JP2024025411A - washing method - Google Patents

Abstract

To provide a washing method that exhibits a superior washing effect and further improves texture of a washing object.SOLUTION: A washing method includes a washing step for bringing washing liquid containing following components (A) and (B) into contact with a washing object, and a spin-drying step for spin-drying the washing object not through rinsing after the washing step. The component (A): a non-soap-based surfactant including a nonionic surfactant (Ax) represented by a following formula (ax1): R11-O-(R12O)n-H (ax1), and the component (B): cellulase.SELECTED DRAWING: None

Description

The present invention relates to a washing method.

In order to maintain the quality of clothing and make it last longer, washing is required to remove stains from clothing while also suppressing deterioration of the texture of clothing.
Items that make you realize how good the texture of textile products such as clothing are are that there are no pilling on the clothes after washing, and that the clothes feel soft after washing.

As a method for improving the texture of clothing, a textile detergent composition containing a silicone compound, an alcohol alkoxylate, and an endo-type cellulase in a specific mass ratio is used to wash the clothing to be washed, and then the clothing is washed. A washing method of rinsing with water has been proposed (Patent Document 1). According to the invention of Patent Document 1, it is intended to impart a smooth texture to the items to be washed.

Japanese Patent Application Publication No. 2021-138890

However, there is a need for further improvement in the texture of washed items after washing.
Therefore, an object of the present invention is to provide a washing method that exhibits a good cleaning effect and can further improve the texture of the items to be washed.

As a result of extensive research, the present inventors found that by washing textile products with a cleaning solution containing a specific surfactant and cellulase, and then dehydrating them without rinsing, the texture of the textile products being washed can be improved. The present invention was completed based on the knowledge that this can be further improved.
The present invention has the following aspects.

<1>
A cleaning step of bringing a cleaning liquid containing the following (A) component and the following (B) component into contact with the object to be washed;
a dehydration step of dehydrating the object to be washed without rinsing after the washing step;
A washing method.
Component (A): A non-soap surfactant containing a nonionic surfactant (Ax) represented by the following formula (ax1).
R ¹¹ -O-(R ¹² O) _n -H...(ax1)
[In formula (ax1), R ¹¹ represents a branched alkyl group having 12 to 16 carbon atoms or a straight chain alkyl group having 12 to 16 carbon atoms, and when R ¹¹ is a straight chain alkyl group, the oxygen atom is a straight chain alkyl group. Bonds to a secondary carbon atom in a chain alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Further, n represents the average number of repetitions of R ¹² O and is from 3 to 10. ]
(B) Component: Cellulase.
<2>
The washing method according to <1>, wherein in the washing step, the content of the component (A) based on the total weight of the washing liquid is 50 to 300 ppm by weight.
<3>
The washing method according to <1> or <2>, wherein in the washing step, the content of the (Ax) component with respect to the total weight of the washing liquid is 10 to 200 ppm by mass.
<4>
The washing method according to any one of <1> to <3>, wherein in the washing step, the content of the component (B) based on the total weight of the washing liquid is 0.1 to 50 ppm by mass.
<5>
The washing method according to any one of <1> to <4>, wherein the washing liquid further contains one or more selected from the following component (C) and component (D) below.
(C) Component: Modified silicone.
(D) Component: Soil release agent.
<6>
The washing method according to <1> to <5>, wherein the washing liquid further contains the following component (E).
(E) Component: Antifoaming silicone.

According to the washing method of the present invention, a good washing effect can be exhibited and the texture of the items to be washed can be further improved.

(Washing method)
The washing method of the present invention includes a washing step in which a washing liquid is brought into contact with the object to be washed, and a dehydration step in which the object to be washed is dehydrated without rinsing after the washing step. That is, the washing method of the present invention includes a washing step and a dehydration step, and does not include a rinsing step between the washing step and the dehydration step.

<Cleaning process>
The cleaning process is a process of bringing a cleaning liquid into contact with the object to be washed.
Examples of the items to be washed include textile products such as clothing, dishcloths, towels, sheets, and curtains. Furthermore, the material of the textile product is not particularly limited, and examples include natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, and blended, woven, or knitted products of these various fibers.
Examples of natural fibers include cotton, wool, linen, and the like.
Examples of synthetic fibers include polyester, nylon, and acrylic.
Examples of semi-synthetic fibers include acetate and the like.
Examples of recycled fibers include rayon, Tencel, polynosic, and the like.

