment agent (A) containing the following (a1) component and the following (a2) component, and a second treatment agent (B) containing the following (b1) component. kit.
(A1) Ingredient: Surfactant.
(A2) Component: An alkylene oxide adduct of polyalkyleneamine.
(B1) Component: Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be partitioned by an ester group or an amide group, a salt thereof, and a quaternized product thereof. At least one compound.
[14] The component (a1) contains the following component (a1-1) and the following component (a1-2), and the mass ratio represented by the component (a1-1) / component (a1-2) is 0.1. The processing kit for textile products according to [13], which is ~ 50.
(A1-1) Ingredient: Nonionic surfactant.
(A1-2) Ingredient: Anionic surfactant.
[15] The treatment kit for textile products according to [13] or [14], wherein the second treatment agent (B) further contains the following component (b2).
(B2) Ingredient: Cyclic dextrin.
[16] The treatment kit for textile products according to [14], wherein the mass ratio represented by {(a1-2) component / (a1) component} / (a2) component is 0.01 to 5.
[17] The content of the component (a1) in the first treatment agent (A) is 20 to 80% by mass with respect to the total mass of the first treatment agent (A), [13] to The processing kit for textile products according to any one of [16].
[18] The content of the component (a2) in the first treatment agent (A) is 0.01 to 5% by mass with respect to the total mass of the first treatment agent (A) [13]. ] To [17]. The processing kit for textile products according to any one of.
[19] The treatment kit for textile products according to any one of [13] to [18], wherein the component (a2) is an alkylene oxide adduct of polyalkyleneimine.
[20] The content of the component (b1) in the second treatment agent (B) is 1 to 50% by mass with respect to the total mass of the second treatment agent (B), [13] to The processing kit for textile products according to any one of [19].
[21] The content of the component (b2) in the second treatment agent (B) is 0.01 to 10% by mass with respect to the total mass of the second treatment agent (B) [15]. ] The processing kit for textile products described in.

According to the present invention, it is possible to provide a method for washing a textile product and a treatment kit for the textile product, which can impart more excellent flexibility to the textile product while exhibiting cleaning performance and anti-recontamination performance.

[How to wash textiles]
In the method for washing textile products of the present invention (hereinafter, also simply referred to as "washing method"), the following steps (1) and the following steps (2) are performed at least once, respectively.
Examples of textile products include clothing, cloths, sheets, curtains and the like.
The material of the textile product is not particularly limited, and may be any of natural fibers such as cotton, silk and wool, and chemical fibers such as polyester and polyamide.

"Process (1)"
The step (1) is a cleaning step of cleaning the textile product in a cleaning liquid containing the following component (a1) and the following component (a2).
In the step (1), the component (a1) and the component (a2) may be used in the state of a mixture or may be used separately. The mixture containing the component (a1) and the component (a2) is also referred to as a "cleaning agent". The dosage form of the cleaning agent may be a solid such as powder, sheet or tablet, or a liquid.

<(A1) component>
The component (a1) is a surfactant.
By using the component (a1) in the step (1), the cleaning performance can be exhibited.
As the component (a1), a known surfactant used as a cleaning agent for textile products can be used, and specifically, the nonionic surfactant (a1-1) (hereinafter, also referred to as "(a1-1) component"). (Referred to as), anionic surfactant (a1-2) (hereinafter, also referred to as “(a1-2) component”), cationic surfactant (a1-3) (hereinafter, also referred to as “(a1-3) component”). ), Amphoteric surfactant (a1-4) (hereinafter, also referred to as “(a1-4) component”) and the like. These may be used alone or in combination of two or more. In particular, it is preferable to use the component (a1-1) and the component (a1-2) in combination in terms of achieving both higher detergency and anti-recontamination performance.

((A1-1) component)
The component (a1-1) is a nonionic surfactant.
Examples of the component (a1-1) include the following (1) to (8).
(1) An average of 3 to 30 mol, preferably 3 to 20 mol, more preferably 5 to 20 mol of an alkylene oxide having 2 to 4 carbon atoms was added to an aliphatic alcohol having 6 to 22 carbon atoms, preferably 8 to 18 carbon atoms. , Polyoxyalkylene alkyl (or alkenyl) ether. Of these, polyoxyethylene alkyl (or alkenyl) ethers and polyoxyethylene polyoxypropylene alkyl (or alkenyl) ethers are preferable. Examples of the aliphatic alcohol used here include primary alcohols and secondary alcohols. Moreover, the alkyl group may have a branched chain. As the aliphatic alcohol, a primary alcohol is preferable.
(2) Polyoxyethylene alkyl (or alkenyl) phenyl ether.
(3) A fatty acid alkyl ester alkoxylate in which an alkylene oxide is added between ester bonds of a long chain fatty acid alkyl ester.
(4) Polyoxyethylene sorbitan fatty acid ester.
(5) Polyoxyethylene sorbitol fatty acid ester.
(6) Polyoxyethylene fatty acid ester.
(7) Polyoxyethylene cured castor oil.
(8) Glycerin fatty acid ester.

As the component (a1-1), those of the above (1) or (3) are preferable, and among them, a compound represented by the following general formula (A1) or a compound represented by the following general formula (A2) is particularly preferable. preferable.
R ^11- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ¹² ... (A1)
R ^21- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (A2)
(In the formula (A1), 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, which is 6 to 20. It is a number, t represents the average number of repetitions of PO, is a number from 0 to 6, u represents the average number of repetitions of EO, is a number from 0 to 20, EO represents an oxyethylene group, and PO is a number. Represents an oxypropylene group.
In formula (A2), 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, 0 to 0. It is a number of 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. )

In formula (A1), R ¹¹ is a hydrocarbon group having 7 to 22 carbon atoms. 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.
From the viewpoint of further improving the detergency, 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.

R ¹² is an alkyl group having 1 to 6 carbon atoms, and may be linear or branched. Of these, a methyl group and an ethyl group are preferable.
In the formula (A1), s and u are numbers that independently represent the average number of repetitions of EO.
s + u is preferably 6 to 20, more preferably 6 to 18, even more preferably 11 to 18, and particularly preferably 14 to 18. When it is equal to or more than the above lower limit value, the liquid stability of the cleaning agent (hereinafter, simply referred to as “liquid stability of the cleaning agent”) when the component (a1) and the component (a2) are used in the form of a liquid cleaning agent becomes more stable. It will be easier to improve. If it is not more than the above upper limit value, the detergency is more likely to be improved.
In the formula (A1), t is a number representing the average number of repetitions of PO.
t is a number from 0 to 6, preferably 0 to 3, and more preferably 0. When it is not more than the above upper limit value, the liquid stability of the cleaning agent is more likely to be improved.
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 this specification, the average number of repetitions can be measured by gas chromatography or the like.

The distribution of EO or PO in the formula (A1) varies depending on the reaction method at the time of production. For example, when ethylene oxide or propylene oxide is added to a raw material using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide, the distribution of s or t becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such ^{as Al 3+} , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ described in JP-A-6-15038 are added. When ethylene oxide or propylene oxide is added to the raw material in use, the distribution of s or t becomes relatively narrow.

In formula (A2), R ²¹ is a hydrocarbon group having 6 to 22 carbon atoms.
In the formula (A2), ^{the carbon number of R 21} is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18 from the viewpoint of further improving the detergency.
R ²¹ may be linear or branched.

Preferred R ^21- O- includes groups represented by the following general formula (A3).
(R ³¹ ) (R ³² ) CH-O-... (A3)
(In the formula (A3), R ³¹ and R ³² each independently represent a hydrogen atom or a chain hydrocarbon group, and the total number of carbon atoms of ^{R 31} and R ^{32 is 5 to 21.)}

The total number of carbon atoms of R ³¹ and R ³² is preferably 9 to 21, more preferably 9 to 19, and even more preferably 9 to 17.
R ³¹ and R ³² may be linear or branched.

Specifically, as R ²¹ , an alkyl group derived from a secondary alcohol having 12 to 14 carbon atoms is preferable.
In the formula (A2), v and x are numbers that independently represent the average number of repetitions of EO.
v + x is preferably 3 to 20, more preferably 5 to 18, still more preferably 6 to 18, and particularly preferably 11 to 18. When it is at least the above lower limit value, the liquid stability is more likely to be improved. If it is not more than the above upper limit value, the detergency is more likely to be improved.
In the formula (A2), w is a number representing the average number of repetitions of PO.
w is a number from 0 to 6, preferably 0 to 3. When it is not more than the above upper limit value, the liquid stability is more likely to be improved.
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 distribution of EO or PO in the formula (A2) varies depending on the reaction method at the time of production. For example, when ethylene oxide or propylene oxide is added to a raw material using a general alkaline catalyst such as sodium hydroxide or potassium hydroxide, the distribution of v or w becomes relatively wide. A specific alkoxylation catalyst such as magnesium oxide to which metal ions such ^{as Al 3+} , Ga ³⁺ , In ³⁺ , Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , and Mn ²⁺ described in JP-A-6-15038 are added. When ethylene oxide or propylene oxide is added to the raw material in use, the distribution of v or w becomes relatively narrow.

As the component (a1-1), the compound represented by the formula (A1) is more preferable, and the compound in which t in the formula (A1) is 0 (that is, the polyoxyethylene fatty acid alkyl ester) is more preferable, and the formula (a1) is more preferable. A polyoxyethylene fatty acid methyl ester (hereinafter referred to as "MEE") in which R ^{12 in} A1) is a methyl group is particularly preferable from the viewpoint of improving detergency and solubility of liquid cleaning agents for clothing.

By using the polyoxyethylene fatty acid alkyl ester as the component (a1-1), the solubility in water is excellent, and high detergency can be easily obtained. Further, when the component (a1) and the component (a2) are used in the form of a liquid cleaning agent, even if the concentration of the component (a1) in the cleaning agent is high, a significant increase in viscosity (gelation) is unlikely to occur, which is good. It is possible to obtain a concentrated type cleaning agent having excellent fluidity and liquid stability.
Polyoxyethylene fatty acid alkyl ester (particularly MEE) is a nonionic surfactant in which the orientation of molecules is weak in an aqueous solution system and micelles are unstable, so gelation does not occur in a high concentration region, and one type of polyoxyethylene fatty acid alkyl ester. It can be used alone in a large amount in a cleaning agent. In addition, it has good solubility in water. Furthermore, it has good fluidity even at high concentrations. Therefore, the polyoxyethylene fatty acid alkyl ester quickly becomes uniform in the washing liquid after being put into the water in the washing tub. As a result, when the polyoxyethylene fatty acid alkyl ester is used, it can be in contact with the textile product at a predetermined concentration from the initial stage of cleaning, so that high detergency can be obtained.
Further, as the polyoxyethylene fatty acid alkyl ester, it is preferable that the content ratio of the ethylene oxide adduct having an addition molar number of EO of 2 or less is 0.5% by mass or less with respect to the total polyoxyethylene fatty acid alkyl ester. , 0.2% by mass or less is more preferable. When the total content ratio is 0.5% by mass or less, it becomes easy to obtain a cleaning agent having a lower raw material odor derived from the polyoxyethylene fatty acid alkyl ester.

The compound represented by the formula (A1) and the compound represented by the formula (A2) preferably have a narrow ratio of 20% by mass or more, and more preferably 30% by mass or more. The higher the narrow ratio, the better the detergency can be obtained. Further, when the narrow ratio is 20% by mass or more, particularly 30% by mass or more, it becomes easy to obtain a cleaning agent having less raw material odor of the surfactant.
When the compound represented by the formula (A1) is produced by a conventional method, the compound represented by the formula (A1) and a component that does not contribute to the detergency, for example, the formula (A1), are contained in the product. A fatty acid ester as a raw material of the compound and an ethylene oxide adduct having an s of 1 or 2 in the compound represented by the formula (A1) coexist to reduce the narrow ratio. Therefore, when the narrow ratio is high, the number of coexisting components is sufficiently small, and the problems of deterioration of detergency and raw material odor are less likely to occur. The same applies to the compound represented by the formula (A2).
The upper limit of the narrow ratio is not particularly limited, but is preferably 80% by mass or less.
The narrow ratio is more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass, because liquid stability and solubility are improved.
Here, in the present specification, the "narrow ratio" indicates the ratio of the distribution of ethylene oxide adducts having different numbers of moles of EO, and is represented by the following mathematical formula (S).

In the formula (S), p _max indicates the number of moles of EO of the ethylene oxide adduct that is most abundant in the total ethylene oxide adduct. i indicates the number of moles of EO added. Yi indicates the proportion (mass%) of the ethylene oxide adduct in which the number of moles of EO added is i, which is present in the whole ethylene oxide adduct.

The narrow ratio can be controlled by, for example, a method for producing the compound represented by the formula (A1) or the compound represented by the formula (A2). The method for producing the compound represented by the formula (A1) is not particularly limited, but for example, ethylene oxide and / or propylene oxide is added to the fatty acid alkyl ester by using a surface-modified composite metal oxide catalyst. It can be easily produced by a method of polymerization (see JP-A-2000-144179). As a method for producing the compound represented by the formula (A2), for example, by using a surface-modified composite metal oxide catalyst, ethylene oxide and / or propylene oxide is addition-polymerized to an alcohol having 6 to 22 carbon atoms. Can be manufactured.
Suitable surface-modified composite metal oxide catalysts used in such methods include, specifically, surface-modified metal ions (Al ³⁺ , Ga ³⁺ , In ³⁺ , In 3+, etc.) with metal hydroxides and the like. Tl ³⁺ , Co ³⁺ , Sc ³⁺ , La ³⁺ , Mn ^2+, etc.) of composite metal oxide catalysts such as magnesium oxide, and hydrotalcite surface-modified with metal hydroxides and / or metal alkoxides. Examples include calcined product catalysts.
In the surface modification using the composite metal oxide catalyst, it is preferable to use the composite metal oxide in combination with the metal hydroxide and / or the metal alkoxide. In this case, the ratio of the metal hydroxide and / or the metal alkoxide to 100 parts by mass of the composite metal oxide is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass. ..

As another method for producing the compound represented by the formula (A1), a method of adding an alkylene oxide to a fatty acid alkyl ester using an alkoxylation catalyst prepared from a mixture of an alkaline earth metal compound and an oxyacid or the like is used. is there. The above-mentioned alkoxylation catalyst is disclosed in Japanese Patent No. 4977609, International Publication No. 1993/004030, International Publication No. 2002/0382869, International Publication No. 2012/028435, etc., for example, alkaline earth of carboxylic acid. Examples thereof include an alkoxylation catalyst prepared from a mixture of an alkaline earth metal salt of a metal salt and / or a hydroxycarboxylic acid and sulfuric acid or the like.

As the component (a1-1), a commercially available product may be used, or a known synthetic method may be used for production.
The component (a1-1) may be used alone or in combination of two or more.
The content of the component (a1-1) in the component (a1) is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and 20 to 70% by mass with respect to the total mass of the component (a1). Is even more preferable. If the content of the component (a1-1) in the component (a1) is at least the above lower limit value, the sebum detergency is more likely to be improved, and if it is at least the above upper limit value, the rinse property and the liquid stability of the cleaning agent Is easier to improve.

The content of the component (a1-1) in the cleaning liquid is preferably 30 to 270 mass ppm, more preferably 50 to 250 mass ppm, still more preferably 65 to 200 mass ppm, based on the total mass of the cleaning liquid. When the content of the component (a1-1) in the cleaning liquid is within the above range, the sebum cleaning power can be effectively enhanced.

((A1-2) component)
The component (a1-2) is an anionic surfactant.
Examples of the component (a1-2) include the following (9) to (20).
(9) A methyl, ethyl or propyl ester salt of a saturated or unsaturated α-sulfofatty acid having 8 to 20 carbon atoms.
(10) A linear or branched alkylbenzene sulfonate (LAS or ABS) having an alkyl group having 8 to 18 carbon atoms.
(11) An alkane sulfonate having 10 to 20 carbon atoms.
(12) α-olefin sulfonate (AOS) having 10 to 20 carbon atoms.
(13) An alkyl sulfate or an alkenyl sulfate (AS) having 10 to 20 carbon atoms.
(14) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide (EO) and propylene oxide (PO) (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1) Polyoxyalkylene alkyl (or alkenyl) ether sulfate (AES) having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added on average 0.5 to 10 mol.
(15) An average of 3 to 30 mol of any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1). An alkyl (or alkenyl) phenyl ether sulfate having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added.
(16) Any of alkylene oxides having 2 to 4 carbon atoms, or ethylene oxide and propylene oxide (molar ratio EO / PO = 0.1 / 9.9 to 9.9 / 0.1), with an average of 0.5 to 0.5 to An alkyl (or alkenyl) ether carboxylic acid salt having a linear or branched alkyl (or alkenyl) group having 10 to 20 carbon atoms added by 10 mol.
(17) An alkyl polyhydric alcohol ether sulfate such as an alkyl glyceryl ether sulfonic acid having 10 to 20 carbon atoms.
(18) Long-chain (8 to 20 carbon atoms) monoalkyl, dialkyl or sesquialkyl phosphates.
(19) Polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate.
(20) Soap. A higher fatty acid salt having an average carbon number of 10 to 20 (preferably 12 to 18 carbon atoms).

As the component (a1-2), an anionic surfactant other than those exemplified above may be used. For example, carboxylic acid type anionic surfactants such as alkyl ether carboxylate, polyoxyalkylene ether carboxylate, alkylamide ether carboxylate or alkenylamide ether carboxylate, acylaminocarboxylate; alkyl phosphate ester salt. , Polyoxyalkylene alkyl phosphate ester salt, polyoxyalkylene alkylphenyl phosphate ester salt, glycerin fatty acid ester monophosphate ester salt and other phosphoric acid ester type anionic surfactants and the like.
As the component (a1-2), those of the above (10) or (14) are preferable.

The polyoxyalkylene alkyl ether sulfate of (14) is preferably a compound represented by the following general formula (A4).
R ^41- O-[(EO) _q / (PO) _r ] -SO ₃ ^- M ⁺ ... (A4)
(In the formula (A4), R ⁴¹ is a linear or branched alkyl group having 8 to 20 carbon atoms. EO represents an oxyethylene group, PO represents an oxypropylene group, and q is an EO. It represents the average number of repetitions and is a number of 1 or more. R represents the average number of repetitions of PO and is a number from 0 to 6. M ⁺ is a countercation.)

The polyoxyalkylene alkyl ether sulfate preferably has a linear or branched alkyl group having 10 to 20 carbon atoms and has an average of 1 to 5 mol of alkylene oxide added.
The number of carbon atoms of the alkyl group is preferably 10 to 20, more preferably 12 to 14. Specific examples thereof include a dodecyl group, a tridecylic group, and a tetradecyl group. Of these, the dodecyl group is preferable.
The average number of repetitions of EO is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
The average number of repetitions of PO is preferably 0 to 3, more preferably 0.

Examples of the salt form of the anionic surfactant include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as magnesium salt; alkanolamine salts such as monoethanolamine salt and diethanolamine salt; and ammonium salts. Be done. Of these, alkali metal salts are preferable.

The component (a1-2) can be produced, for example, by a method in which alkylbenzene is sulfonated with anhydrous sulfuric acid and neutralized with an alkali when the component (a1-2) is LAS. When the component (a1-2) is AES, it can be produced by reacting polyoxyalkylene alkyl ether with anhydrous sulfuric acid or by reacting with chlorosulfonic acid to sulfonate and neutralizing with alkali.

The component (a1-2) may be used alone or in combination of two or more.
The content of the component (a1-2) in the component (a1) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and 10 to 40% by mass with respect to the total mass of the component (a1). Is more preferable, and 20 to 40% by mass is particularly preferable. If the content of the component (a1-2) in the component (a1) is at least the above lower limit value, the recontamination prevention effect is more likely to be improved, and if it is at least the above upper limit value, the effect of the component (a2) is impaired. Without, and the rinsability and liquid stability of the cleaning agent are more likely to be improved.

The content of the component (a1-2) in the cleaning liquid is preferably 15 to 165 mass ppm, more preferably 30 to 150 mass ppm, still more preferably 30 to 120 mass ppm, based on the total mass of the cleaning liquid. When the content of the component (a1-2) in the cleaning liquid is within the above range, the contamination prevention performance is further improved without impairing the effect of the component (a2).

The mass ratio represented by the component (a1-1) / component (a1-2) (hereinafter, also referred to as “(a1-1) / (a1-2) ratio”) is preferably 0.1 to 50. 0.5 to 25 is more preferable, and 1.0 to 10 is even more preferable. When the ratio (a1-1) / (a1-2) is within the above range, the component (a2) is likely to adhere to the textile product, and due to the synergistic effect with the component (b1) used in the step (2) described later. While increasing flexibility, it can exhibit better cleaning performance and recontamination prevention performance.