≪Cleaning liquid≫
The cleaning liquid contains the following (A) component and the following (B) component. The cleaning liquid may be an aqueous solution or an aqueous dispersion.

The cleaning liquid may be an aqueous solution in which each component of the cleaning composition is dispersed in water, or an aqueous solution in which an integrated cleaning composition is dispersed in water. As the cleaning composition, a liquid cleaning composition is preferred.

[(A) Component]
Component (A) is a non-soap surfactant. Component (A) may be used alone or in combination of two or more.
A "non-soap surfactant" is a surfactant excluding higher fatty acids or salts thereof (so-called soaps). "Higher fatty acids" are saturated or unsaturated fatty acids having 8 to 24 carbon atoms. That is, component (A) is a surfactant excluding saturated or unsaturated fatty acids having 8 to 24 carbon atoms and salts thereof.
Component (A) includes nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, semipolar surfactants, and the like.

Component (A) includes a nonionic surfactant (component (Ax)) represented by the following formula (ax1). Furthermore, it is preferable that the component (A) contains one or more selected from the components (A1) and (A2) described below.
By containing the component (A), the cleaning liquid can enhance the cleaning effect on the items to be washed. In addition, since the (A) component contains the (Ax) component, the (Ax) component penetrates into the items to be washed, increasing the cleaning effect, increasing the penetration power of the (B) component into the items to be washed, and increasing the cleaning effect. The texture of objects (pilling prevention, flexibility) can be further enhanced.

The component (Ax) is a nonionic surfactant represented by the following formula (ax1).

R ¹¹ -O-(R ¹² O) _n -H...(ax1)
[In formula (ax1), R ¹¹ represents a branched alkyl group having 12 to 16 carbon atoms or a straight chain alkyl group having 12 to 16 carbon atoms, and when R ¹¹ is a straight chain alkyl group, the oxygen atom is a straight chain alkyl group. Bonds to a secondary carbon atom in a chain alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Further, n represents the average number of repetitions of R ¹² O and is from 3 to 10. ]

In formula (ax1), R ¹¹ is an alkyl group.
The number of carbon atoms in R ¹¹ is 12 to 16, more preferably 12 to 14. When the number of carbon atoms in R ¹¹ is at least the above lower limit, the cleaning effect can be further enhanced. When the number of carbon atoms in R ¹¹ is less than or equal to the above upper limit, the texture of the items to be washed can be further improved.

R ¹¹ may be a straight chain alkyl group or a branched alkyl group.
When R ¹¹ is a straight-chain alkyl group, the oxygen atom connected to (R ¹² O) is bonded to the secondary carbon atom in R ¹¹ .

Examples of R ¹² O include oxyethylene group, oxypropylene group, and oxybutylene group. Among these, R ¹² O is preferably oxyethylene group or oxypropylene group, and oxyethylene group alone or oxyethylene group and oxyethylene group are preferable. More preferably, both are propylene groups. When it is both an oxyethylene group and an oxypropylene group, the oxyethylene group and the oxypropylene group may be random or block.
n is the average number of R ¹² O repeats. n is 3 to 10, preferably 3 to 7, and more preferably 3 to 5.