((A1-3) component)
The component (a1-3) is a cationic surfactant.
Examples of the component (a1-3) include a cationic surfactant of an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylbenzyldimethylammonium salt, and an alkylpyridinium salt. Examples of these salts include halogen salts such as chlorine and alkyl sulfates such as methyl sulfuric acid and ethyl sulfuric acid.

As the component (a1-3), one type may be used alone, or two or more types may be used in combination.
The content of the component (a1-3) in the component (a1) is preferably 0 to 15% by mass, more preferably 0 to 10% by mass, and 0 to 5% by mass with respect to the total mass of the component (a1). Is even more preferable. When the content of the component (a1-3) in the component (a1) is not more than the above upper limit value, the rinsing property and the liquid stability of the cleaning agent can be more easily improved without interfering with the recontamination prevention effect.

((A1-4) component)
The component (a1-4) is an amphoteric surfactant.
Examples of the component (a1-4) include alkylbetaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric tenside agent. And so on.

The component (a1-4) may be used alone or in combination of two or more.
The content of the component (a1-4) in the component (a1) is preferably 0 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the component (a1). When the content of the component (a1-4) in the component (a1) is not more than the above upper limit value, the rinsing property and the liquid stability of the cleaning agent can be more easily improved without interfering with the recontamination prevention effect.

When the component (a1) is used as a cleaning agent, the content of the component (a1) is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, based on the total mass of the cleaning agent. When the content of the component (a1) in the cleaning agent is at least the above lower limit value, the recontamination prevention effect is more likely to be improved, and when it is at least the above upper limit value, the rinsing property and the liquid stability of the cleaning agent are further improved. It will be easier to do.
The total of the components (a1) does not exceed 100% by mass with respect to the total mass of the components (a1).

<(A2) component>
The component (a2) is an alkylene oxide adduct of polyalkyleneamine.
Examples of the component (a2) include the following component (a2-1) and the following component (a2-2).

((A2-1) component)
The component (a2-1) is an alkylene oxide adduct of polyalkyleneimine.
The polyalkyleneimine component (a2-1) is represented by, for example, the following general formula (A5).
^{_{NH 2 -R 51 - (NA-}} R 51) n -NH 2 ··· (A5)
(In the formula (A5), R ⁵¹ is an alkylene group having 2 to 6 carbon atoms independently, A represents another polyamine chain by a hydrogen atom or a branch, and n is a number of 1 or more. However, not all of A are hydrogen atoms.)
That is, the polyalkyleneimine represented by the formula (A5) has a polyamine chain branched in the structure.

R ⁵¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ⁵¹ preferably has an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
The polyalkyleneimine is obtained by polymerizing one or more of the alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of the alkyleneimine having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine and the like.
As the polyalkyleneimine, polyethyleneimine (PEI) and polypropyleneimine are preferable, and PEI is more preferable. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary and tertiary amine nitrogen atoms in its structure.

The mass average molecular weight of the polyalkyleneimine is preferably 200 to 2000, more preferably 300 to 1500, further preferably 400 to 1000, and particularly preferably 500 to 800.
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 polyalkyleneimine preferably has 5 to 30 active hydrogens in one molecule, more preferably 7 to 25 hydrogens, and even more preferably 10 to 20 hydrogens.

The component (a2-1) is obtained by adding an alkylene oxide to polyalkyleneimine. As this method, for example, in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate, an alkylene oxide such as ethylene oxide is added to the starting material polyalkyleneimine at 100 to 180 ° C. There is a method of making it.
Examples of the alkylene oxide include an alkylene oxide having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferable, and ethylene oxide being more preferable.

Examples of the component (a2-1) include an ethylene oxide adduct of polyalkyleneimine, a propylene oxide adduct of polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of polyalkyleneimine. The ethylene oxide-propylene oxide adduct of the polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to the polyalkyleneimine, and the addition order and addition form (block shape, random shape) of ethylene oxide and propylene oxide to the polyalkyleneimine. ) Is optional.
As the component (a2-1), an ethylene oxide adduct of polyalkyleneimine and an ethylene oxide-propylene oxide adduct of polyalkyleneimine are preferable, and an ethylene oxide adduct of polyalkyleneimine is more preferable.

As the component (a2-1), an average of 5 to 40 alkylene oxides is added to one active hydrogen atom of the raw material polyalkyleneimine, and an average of 10 to 30 alkylene oxides are added. It is more preferable. That is, it is preferable that an average of 5 to 40 mol of alkylene oxide is added to 1 mol of active hydrogen contained in the raw material polyalkyleneimine, and more preferably 10 to 30 mol of alkylene oxide is added.

The mass average molecular weight of the component (a2-1) is preferably 1000 to 80000, more preferably 2000 to 50000, further preferably 5000 to 30000, and particularly preferably 1000 to 20000.
Examples of the component (a2-1) include compounds represented by the following general formula (A5-1).

In the formula (A5-1), R ⁵² is an alkylene group having 2 to 6 carbon atoms independently, and m is independently a number of 1 or more.
R ⁵² is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. m is ^{the average number of repetitions of (R 52} O), preferably 5 to 40, more preferably 10 to 30.

As the component (a2-1), a synthetic product or a commercially available product may be used.
Examples of commercially available products include the trade name "Sokalan HP20" manufactured by BASF.

((A2-2) component)
The component (a2-2) is an alkylene oxide adduct of a polyalkylene amine represented by the following general formula (A6).
NH ₂ (R ⁶¹ NH) _l H ... (A6)
(In the formula (A6), R ⁶¹ is an alkylene group having 2 to 6 carbon atoms, and l is a number of 1 or more.)

R ⁶¹ is a linear alkylene group having 2 to 6 carbon atoms or a branched alkylene group having 3 to 6 carbon atoms. R ⁶¹ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
As the polyalkylene amine, polyethylene amine is preferable. Examples of polyethyleneamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like. In addition, these polyethylene amines can be obtained by reacting a known production method, for example, ammonia and ethylene dichloride.

The mass average molecular weight of the polyalkylene amine is preferably 60 to 1800, more preferably 60 to 1000, and even more preferably 60 to 800.

As the polyalkylene amine, one having 6 to 30 active hydrogens in one molecule thereof is preferable, and one having 7 to 20 active hydrogens is more preferable.

The component (a2-2) is obtained by adding an alkylene oxide to a polyalkylene amine. This reaction can be carried out in the same manner as the component (a2-1). Examples of the alkylene oxide include an alkylene oxide having 2 to 4 carbon atoms. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferable, and ethylene oxide being more preferable.

Examples of the component (a2-2) include an ethylene oxide adduct of polyalkyleneamine, a propylene oxide adduct of polyalkyleneamine, and an ethylene oxide-propylene oxide adduct of polyalkyleneamine.
As the alkylene oxide adduct of polyalkyleneamine, an ethylene oxide adduct of polyalkyleneamine and an ethylene oxide-propylene oxide adduct of polyalkyleneamine are preferable, and an ethylene oxide adduct of polyalkyleneamine is more preferable.

As the component (a2-2), it is preferable that an average of 5 to 40 alkylene oxides are added to 1 atom of active hydrogen contained in the raw material polyalkylene amine, and an average of 10 to 30 alkylene oxides are added. It is more preferable. That is, it is preferable that an average of 5 to 40 mol of alkylene oxide is added to 1 mol of active hydrogen contained in the raw material polyalkylene amine, and more preferably 10 to 30 mol of alkylene oxide is added.

The mass average molecular weight of the component (a2-2) is preferably 1000 to 80000, more preferably 2000 to 50000, further preferably 5000 to 30000, and particularly preferably 1000 to 20000.

As the component (a2), the component (a2-1) is preferable. Among the components (a2-1), the compound represented by the formula (A5-1) is particularly preferable.

The component (a2) may be used alone or in combination of two or more.
The content of the component (a2) in the cleaning liquid is preferably 0.03 to 20% by mass, more preferably 0.15 to 10% by mass, and further preferably 0.3 to 6% by mass, based on the total mass of the cleaning liquid. preferable. When the content of the component (a2) in the cleaning liquid is within the above range, it can be efficiently adsorbed on the fibers and the softening effect can be further enhanced.

When the component (a2) is used as a cleaning agent, the content of the component (a2) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, based on the total mass of the cleaning agent. It is preferable, 0.1 to 2% by mass is more preferable. If the content of the component (a2) in the cleaning agent is at least the above lower limit value, the softening effect is further enhanced, and it becomes easier to obtain a cleaning agent having excellent appearance stability. If it is at least the above upper limit value, other components It becomes easier to maintain the degree of freedom in the formulation of.

Further, the mass ratio represented by {(a1-2) component / (a1) component} / (a2) component (hereinafter, also referred to as “{(a1-2) / (a1)} / (a2) ratio”) is , 0.01 to 5, more preferably 0.05 to 2, and even more preferably 0.1 to 1. When the {(a1-2) / (a1)} / (a2) ratio is within the above range, more excellent cleaning performance and recontamination prevention performance can be exhibited while increasing flexibility.

<Other ingredients>
In the step (1), the textile product may be washed by adding a component other than the component (a1) and the component (a2) (hereinafter, also referred to as “arbitrary component (a)”) to the cleaning liquid.
The optional component (a) may be mixed with the component (a1) and the component (a2) and used as a cleaning agent, or the component (a1) and the component (a2) may be added to the cleaning solution separately.

Optional components (a) include solvents such as water, enzymes such as proteases, water-miscible organic solvents such as ethanol, propylene glycol and butylcarbitol, alkaline agents such as monoethanolamine, and antioxidants such as dibutylhydroxytoluene. , Preservatives such as sodium benzoate, enzyme stabilizers such as calcium chloride and sodium lactate, fragrances, pigments and the like.

In the step (1), the following component (b1) may be contained in the cleaning liquid. In this case, the content of the component (b1) in the cleaning liquid is preferably 20 mass ppm or less with respect to the total mass of the cleaning liquid.

<Washing method>
In the step (1), for example, the components (a1) and (a2) and the optional component (a) are dissolved in water to prepare a cleaning solution, and the textile product is washed in the obtained cleaning solution. Further, the components (a1) and (a2) and the optional component (a) are mixed in advance to produce a cleaning agent, and the obtained cleaning agent is dissolved in water to prepare a cleaning solution. You may.
The method for cleaning the textile product is not particularly limited, and examples thereof include a method using a commercially available washing machine, a method by hand washing, and a method of washing by soaking.

Step (1) is performed one or more times. When the step (1) is performed twice or more, the step (1) may be performed continuously, or the step (1) may be performed again after the step (2). However, when the step (1) is performed again after the step (2), the step (2) is further performed after that.
The number of steps (1) is not particularly limited and may be determined according to the degree of contamination of the textile product, but usually 1 to 3 times is preferable, and 1 to 2 times is more preferable.

The temperature of the cleaning liquid is not particularly limited, but is preferably 0 to 60 ° C.
The pH of the cleaning solution is not particularly limited, but 4 to 12 is preferable.
The bath ratio is not particularly limited, but is preferably 2 to 40 times.
The washing time is not particularly limited, but it is preferably 3 to 25 minutes for each step (1).

"Process (2)"
The step (2) is a step of separating the textile product from the cleaning liquid after the step (1) and rinsing the textile product separated from the cleaning liquid in rinsing water containing the following component (b1).
The rinse water preferably contains the following component (b2).
In step (2), the component (b1) may be used in the form of a mixture mixed with other components such as the component (b2). The mixture containing the component (b1) is also referred to as a "softener". The dosage form of the softener may be a solid such as powder, sheet or tablet, or a liquid. When the component (b1) is used in combination with other components such as the component (b2), these may be used separately.

<(B1) component>
The component (b1) is composed of a group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be separated by an ester group or an amide group, a salt thereof, and a quaternary compound thereof. At least one compound of choice.
A hydrocarbon group having 10 to 26 carbon atoms is also referred to as a “long-chain hydrocarbon group”.

The long-chain hydrocarbon group has 10 to 26 carbon atoms, preferably 17 to 26, and more preferably 19 to 24. When the number of carbon atoms is 10 or more, the flexibility is good, and when it is 26 or less, the handleability is good.
The long-chain hydrocarbon group may be saturated or unsaturated. If the long-chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but if there is one double bond, the position of the double bond is long-chain hydrocarbon. It is preferably distributed at the center of the hydrocarbon group or around the median value.
The long-chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group having a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be either linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long-chain hydrocarbon group may be separated by an ester group (-COO-) or an amide group (-NHCO-). That is, the long-chain hydrocarbon group has at least one dividing group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is divided by the dividing group. You may. Having the dividing group is preferable from the viewpoint of improving biodegradability.
When it has the above-mentioned dividing groups, the number of dividing groups in one long-chain hydrocarbon group may be one or two or more. That is, the long-chain hydrocarbon group may be divided at one place or at two or more places by the dividing group. When having two or more dividing groups, each dividing group may be the same or different.
When a dividing group is contained in the carbon chain, 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 palm and oil palm. It is 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.

As the amine compound, a secondary amine compound and a tertiary amine compound are preferable, and a tertiary amine compound is more preferable.
More specifically, examples of the amine compound include compounds represented by the following general formula (B1).

In formula (B1), R ^{71 to} R ⁷³ are independently hydrocarbon groups having 10 to 26 carbon atoms, −CH ₂ CH (Y) OCOR ⁷⁴ (Y is a hydrogen atom or CH ₃ , and R ⁷⁴ is carbon. (CH ₂ ) _p NHCOR ⁷⁵ (p is 2 or 3 and R ⁷⁵ is a hydrocarbon group with 7 to 21 carbon atoms), hydrogen atom, Alkyl groups with 1 to 4 carbon atoms, -CH ₂ CH (Y) OH, or-(CH ₂ ) _p NH ₂ , and ^{at least one of R 71 to} R ⁷³ is a hydrocarbon having 10 to 26 carbon atoms. Hydrocarbon groups, -CH ₂ CH (Y) OCOR ⁷⁴ , or-(CH ₂ ) _p NHCOR ⁷⁵ .

In the formula (B1), the number of carbon atoms of the hydrocarbon group having 10 to 26 carbon atoms in ^{R 71 to} R ^{73 is preferably 17 to 26, more preferably 19 to 24.} This hydrocarbon group may be saturated or unsaturated. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable.
-CH _{2 In} CH (Y) OCOR ⁷⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable.
R ⁷⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When R ⁷⁴ is more present in the compounds represented by formula (B1), the plurality of R ⁷⁴ may be the same as each other, may be different.
Hydrocarbon group R ⁷⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms ^(R 74 COOH) (fatty acid ^residue), fatty acids as the under ^{R 74 (R} 74 COOH) is , Saturated fatty acid or unsaturated fatty acid, and may be linear fatty acid or branched fatty acid. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the softened textile product, the saturation / unsaturated ratio (mass ratio) of the fatty acid ^{that is the source of R 74 is preferably 90/10 to 0/100, and is 80/20 to 0.} It is preferable to 0/100.
When R ⁷⁴ is an unsaturated fatty acid residue, cis and trans isomers are present, but the mass ratio of cis isomer / trans isomer is preferably 40/60 to 100/0, preferably 70/30 to 90/10. Especially preferable.

Specific examples of the fatty acids that form the basis of R ⁷⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), and partial Examples thereof include hydrogenated beef fatty acid (iodine value 10 to 60). Among them, fatty acids prepared by combining two or more kinds selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (1) to (3). It is preferable to use the composition.
Condition (1): The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100.
Condition (2): The ratio (mass ratio) of the cis-form / trans-form is 40/60 to 100/0, more preferably 70/30 to 90/10.
Condition (3): Fatty acid having 18 carbon atoms is 60% by mass or more, preferably 80% by mass or more, fatty acid having 20 carbon atoms is less than 2% by mass, and fatty acid having 21 to 22 carbon atoms is less than 1% by mass. Is.

-(CH ₂ ) _{p In} NHCOR ⁷⁵ , p is 2 or 3, with 3 being particularly preferred.
R ⁷⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When R ⁷⁵ in the compounds represented by formula (B1) there are a plurality, the plurality of R ⁷⁵ may be the same as each other, may be different.
Specific examples of R ⁷⁵ include ^{those similar to R 74.}

At ^{least one of R 71 to} R ⁷³ is a long-chain hydrocarbon group (hydrocarbon group having 10 to 26 carbon atoms, −CH ₂ CH (Y) OCOR ⁷⁴ , or − (CH ₂ ) _p NHCOR ⁷⁵ ). Two are preferably long-chain hydrocarbon groups.
When ^{one or two of R 71 to} R ⁷³ are long-chain hydrocarbon groups, the remaining two or one are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, -CH ₂ CH (Y). It is preferably OH, or − (CH ₂ ) _p NH ₂ , an alkyl group having 1 to 4 carbon atoms, −CH ₂ CH (Y) OH, or − (CH ₂ ) _p NH ₂ . Of these, as the alkyl group having 1 to 4 carbon atoms, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable. Y in −CH ₂ CH (Y) OH is the same as Y in −CH ₂ CH (Y) OCOR ⁷⁴ . -(CH ₂ ) _{p p in} NH ₂ is similar to _p in-(CH ₂ ) ^{p NHCOR 75.}

Preferred examples of the compound represented by the formula (B1) include compounds represented by the following general formulas (B1-1) to (B1-8).

In formulas (B1-1) to (B1-8), R ⁷⁶ and R ⁷⁷ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁷⁸ and R ⁷⁹ are each independently a hydrocarbon group having 7 to 21 carbon atoms.

Examples of the hydrocarbon group in R ⁷⁶ and R ⁷⁷ include the same hydrocarbon groups having 10 to 26 carbon atoms in ^{R 71 to} R ^73.
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁷⁸ and R ⁷⁹ include the same hydrocarbon groups having 7 to 21 carbon atoms in ^{R 74.} When R ⁷⁸ is more present in the formula, the plurality of R ⁷⁸ may be the same as each other, may be different.

The salt of the amine compound is obtained by neutralizing the amine compound with an acid. The acid used for neutralizing the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be carried out by a known method.
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. The quaternization of the amine compound can be carried out by a known method.

As the component (b1), at least one selected from the group consisting of the compound represented by the formula (B1), a salt thereof and a quaternized product thereof is preferable, and formulas (B1-1) to (B1-8), the same. At least one selected from the group consisting of salts and quaternized compounds thereof is more preferable, and at least one species selected from the group consisting of salts thereof and quaternized compounds thereof of formulas (B1-4) to (B1-6) is further preferable. preferable.

As the compound represented by the formula (B1), a salt thereof and a quaternized product thereof, a commercially available compound may be used, or a compound produced by a known method may be used.
For example, a compound represented by the formula (B1-2) (hereinafter referred to as “compound (B1-2)”) and a compound represented by the formula (B1-3) (hereinafter referred to as “compound (B1-3)”) , The fatty acid composition, or a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is replaced with the methyl ester of the fatty acid, can be synthesized by a condensation reaction of methyl diethanolamine. At that time, from the viewpoint of improving the flexibility, the compound (B1-2) / compound (B1-3) should be synthesized so that the abundance ratio is 99/1 to 50/50 in terms of mass ratio. Is preferable.
Further, when a quaternized compound (B1-2) or compound (B1-3) is used, it is more preferable to use dimethyl sulfate as the quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by the quaternized compound (B1-2) / the quaternized compound (B1-3) is such that the mass ratio is 99/1 to 50/50. It is preferable to synthesize with.

The compound represented by the formula (B1-4) (hereinafter referred to as "compound (B1-4)"), the compound represented by the formula (B1-5) (hereinafter referred to as "compound (B1-5)") and the formula ( The compound represented by B1-6) (hereinafter referred to as “compound (B1-6)”) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition with triethanolamine. At that time, the content ratio of each component to the total mass of the compounds (B1-4), (B1-5), and (B1-6) is 1 to 60 masses of the compound (B1-4) from the viewpoint of flexibility. %, Compound (B1-5) is preferably 5 to 98% by mass, compound (B1-6) is preferably 0.1 to 40% by mass, compound (B1-4) is 30 to 60% by mass, and compound (B1-4) is 30 to 60% by mass. It is more preferable that B1-5) is 10 to 55% by mass and the compound (B1-6) is 5 to 35% by mass.
Further, when a quaternized compound (B1-4), compound (B1-5), or compound (B1-6) is used, dimethyl is used as the quaternizing agent in that the quaternization reaction proceeds sufficiently. It is more preferable to use sulfuric acid. The abundance ratio of each quaternized product of compound (B1-4), compound (B1-5), and compound (B1-6) is a mass ratio from the viewpoint of flexibility, and the quaternized product of compound (B1-4) is It is preferable that 1 to 60% by mass, the quaternized product of the compound (B1-5) is 5 to 98% by mass, and the quaternized product of the compound (B1-6) is 0.1 to 40% by mass, and the compound (B1). -4) The quaternized product is 30 to 60% by mass, the quaternized product of compound (B1-5) is 10 to 55% by mass, and the quaternized product of compound (B1-6) is 5 to 35% by mass. Is more preferable. Further, when the compound (B1-4), the compound (B1-5), and the compound (B1-6) are quaternized, generally, the esteramine that has not been quaternized remains even after the quaternization reaction. At that time, the ratio of the quaternized / non-quaternized esteramine is preferably in the range of 70/30 to 99/1 by mass ratio.