As the component (Ax), a commercially available product may be used. Commercially available products include, for example, Diadol (registered trademark) manufactured by Mitsubishi Chemical Corporation (C13, the number after C indicates the number of carbon atoms in the alcohol. The same applies hereinafter), and Neodol (registered trademark) manufactured by Shell. (mixture of C12 and C13), Sasol (registered trademark) 23 (mixture of C12 and C13), EXXAL (registered trademark) 13 (C13), etc. Added ethylene oxide;
A product in which ethylene oxide equivalent to 3, 5, or 7 moles is added to a C13 alcohol obtained by subjecting a C12 alkene obtained by trimerizing butene to the oxo method (Lutensol (registered trademark)). TO3, Lutensol TO5, Lutensol TO7, manufactured by BASF);
A product obtained by adding 9 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a garbet reaction (Lutensol XP90, manufactured by BASF);
A product obtained by adding 7 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a garbet reaction (Lutensol XL70, manufactured by BASF);
A product obtained by adding 6 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a garbet reaction (Lutensol XA60, manufactured by BASF);
A product obtained by adding 5 moles of ethylene oxide to a C10 alcohol obtained by subjecting pentanol to a garbet reaction (Lutensol XP50, manufactured by BASF);
Addition of 3, 5, 7 or 9 moles of ethylene oxide to a C12-14 secondary alcohol (Softanol (registered trademark) 30, Softanol 50, Softanol 70, Softanol 90, manufactured by Nippon Shokubai Co., Ltd.) etc.
The (Ax) component may be used alone or in combination of two or more.

Component (A1) is a nonionic surfactant other than component (Ax).
By using the (Ax) component together with a nonionic surfactant other than the (Ax) component, good detergency and rinsing properties can be obtained.
Examples of the component (A1) include polyoxyalkylene type nonionic surfactants other than the component (Ax).
Examples of the component (A1) include a compound represented by the following formula (a1) (component (a1)). However, component (a1) does not include component (Ax).
Component (a1) is suitable for a washing method that does not involve rinsing because it produces little foaming.

R ² -X-[(EO) _s / (PO) _t ]-(EO) _u -R ³ ...(a1)

In formula (a1), R ² is a hydrocarbon group having 8 to 22 carbon atoms, X is O, COO, or CON, and R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number It is an alkenyl group of 2 to 6, s represents the average repeating number of EO and is a number from 3 to 25, t represents the average repeating number of PO and is a number from 0 to 6, and u is the average repeating number of EO. It represents the repeating number and is a number from 0 to 25, EO represents an oxyethylene group, and PO represents an oxypropylene group.
[(EO) _s /(PO) _t ] indicates that it may be a random chain or a block chain of EO and PO. The average number of repetitions can be measured by gas chromatography or the like.

In formula (a1), the hydrocarbon group of R ² may be linear or branched. It may have an unsaturated bond. The number of carbon atoms is preferably 8 to 22, more preferably 10 to 20, even more preferably 10 to 18. Examples of R ² include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides.
The alkyl group for R ³ is preferably an alkyl group having 1 to 3 carbon atoms. The alkenyl group for R ³ is preferably an alkenyl group having 2 to 3 carbon atoms. R ³ is preferably a hydrogen atom.
In formula (a1), X is preferably O or COO because of its excellent effect of improving detergency.

s is a number from 3 to 25, preferably from 3 to 20, more preferably from 3 to 18, and even more preferably from 3 to 15. When s is within the above range, detergency is likely to be improved.
t is preferably 0 to 6, more preferably 0 to 3.
u is preferably 0 to 25, more preferably 0 to 15, even more preferably 0 to 10.
s+u is preferably 3 to 30, more preferably 10 to 30, even more preferably 12 to 25, particularly preferably 12 to 22, and most preferably 12 to 18.

Component (a1) may be a commercially available product, or at least ethylene oxide of ethylene oxide and propylene oxide may be added to commercially available raw materials (primary or secondary higher alcohol, higher fatty acid, higher fatty acid amide, etc.) by a known method. It may be added.
As a specific example of component (a1), ethylene oxide equivalent to 12 moles or 15 moles is added to natural alcohol such as CO-1214 (trade name) or CO-1270 (trade name) manufactured by P&G. 15 mol equivalent of ethylene oxide added to methyl coconut fatty acid (lauric acid/myristic acid = 8/2) using an alkoxylation catalyst (polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)) etc.

In particular, as component (a1), X is an oxygen atom, t is 0, ^R3 is a hydrogen atom, ^R2 is a straight-chain alkyl group, and the oxygen atom of X is in the straight-chain alkyl group. A linear polyoxyethylene alkyl ether (linear AE) bonded to the primary carbon atom of is preferred.
In linear AE, the number of carbon atoms in R ² is preferably 8 to 22, more preferably 10 to 18.
The average number of repetitions of EO (s+u) is preferably 10 to 30, more preferably 12 to 18.
When component (Ax) and linear AE are used in combination, good detergency and good texture can be easily achieved in a well-balanced manner, and rinsability is also improved.