The compound represented by the formula (B1-7) (hereinafter referred to as “compound (B1-7)”) and the compound represented by the formula (B1-8) (hereinafter referred to as “compound (B1-8)”) are described above. From the fatty acid composition and the adduct of N-methylethanolamine and acrylonitrile, J. Org. Chem. , 26, 3409 (1960), can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylene diamine synthesized by a known method. At that time, it is preferable to synthesize so that the abundance ratio represented by the compound (B1-7) / compound (B1-8) is 99/1 to 50/50 in terms of mass ratio.
When a quaternized compound (B1-7) or compound (B1-8) is used, it is preferable to use methyl chloride as the quaternizing agent, and the quaternized compound / compound of compound (B1-7) (B1-7). It is preferable to synthesize the compound so that the abundance ratio represented by the quaternized compound of B1-8) is 99/1 to 50/50 in terms of mass ratio.

The component (b1) may be used alone or in combination of two or more.
The content of the component (b1) in the rinse water is preferably 1 to 100 mass ppm, more preferably 5 to 80 mass ppm, still more preferably 10 to 50 mass ppm, based on the total mass of the rinse water. When the content of the component (b1) in the rinse water is within the above range, it can be efficiently adsorbed on the fibers and the softening effect can be further enhanced.

In addition, the component (a1) and the component (a2) used in the step (1) may be brought into the rinse water. It is considered that this is because the component (a1) and the component (a2) adhering to the textile product washed in the step (1) are eluted in the rinse water.
The content of the component (b1) in the rinse water is preferably higher than the content of the component (a1-2). If a large amount of the component (a1-2) is present in the rinse water, the component (a1-2) may prevent the component (b1) from being adsorbed on the textile product. When the content of the component (b1) in the rinse water is larger than the content of the component (a1-2), the adsorption of the component (b1) to the textile product is less likely to be hindered, and higher flexibility can be obtained.

When the component (b1) is used as a softener, the content of the component (b1) is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, and 5 to 5% by mass, based on the total mass of the softener. 25% by mass is more preferable. When the content of the component (b1) in the softener is at least the above lower limit value, the softening effect is further enhanced, and when it is at least the above upper limit value, freeze stability can be maintained.

<(B2) component>
The component (b2) is cyclic dextrin.
By using the component (b2) in the step (2), the recontamination prevention performance is further enhanced.

The component (b2) 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.

Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and the like. These cyclodextrins have the largest internal volume per molecular weight in the order of γ, β, and α. The larger the internal volume per molecular weight, the higher the ability to capture, so it is thought that dirt can be easily captured and the detergency and deodorant effect can be enhanced. Therefore, as the cyclodextrin, β-cyclodextrin and γ-cyclodextrin are preferable. Β-Cyclodextrin is preferable in that it can be obtained at a low cost and the production cost of a liquid cleaning agent can be suppressed.

As α-cyclodextrin, Celdex A-100 (trade name, manufactured by Nippon Foods Kako Co., Ltd.), etc., and as β-cyclodextrin, Celdex B-100 (trade name, manufactured by Nippon Foods Kako Co., Ltd.), etc. Examples of γ-cyclodextrin include CAVAMAX (R) W8 Food (trade name, manufactured by Cyclochem Co., Ltd.) and the like.

Highly bifurcated cyclic dextrin is a glucan having an inner bifurcated cyclic structural portion and an outer bifurcated cyclic structural portion. The inner branched cyclic structure portion is a cyclic glucan chain formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the outer branched structure portion is bound to the inner branched cyclic structure portion. It is composed of an acyclic glucan chain. Such highly branched cyclic dextrins are also called cluster dextrins.
The highly branched cyclic dextrin has one intracellularly branched cyclic structure portion in the molecule, and mainly contains a weight average degree of polymerization of about 2500 in which a large number of acyclic glucan chains are bonded to the internally branched cyclic structure portion.

The degree of polymerization of the highly branched cyclic dextrin is preferably 50 to 10000, more preferably 50 to 5000.
The molecular weight of the highly branched cyclic dextrin is preferably 30,000 to 1,000,000, for example.
The degree of polymerization of the internally branched cyclic structure portion of the highly branched cyclic dextrin is preferably 10 to 100, for example.
The degree of polymerization of the outer branch structure portion of the highly branched cyclic dextrin is preferably 40 or more, for example.
The degree of polymerization of each glucan chain constituting the outer bifurcated structural portion of the highly branched cyclic dextrin is preferably 10 to 20 on average, for example.

Highly branched cyclic dextrin is produced, for example, from starch as a raw material by the action of an enzyme called blanching enzyme.
Starch, which is a raw material, is composed of amylose in which glucose is linearly bound by an α-1,4-glucosidic bond and amylopectin having a structure branched by an α-1,6-glucosidic bond. Amylopectin is a macromolecule in which a large number of cluster structures are linked.
Blanching enzyme is a glucan chain transferase that is widely distributed in animals, plants and microorganisms, and acts on the seams of the cluster structure of amylopectin to catalyze the reaction of cyclizing it.
Examples of the highly branched cyclic dextrin include glucans described in JP-A-8-134104, which have an inwardly branched cyclic structure portion and an outerly branched cyclic structure portion and have a degree of polymerization in the range of 50 to 10,000. The highly branched cyclic dextrin has a specific structure as described above and has a large degree of polymerization (molecular weight), and is α-cyclodextrin (glucose unit = 6), β-cyclodextrin (glucose unit = 7), It is different from general cyclodextrin in which 6 to 8 glucoses are bound, such as γ-cyclodextrin (glucose unit = 8).
Examples of the highly branched cyclic dextrin include cluster dextrin (registered trademark, manufactured by Glico Foods Co., Ltd.).

The component (b2) may be used alone or in combination of two or more.
The content of the component (b2) in the rinse water is preferably 0.1 to 10 mass ppm, more preferably 0.5 to 8 mass ppm, still more preferably 1 to 5 mass ppm, based on the total mass of the rinse water. .. When the content of the component (b2) in the rinse water is within the above range, the recontamination prevention performance is further enhanced.

When the component (b2) is used as a softener, the content of the component (b2) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the softener. It is preferable, and 0.1 to 5% by mass is more preferable. When the content of the component (b2) in the softener is at least the above lower limit value, the recontamination prevention performance is further enhanced, and when it is at least the above upper limit value, the appearance stability can be improved.

<Other ingredients>
In the step (2), the textile product may be treated by adding a component other than the component (b1) and the component (b2) (hereinafter, also referred to as “arbitrary component (b)”) to the rinse water.
The optional component (b) may be mixed with the component (b1) or the like and used as a softening agent, or may be added to the cleaning liquid separately from the component (b1) or the like.

Examples of the optional component (b) include water, water-soluble solvents, nonionic surfactants, fragrances, dyes, pigments, preservatives, ultraviolet absorbers, antibacterial agents and the like.

In the step (2), the component (a1) and the component (a2) may be contained in the rinse water. In this case, the content of the component (a1) and the component (a2) in the rinse water is preferably 30 mass ppm or less with respect to the total mass of the rinse water, respectively.

<Processing method>
In the step (2), first, the textile product is separated from the cleaning liquid after the step (1). Examples of the separation method include dehydration.
Then, for example, the component (b1) and, if necessary, the component (b2) and the optional component (b) are dissolved in water to obtain rinse water, and the textile product is rinsed in the obtained rinse water. Further, the component (b1) is mixed in advance with the component (b2) and the optional component (b) as needed to produce a softener, and the obtained softener is dissolved in water to rinse water. May be prepared.

The method for rinsing the textile product is not particularly limited, and the rinse water containing the component (b1) or the like may be stored in a washing tub or the like for rinsing, or the rinse water containing the component (b1) or the like may be circulated for rinsing. , (B1) component and the like may be added and rinsed while circulating water. The method of rinsing by collecting rinsing water in a washing tub or the like is also called "reservoir rinsing".

Step (2) is performed one or more times. Further, the step (2) is performed one or more times after the final step (1).
For example, when both the step (1) and the step (2) are performed once, the step (1) and the step (2) are performed in this order.
When the step (1) is performed twice and the step (2) is performed once, the steps (1), the step (1), and the step (2) are performed in this order.
When the step (1) is performed once and the step (2) is performed twice, the steps (1), the step (2), and the step (2) are performed in this order.
When both step (1) and step (2) are performed twice, the order of step (1), step (2), step (1), step (2), or step (1), step (1), step ( 2) and step (2) are performed in this order.

The number of steps (2) is not particularly limited and may be determined according to the degree of contamination of the textile product, but usually 1 to 2 times is preferable, and 1 time is more preferable. That is, it is more preferable that the step (1) is performed once or more and then the step (2) is performed once.

The temperature of the rinse water is not particularly limited, but is preferably 0 to 60 ° C.
The pH of the rinse water is not particularly limited, but is preferably 3 to 10.
The bath ratio is not particularly limited, but is preferably 2 to 40 times.
The rinsing time is not particularly limited, but it is preferably 2 to 20 minutes for each step (2).

"Action effect"
According to the washing method of the present invention described above, it is possible to impart more excellent flexibility to the textile product while exhibiting cleaning performance and recontamination prevention performance. The reason for this is not clear, but it can be considered as follows.
That is, the use of the component (a2) in the step (1) gives the textile product a silky feel and smoothness, and the use of the component (b1) which is a soft base in the step (2) further gives the textile product a silky feel and smoothness. Is given a soft feel. It is considered that such different feels are mixed and higher flexibility can be exhibited.
It should be noted that the flexibility can be imparted by not using the component (a2) in the step (1) but using the component (a2) in the step (2). However, if the component (a2) is not used in the step (1), the recontamination prevention performance cannot be exhibited.
By using the component (a2) in the step (1), recontamination in the step (1) can be prevented.
Further, by using the component (a1) in the step (1), the cleaning performance can be exhibited.

In addition, the step of rinsing the textile product with only water may be performed between the step (1) and the step (2).

The textile product washed by the washing method of the present invention is then dehydrated and dried, and then stored or worn.
The dehydration method and the drying method are not particularly limited.

[Treatment kit for textile products]
The treatment kit for textile products of the present invention includes a first treatment agent (A) and a second treatment agent (B).

"First treatment agent (A)"
The first treatment agent (A) contains the following component (a1) and the following component (a2).
The dosage form of the first treatment agent (A) may be a solid such as powder, sheet or tablet, or a liquid.

<(A1) component>
The component (a1) is a surfactant.
Examples of the component (a1) include the component (a1) exemplified above in the description of the washing method of the present invention.

The content of the component (a1-1) in the component (a1) is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, and 20 to 70% by mass with respect to the total mass of the component (a1). % Is more preferable. When the content of the component (a1-1) in the component (a1) is at least the above lower limit value, the sebum detergency is more likely to be improved, and when it is at least the above upper limit value, the rinse property and the first treatment agent ( The liquid stability of A) is more likely to be improved.
The content of the component (a1-2) in the component (a1) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and 10 to 40% by mass with respect to the total mass of the component (a1). % Is more preferable. If the content of the component (a1-2) in the component (a1) is at least the above lower limit value, the recontamination prevention effect is more likely to be improved, and if it is at least the above upper limit value, the effect of the component (a2) is impaired. In addition, the rinse property and the liquid stability of the first treatment agent (A) are more likely to be improved.
The content of the component (a1-3) in the component (a1) is preferably 0 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the component (a1). When the content of the component (a1-3) in the component (a1) is not more than the above upper limit value, the rinsing property and the liquid stability of the first treatment agent (A) are more improved without interfering with the anti-recontamination effect. It will be easier to improve.
The content of the component (a1-4) in the component (a1) is preferably 0 to 10% by mass, more preferably 1 to 5% by mass, based on the total mass of the component (a1). When the content of the component (a1-4) in the component (a1) is not more than the above upper limit value, the rinsing property and the liquid stability of the first treatment agent (A) are more improved without interfering with the anti-recontamination effect. It will be easier to improve.

The component (a1) preferably contains the above-mentioned (a1-1) component and the above-mentioned (a1-2) component in terms of achieving both higher detergency and anti-recontamination performance.
The ratio (a1-1) / (a1-2) is preferably 0.1 to 50, more preferably 0.5 to 25, and even more preferably 1.0 to 10. When the ratio (a1-1) / (a1-2) is within the above range, the component (a2) is likely to adhere to the textile product, and the flexibility is enhanced by the synergistic effect with the component (b1) described later. It can exhibit better cleaning performance and recontamination prevention performance.

The content of the component (a1) is preferably 20 to 80% by mass, more preferably 25 to 70% by mass, based on the total mass of the first treatment agent (A). When the content of the component (a1) in the first treatment agent (A) is at least the above lower limit value, the recontamination prevention effect is more likely to be improved, and when it is at least the above upper limit value, the rinse property and the first The liquid stability of the treatment agent (A) is more likely to be improved.
The total of the components (a1) does not exceed 100% by mass with respect to the total mass of the components (a1).

<(A2) component>
The component (a2) is an alkylene oxide adduct of polyalkyleneamine.
Examples of the component (a2) include the component (a2) exemplified above in the description of the washing method of the present invention.
As the component (a2), the above component (a2-1) is preferable. Among the components (a2-1), the compound represented by the formula (A5-1) is particularly preferable.

The content of the component (a2) is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass, and 0.1 to 2 with respect to the total mass of the first treatment agent (A). Mass% is more preferred. When the content of the component (a2) in the first treatment agent (A) is at least the above lower limit value, the softening effect is further enhanced and the first treatment agent (A) having excellent appearance stability can be easily obtained. Therefore, if it is equal to or less than the above upper limit value, it becomes easy to maintain the degree of freedom in blending other components.

The {(a1-2) / (a1)} / (a2) ratio is preferably 0.01 to 5, more preferably 0.05 to 2, and even more preferably 0.1 to 1. When the {(a1-2) / (a1)} / (a2) ratio is within the above range, more excellent cleaning performance and recontamination prevention performance can be exhibited while increasing flexibility.

<Other ingredients>
The first treatment agent (A) may contain a component other than the component (a1) and the component (a2) (hereinafter, also referred to as "arbitrary component (a)").
Examples of the optional component (a) include the optional component (a) exemplified above in the description of the washing method of the present invention.

The first treatment agent (A) may or may not contain the component (b1), but may be partitioned by an ester group or an amide group. A hydrocarbon group having 10 to 26 carbon atoms. It is preferable that the amine compound having 1 to 3 in the molecule, a salt thereof, and a quaternized product thereof are not contained.

"Second treatment agent (B)"
The second treatment agent (B) contains the following component (b1). Further, the second treatment agent (B) preferably contains the following component (b2).
The dosage form of the second treatment agent (B) may be a solid such as powder, sheet or tablet, or a liquid.

<(B1) component>
The component (b1) is composed of a group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be separated by an ester group or an amide group, a salt thereof, and a quaternary compound thereof. At least one compound of choice.
Examples of the component (b1) include the component (b1) exemplified above in the description of the washing method of the present invention.

The content of the component (b1) is preferably 1 to 50% by mass, more preferably 3 to 35% by mass, still more preferably 5 to 25% by mass, based on the total mass of the second treatment agent (B). When the content of the component (b1) in the second treatment agent (B) is at least the above lower limit value, the softening effect is further enhanced, and when it is at least the above upper limit value, freeze stability can be maintained.

<(B2) component>
The component (b2) is cyclic dextrin.
Examples of the component (b2) include the component (b2) exemplified above in the description of the washing method of the present invention.

The content of the component (b2) is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and 0.1 to 5 with respect to the total mass of the second treatment agent (B). Mass% is more preferred. When the content of the component (b2) in the second treatment agent (B) is at least the above lower limit value, the recontamination prevention performance is further enhanced, and when it is at least the above upper limit value, the appearance stability can be improved.

<Other ingredients>
The second treatment agent (B) may contain a component other than the component (b1) and the component (b2) (hereinafter, also referred to as "arbitrary component (b)").
Examples of the optional component (b) include the optional component (b) exemplified above in the description of the washing method of the present invention.

The second treatment agent (B) may or may not contain the component (a1) and the component (a2), but may not contain either the component (a1) and the component (a2). preferable.

"use"
The processing kit for textile products of the present invention can be used, for example, in the above-mentioned method for washing textile products of the present invention. Specifically, in the step (1), the textile product is washed in the cleaning liquid containing the first treatment agent (A), and in the step (2), from the cleaning liquid in the rinsing water containing the second treatment agent (B). Process the separated textile products. The first treatment agent (A) corresponds to the above-mentioned cleaning agent, and the second treatment agent (B) corresponds to the above-mentioned softener.

"Action effect"
According to the processing kit for textile products of the present invention described above, it is possible to impart more excellent flexibility to textile products while exhibiting cleaning performance and recontamination prevention performance. The reason for this is not clear, but it can be considered as follows.
That is, when the textile product is washed with the first treatment agent (A) containing the component (a2), the textile product can be imparted with a silky feel and smoothness. Further, after the washing step, when the textile product is treated with the second treatment agent (B) containing the component (b1) which is a soft base, the textile product can be given a soft feel. It is considered that such different feels are mixed and higher flexibility can be exhibited.
Even if the first treatment agent (A) does not contain the component (a2) and the second treatment agent (B) contains the component (a2), flexibility can be imparted. However, when the first treatment agent (A) does not contain the component (a2), the recontamination prevention performance cannot be exhibited.
When the first treatment agent (A) contains the component (a2), the recontamination prevention performance can be exhibited in the cleaning step.
Further, when the first treatment agent (A) contains the component (a1), the cleaning performance can be exhibited.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following description. The blending amount of the components used in each example is a net conversion value unless otherwise specified. Examples 4, 5 and 8 are reference examples.

[Ingredients used]
"(A1) component"
The following compounds were used as the component (a1).
MEE: Fatty acid methyl ester ethoxylate (fatty acid having 12 to 14 carbon atoms, EO having an average number of added moles of 15), in the above general formula (A1), R ¹¹ = an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms. , R ¹² = methyl group, s = 15, t = 0, u = 0. Synthesized by the following synthesis method.
-AE (15EO): Natural alcohol with 15 mol of ethylene oxide added. In the above general formula (A2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 15, w = 0, x = 0. Synthesized by the following synthesis method.
-AE (7EO): Natural alcohol with 7 mols of ethylene oxide added. In the above general formula (A2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 7, w = 0, x = 0. Synthesized by the following synthesis method.
-EO / PO nonion: 8 mol of ethylene oxide, 2 mol of propylene oxide, and 8 mol of ethylene oxide are added to natural alcohol (12 carbons by mass ratio / 14 carbons = 7/3) in this order. Block added. In the above general formula (A2), R ²¹ = an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, v = 8, w = 2, x = 8.
-Sophthalol: 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 general formula (A2), 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.
-AES: Polyoxyethylene alkyl ether sodium sulfate. In the above general formula (A4), R ⁴¹ = a linear alkyl group having 12 to 14 carbon atoms, q = 1, r = 0, M = sodium. Synthesized by the following synthesis method.
AEPS: Monoethanolamine salt of polyoxyalkylene alkyl ether sulfate. Synthesized by the following synthesis method.
-LAS: Sodium linear alkylbenzene sulfonate, manufactured by Lion Corporation, trade name "Rypon LH-200".
-Palm fatty acid: Made by NOF CORPORATION, trade name "Palm fatty acid".

<Synthesis of MEE>
It was synthesized according to the synthesis method described in JP-A-2000-144179.
Alumina hydroxide / magnesium hydroxide (manufactured by Kyowa Chemical Industry Co., Ltd., trade name "Kyoward 300") having a composition of 2.5 MgO / Al ₂ O ₃ / _{zH 2 O is fired at 600 ° C. for 1 hour in a nitrogen atmosphere.} A fired alumina-magnesium hydroxide (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 each of activated clay and diatomaceous earth as filtration aids were added and mixed, and then the catalyst was filtered off to obtain MEE. The narrow ratio of MEE was 30% by mass.

<Synthesis of AE (15EO)>
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 in 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 AE (15EO) was added. Obtained.

<Synthesis of AE (7EO)>
AE (7EO) was obtained in the same manner as AE (15EO) except that the amount of ethylene oxide (gaseous) used was changed from 760.6 g to 355.0 g.

<Synthesis of AES>
In an autoclave with a capacity of 4 L, 400 g of P &G's trade name CO1270 alcohol (a mixture of alcohol having 12 carbon atoms and alcohol having 14 carbon atoms in a mass ratio of 75/25) as a raw material alcohol and potassium hydroxide as a reaction catalyst 0.8 g 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, L25 m x φ0.2 mm x T0.11 μm) 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 AES.

<Synthesis of AEPS>
In an autoclave equipped with a stirrer, temperature control device and automatic introduction device, a linear primary alcohol with 12 carbon atoms [manufactured by Tokyo Chemical Industry Co., Ltd., trade name: 1-dodecanol (molecular weight 186.33), purity> 99 %] 640 g and 1.0 g of KOH were charged and dehydrated at 110 ° C. and 1.3 kPa for 30 minutes. After dehydration, nitrogen substitution was performed, the temperature was raised to 120 ° C., and then 199 g of propane-1,2-diyloxide was charged. Then, after performing an addition reaction and aging at 120 ° C., the temperature was raised to 145 ° C., and 303 g of ethylene oxide was charged. Then, after carrying out an addition reaction and aging at 145 ° C., the mixture was cooled to 80 ° C. and unreacted ethylene oxide was removed at 4.0 kPa. After removing unreacted ethylene oxide, 1.0 g of acetic acid was added to the autoclave, and the mixture was stirred at 80 ° C. for 30 minutes and then extracted. The average number of moles of propylene oxide added was 1.0, and the average number of moles of ethylene oxide added. An alkoxylate having a value of 2.0 was obtained.
The obtained alkoxylate was sulfated with a descending thin film reactor using _{SO 3 gas.} AEPS was obtained by neutralizing the obtained sulfated product with monoethanolamine.

"(A2) component"
The following compounds were used as the component (a2) and its comparative product (a2') component.
-HP20: Ethylene oxide adduct of polyethyleneimine, manufactured by BASF, trade name "Sokalan HP20". In the above general formula (A5-1), R ⁵² = ethylene group, m = 20.
-PEI: Polyethylenimine (mass average molecular weight about 750000), manufactured by BASF, trade name "Lupazole P".

"(B1) component"
The following compounds were used as the component (b1).
TES: Cationic surfactant (compound according to Example 4 of JP-A-2003-12471). Synthesized by the following synthesis method.
DES: N, N-di (taro oil oxyethyl) -N, N-dimethylammonium chloride.

<Synthesis of 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, amount of catalyst used relative to total mass of said fatty acid lower alkyl ester and triethanolamine: 0.10 mass%), stirrer, demultiplexer, cooler, temperature. It was charged in a 2 L four-necked flask equipped with a meter and a nitrogen 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.

"(B2) component"
The following compounds were used as the component (b2).
-CCD: Highly branched cyclic dextrin, manufactured by Glico Foods Co., Ltd., trade name "cluster dextrin (registered trademark)". The main component of cluster dextrin (registered trademark) has a molecular weight of about 30,000 to 1,000,000, has one cyclic structure in the molecule, and has a mass average degree of polymerization of 2500 in which a large number of glucan chains are bonded to the cyclic portion. Degree of 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.

"Arbitrary ingredient"
The following compounds were used as the optional component (a).
-Protease: Made by Novozymes, trade name "Alcalase 2.5L".
-MEA: Monoethanolamine (alkaline agent), manufactured by Nippon Shokubai Co., Ltd., trade name "monoethanolamine".
-BHT: Dibutylhydroxytoluene (antioxidant), manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER BHT-R".
-Ethanol: Water-miscible organic solvent, manufactured by Japan Alcohol Trading Co., Ltd., trade name "Specific alcohol 95 degree synthesis".
-BC: Butylcarbitol, manufactured by Nippon Emulsifier Co., Ltd., trade name "Butyldiglycol".
-PG: Propylene glycol (water-miscible organic solvent), manufactured by BASF.
-Na lactate: Sodium lactate (enzyme stabilizer), manufactured by Kanto Chemical Co., Inc., trade name "sodium lactate".
-Na benzoate: Sodium benzoate (preservative), manufactured by Toa Synthetic Co., Ltd., trade name "sodium benzoate".
Perfume: Fragrance, Perfume Composition A according to Tables 11 to 18 of JP-A-2002-146399.
-Pigment: Colorant, trade name "Green No. 3", manufactured by Ayumi Kasei Co., Ltd.

The following compounds were used as the optional component (b).
EO20: (Nonion surfactant), a compound obtained by adding an average of 20 mol of ethylene oxide to lauryl alcohol. Made by Nippon Emulsion Co., Ltd., trade name "Emarex 720".
EO60: (Nonion surfactant), 60 mol of ethylene oxide adduct of primary isotridecyl alcohol, and ethylene oxide added to BASF's lutenzole TO3. Product name "TA600-75" manufactured by BASF.
-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").

[Preparation of first treatment agents (A1) to (A10)]
The first treatment agents (A1) to (A10) were prepared by mixing each component according to the compounding composition shown in Table 1.
In Table 1, "balance" is the blending amount (mass%) of water required to make 100% by mass of the entire first treatment agent.

[Preparation of second treatment agents (B1) to (B4)]
The second treatment agents (B1) to (B4) were prepared by mixing each component according to the compounding composition shown in Table 2.
In Table 2, "balance" is the blending amount (mass%) of water required to make 100% by mass of the entire second treatment agent.

[Examples 1 to 11 and Comparative Examples 1 to 3]
Using the first treatment agent (A) and the second treatment agent (B) in the combinations shown in Table 3, the textile products were washed as follows, and the flexibility, cleaning performance, and recontamination performance were evaluated. .. In addition, the appearance stability of the first treatment agent (A) used in each example was evaluated. These results are shown in Table 3.

"Evaluation of flexibility"
<Washing>
The following cotton towels, underwear and shirts were used as textile products.
Cotton towels: 6 sheets (400 g) of pretreated cotton towels prepared by the following method.
Underwear: 1.0 kg of unworn underwear made of cotton.
Shirts: 0.6 kg of unworn shirts made of cotton / polyester blend.

40 L of water used according to JIS K3362: 1998 was put into the washing tub of a two-tank washing machine (manufactured by Toshiba Corporation, product name "Galaxy 3.6"), and the textile product was put therein. Further, the concentration of the first treatment agent (A) in the cleaning liquid is 0.33 g / L in Examples 1 to 5, 7, 9 to 11, Comparative Examples 1 to 3, and 0.83 g / L in Examples 6 and 8. The first treatment agent (A) of the type shown in Table 3 was added so as to be L, and the mixture was washed for 10 minutes as standard (step (1)).
Then, after dehydrating the textile product for 1 minute to separate it from the washing liquid, 40 L of tap water was added so that the concentration of the second treatment agent (B) in the rinse water was 0.33 g / L. The second treatment agent (B) of the type shown in No. 3 was added, and the mixture was stirred and rinsed as standard for 5 minutes (step (2)).
The textile was then dehydrated for 1 minute to separate it from the rinse water and then air dried indoors (drying step). A similar operation was performed using the index detergent described in JIS K 3362: 1998.
In Comparative Example 3, in the step (2), the component (a2) (HP20) was added to the rinse water together with the second treatment agent (B1). The concentration of component (a2) in the rinse water was 4 mass ppm.

<Evaluation>
Two optional towels were extracted from the six cotton towels washed by the above method, and these were used as treated towels.
Separately, two sheets were arbitrarily extracted from the standard towel 1 or the standard towel 2 prepared by the following method, and used as the target cloth.
The feel of the treated towel was compared with the target cloth by 10 panelists (male in their 30s) and scored according to the following criteria, and the average value of the scoring results of the 10 panelists was calculated. The difference of 0.4 evaluation points can be sufficiently recognized as a superiority difference.

(Comparison with standard towel 1)
-1 point: Not softer than standard towel 1.
0 points: Equivalent to standard towel 1.
1 point: Finished slightly softer than standard towel 1.
2 points: Finished softer than standard towel 1.
3 points: Very soft finish compared to standard towel 1.

(Comparison with standard towel 2)
-3 points: Very soft and not finished compared to standard towel 2.
-2 points: Compared to standard towel 2, it is not finished softly.
-1 point: Not finished slightly softer than standard towel 2.
0 points: Equivalent to standard towel 2.
1 point: Finished softer than standard towel 2.

<Preparation method for pretreated cotton towel>
In advance, using the index detergent described in JIS K 3362: 1998, 24 cotton towels (100% cotton, about 34 cm x 86 cm, about 68 g / per sheet) are fully automatic washing machine (manufactured by Hitachi, Ltd., product name). "NW-6CY") was washed 5 times and dried indoors to remove excess chemicals to prepare a pretreated cotton towel (detergent concentration 0.0667% by mass, tap water 47L used, water temperature 20). ℃, washing 10 minutes, rinsing twice).

<Preparation method for standard towel 1>
The above-mentioned step (1) was performed using the first treatment agent (A9). The concentration of the first treatment agent (A9) in the cleaning liquid was 0.33 g / L.
Next, after dehydrating the textile product for 1 minute to separate it from the cleaning liquid, 40 L of tap water is added, and the same type as the second treatment agent (B) used in each example is used in the above step (2). ) Was performed. That is, the standard towel 1 used in Examples 1 to 8 and Comparative Examples 1 to 3 was treated with the second treatment agent (B1). The standard towel 1 used in Example 9 was treated with the second treatment agent (B2). The standard towel 1 used in Example 10 was treated with the second treatment agent (B3). The standard towel 1 used in Example 11 was treated with a second treatment agent (B4). The concentration of the second treatment agent (B) in the rinse water was 0.33 g / L.
The textile was then dehydrated for 1 minute to separate it from the rinse water, then air dried indoors and the cotton towels were washed. This was designated as standard towel 1. That is, the standard towel 1 is a towel that has been rinsed once and then treated by adding a second treatment agent (B) at the time of the first rinse.

<Preparation method for standard towel 2>
The above-mentioned step (1) was performed using the first treatment agent (A9). The concentration of the first treatment agent (A9) in the cleaning liquid was 0.33 g / L.
Then, after dehydrating the textile product for 1 minute to separate it from the washing liquid, 40 L of tap water was added, and the mixture was rinsed with standard stirring for 5 minutes without adding the second treatment agent (B).
Subsequently, after dehydration for 1 minute, 40 L of tap water is added, and the same type of second treatment agent (B) used in each example is used for rinsing with standard stirring for 5 minutes in the same manner as in the preparation of standard towel 1. Was done. The concentration of the second treatment agent (B) in the second rinse water was 0.33 g / L.
The textile was then dehydrated for 1 minute to separate it from the rinse water, then air dried indoors and the cotton towels were washed. This was designated as standard towel 2. That is, the standard towel 2 is a towel that has been rinsed twice and treated by adding a second treatment agent (B) at the time of the second rinse.

"Evaluation of cleaning performance"
<Washing>
The following cotton cloth, wet artificially contaminated cloth and skin shirt were used as textile products.
Cotton cloth: Five cotton knitted fabrics (manufactured by Tanito Shoten) 5 cm x 5 cm as a recontamination judgment cloth.
Wet artificial contaminated cloth: Contaminated cloth manufactured by the Laundry Science Association (white cloth (raw cloth), oleic acid 28.3%, triolein 15.6%, cholesterol oleate 12.2%, liquid paraffin 2.5%, 10 sheets of squalene 2.5%, cholesterol 1.6%, gelatin 7.0%, mud 29.8%, carbon black 0.5% (mass ratio) with stains attached).
Skin shirt: BVD skin shirt (LL size, manufactured by Fujibo Holdings, Inc.) cut into small pieces (about 3 cm x 3 cm).

900 mL of 3 ° DH hard water at 25 ° C. was placed in a Terg-o-tometer (manufactured by UNITED TESTES TESTING), and the amount of the first treatment agent (A) used was determined in Examples 1 to 5, 7, and 9. ~ 11, the first treatment agent (A) of the type shown in Table 3 was added so as to weigh 0.3 g in Comparative Examples 1 to 3 and 0.75 g in Examples 6 and 8, and then the textile product was added. I put it in. Then, 3 ° DH hard water was added to adjust the bath ratio 20 times, and the mixture was washed at 120 rpm and 25 ° C. for 10 minutes (step (1)).
Then, after dehydrating the textile product for 1 minute to separate it from the washing liquid, 900 mL of 3 ° DH hard water at 25 ° C. was added, and the mixture was stirred and rinsed at 120 rpm and 25 ° C. for 3 minutes.
Subsequently, after dehydration for 1 minute, 900 mL of 3 ° DH hard water at 25 ° C. was added, and the second treatment agent (B) of the type shown in Table 3 was added so that the concentration of the second treatment agent (B) in the rinse water was 0.33 g / L. (B) was added, and the mixture was stirred and rinsed for 3 minutes (step (2)).
The textile was then dehydrated for 1 minute to separate it from the rinse water, then the wet artificial contaminated cloth was removed, sandwiched between filter papers and ironed to dry.
In Comparative Example 3, in the step (2), the component (a2) (HP20) was added to the rinse water together with the second treatment agent (B1). The concentration of component (a2) in the rinse water was 4 mass ppm.

<Evaluation>
Uncontaminated cloth (white cloth (original cloth) before adhering dirt) and wet artificially contaminated cloth before and after washing (hereinafter, wet artificially contaminated cloth before washing is referred to as "contaminated cloth before washing" and wet artificial cloth after washing. For the contaminated cloth (referred to as "contaminated cloth after cleaning"), the reflectance of each is measured with a spectral color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "SE2000"), and the cleaning rate is calculated from the following formula (i). (%) Was calculated.
Cleaning rate (%) = (K / S of contaminated cloth before cleaning-K / S of contaminated cloth after cleaning) / (K / S of contaminated cloth before cleaning-K / S of uncontaminated cloth) x 100・ ・ (I)

K / S is (1-R / 100) ² / (2R / 100) (however, R is the reflectance of the uncontaminated cloth, the reflectance of the contaminated cloth before cleaning, or the contaminated cloth after cleaning. It shows the reflectance (%).)
The average value of the cleaning rate of 10 wet artificially contaminated cloths was obtained, and the cleaning performance was evaluated according to the following evaluation criteria using this average value as an index.
◯: The cleaning rate is 60% or more.
Δ: The cleaning rate is 50% or more and less than 60%.
X: The cleaning rate is less than 50%.

"Evaluation of recontamination prevention performance"
<Washing>
The process (2) was carried out in the same manner as in the evaluation of the cleaning performance, and after dehydrating the textile product for 1 minute to separate it from the rinse water, a cotton cloth (recontamination judgment cloth) was taken out, sandwiched between filter papers, and dried with an iron.
The dried cotton cloth and a new wet artificially contaminated cloth and skin shirt were used as textile products, and the process (2) was carried out again in the same manner as in the evaluation of the cleaning performance.
The textile was then dehydrated for 1 minute to separate it from the rinse water, then the cotton cloth was removed, sandwiched between filter papers and ironed dry.
In Comparative Example 3, in the step (2), the component (a2) (HP20) was added to the rinse water together with the second treatment agent (B1). The concentration of component (a2) in the rinse water was 4 mass ppm.

<Evaluation>
Using a reflectance meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "spectral color difference meter SE2000"), measure the reflectance (Z value) of the recontamination judgment cloth before and after washing, and use ΔZ from the following formula (ii). Asked.
ΔZ = (Z value before washing)-(Z value after washing) ・ ・ ・ (ii)

The average value of ΔZ of five recontamination determination cloths was obtained, and the cleaning performance was evaluated according to the following evaluation criteria using this average value as an index.
⊚: ΔZ is less than 5.
◯: ΔZ is 5 or more and less than 7.
Δ: ΔZ is 7 or more and less than 9.
X: ΔZ is 9 or more.

"Evaluation of appearance stability"
30 mL of the first treatment agent (A) was taken in a cylindrical glass bottle, and the lid was closed to seal it. In this state, it was left in a constant temperature bath at 40 ° C. and stored for 1 month.
Then, it was taken out from the constant temperature bath, the transparency uniformity and fluidity of the first treatment agent (A) were visually observed, and the appearance stability of the first treatment agent (A) was evaluated based on the following criteria.
◯: It was transparent and uniform, and showed fluidity.
Δ: A precipitate was observed at the bottom of the glass bottle, but the precipitate disappeared (dissolved) by gently shaking the glass bottle.
X: A precipitate was observed at the bottom of the glass bottle, and the precipitate did not disappear even when the glass bottle was shaken lightly. Alternatively, the first treatment agent (A) was solidified.

As is clear from Table 3, in the case of each example, it was possible to impart more excellent flexibility to the textile product while exhibiting cleaning performance and recontamination prevention performance. In addition, the first treatment agent (A) used in each example was also excellent in appearance stability.
On the other hand, in the cases of Comparative Examples 1 and 2, sufficient flexibility could not be imparted to the textile product. In particular, in the case of the comparative example, the recontamination prevention performance was also inferior.
In the case of Comparative Example 3, since the second treatment agent (B) and the component (a2) were used in combination in the step (2), it was possible to impart the same flexibility as in each example to the textile product. Since the step (1) was performed using the first treatment agent (A10) containing no component (a2), the recontamination prevention performance was inferior.

Claims (7)

A method for washing textile products, wherein the following steps (1) and the following steps (2) are performed one or more times each, and after the final step (1), one or more steps (2) are performed.
Step (1): the following component (a1) and the following (a2) viewed including the components, the following (a1-1) component / the following (a1-2) mass ratio represented by components 0.5 to 2.5 A cleaning process that cleans textiles in a cleaning solution.
Step (2): After the step (1), the textile product is separated from the cleaning liquid, and the textile product separated from the cleaning liquid is rinsed in rinsing water containing the following component (b1).
(A1) component: A surfactant containing the following (a1-1) component and the following (a1-2) component.
Component (a1-1): A nonionic surfactant containing one or more selected from the compound represented by the following general formula (A1) and the compound represented by the following general formula (A2).
R ^11- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ¹² ... (A1)
R ^21- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (A2)
(In the formula (A1), R ¹¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ¹² is an alkyl group having 1 to 6 carbon atoms, s and u represent the average number of repetitions of EO, and s + u is. It is a number of 6 to 20, where t represents the average number of repetitions of PO, 0, EO represents an oxyethylene group, and PO represents an oxypropylene group.
In formula (A2), R ²¹ is a hydrocarbon having 6 to 22 carbon atoms, v and x represent the average number of repetitions of EO, v + x is a number of 11 to 18, and w represents the average number of repetitions of PO. Represented by 0, EO represents an oxyethylene group and PO represents an oxypropylene group. )
(A1-2) Ingredient: Anionic surfactant.
(A2) Component: An alkylene oxide adduct of polyalkyleneamine.
(B1) Component: Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be partitioned by an ester group or an amide group, a salt thereof, and a quaternized product thereof. At least one compound. The method for washing a textile product according to claim 1, wherein the mass ratio represented by {the (a1-2) component / the (a1) component} / the (a2) component is 0.1 to 1. The method for washing a textile product according to claim 1 or 2, wherein the rinse water further contains the following component (b2).
(B2) Ingredient: Cyclic dextrin. The method for washing a textile product according to any one of claims 1 to 3, wherein the step (2) is performed once. Following component (a1) and the following component (a2) only contains the first processing following (a1-1) component / the following (a1-2) mass ratio represented by component is 0.5 to 2.5 A treatment kit for textile products comprising the agent (A) and the second treatment agent (B) containing the following component (b1).
(A1) component: A surfactant containing the following (a1-1) component and the following (a1-2) component.
Component (a1-1): A nonionic surfactant containing one or more selected from the compound represented by the following general formula (A1) and the compound represented by the following general formula (A2).
R ^11- C (= O) O-[(EO) _s / (PO) _t ]-(EO) _u- R ¹² ... (A1)
R ^21- O-[(EO) _v / (PO) _w ]-(EO) _x- H ... (A2)
(In the formula (A1), R ¹¹ is a hydrocarbon group having 7 to 22 carbon atoms, R ¹² is an alkyl group having 1 to 6 carbon atoms, s and u represent the average number of repetitions of EO, and s + u is. It is a number of 6 to 20, where t represents the average number of repetitions of PO, 0, EO represents an oxyethylene group, and PO represents an oxypropylene group.
In formula (A2), R ²¹ is a hydrocarbon having 6 to 22 carbon atoms, v and x represent the average number of repetitions of EO, v + x is a number of 11 to 18, and w represents the average number of repetitions of PO. Represented by 0, EO represents an oxyethylene group and PO represents an oxypropylene group. )
(A1-2) Ingredient: Anionic surfactant.
(A2) Component: An alkylene oxide adduct of polyalkyleneamine.
(B1) Component: Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be partitioned by an ester group or an amide group, a salt thereof, and a quaternized product thereof. At least one compound. The processing kit for textile products according to claim 5, wherein the mass ratio represented by {the (a1-2) component / the (a1) component} / the (a2) component is 0.1 to 1. The treatment kit for textile products according to claim 5 or 6, wherein the second treatment agent (B) further contains the following component (b2).
(B2) Ingredient: Cyclic dextrin.