Component (A2) is a non-soap anionic surfactant.
By using the (Ax) component and the (A2) component together, good detergency and flexibility can be obtained.
As the component (A2), for example, linear alkylbenzenesulfonic acid or its salt (LAS), α-olefin sulfonic acid or its salt (AOS), internal olefin sulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt, etc. salt, linear or branched alkyl sulfate or its salt, polyoxyalkylene alkyl ether sulfate or its salt (AES), polyoxyalkylene alkenyl ether sulfate or its salt, alkanesulfonic acid having an alkyl group or its salt, α-sulfo fatty acid ester or its salt (MES), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkyl amide ether carboxylic acid or its salt, alkenyl amide ether carboxylic acid or its salt , acylaminocarboxylic acid or its salt, alkyl phosphate ester or its salt, polyoxyalkylene alkyl phosphate ester or its salt, polyoxyalkylene alkyl phenyl phosphate ester or its salt, glycerin fatty acid ester monophosphate ester or its salt, etc. can be mentioned.
Examples of the salt in component (A2) include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; and alkanolamine salts such as monoethanolamine salts and diethanolamine salts.
Component (A2) may be produced by a conventional method, or a commercially available product may be used.

Components (A2) include linear alkylbenzenesulfonic acids or salts thereof, α-olefinsulfonic acids or salts thereof, internal olefinsulfonic acids or salts thereof, and polyoxyalkylene alkyl ether sulfuric esters in terms of suppressing foaming of the cleaning liquid. or a salt thereof, and one or more selected from the group consisting of polyoxyalkylene alkenyl ether sulfate or a salt thereof.

The linear alkylbenzenesulfonic acid or its salt preferably has a linear alkyl group having 8 to 16 carbon atoms, particularly preferably a linear alkyl group having 10 to 14 carbon atoms.
The α-olefin sulfonate and internal olefin sulfonate preferably have 10 to 20 carbon atoms.
Examples of the polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt include a compound represented by the following general formula (a2) (component (a2)).

R ¹ -O-[(EO) _j /(PO) _k ]-SO ₃ -M ⁺ ...(a2)

In formula (a2), R ¹ is a linear or branched alkyl group having 8 to 20 carbon atoms or a linear or branched alkenyl group having 8 to 20 carbon atoms, and EO is an oxyethylene group. , PO is an oxypropylene group, j is a number of 0.5 or more indicating the average repeating number of EO, k is a number from 0 to 6 indicating the average repeating number of PO, and M+ is the counter cation. It is. [(EO) _j /(PO) _k ] indicates that there is no limitation on the arrangement order of EO and PO.

R ¹ is preferably a straight or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, more preferably a straight or branched alkyl group or alkenyl group having 12 to 14 carbon atoms.
In particular, a straight-chain alkyl group having 10 to 20 carbon atoms is preferred, and a straight-chain alkyl group having 12 to 14 carbon atoms is more preferred.
j is preferably 0.5 to 5, more preferably 0.5 to 4, even more preferably 0.5 to 3.5, particularly preferably 1.5 to 2.5.
k is preferably 0 to 3, more preferably 0.
j+k is preferably 0.5 or more, more preferably 0.5 to 5.
In [(EO) _j /(PO) _k ] in formula (a2), EO and PO may be arranged in a mixed manner. When EOs and POs are arranged in a mixed manner, they may be arranged in a random pattern or in a block pattern. The distribution of added moles of ethylene oxide and propylene oxide is not particularly limited.
Examples of M ⁺ include alkali metal ions such as sodium ions and potassium ions; alkaline earth metal ions such as magnesium ions; and alkanolamines with monoethanolamine, diethanolamine, etc.
Component (a2) may be produced by a conventional method, or a commercially available product may be used.

Examples of component (A) other than the above include cationic surfactants, amphoteric surfactants, and semipolar surfactants.
Examples of the cationic surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. Counter ions for these salts include halogen ions, alkyl sulfate ions, and the like. Examples of the halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions. The alkyl sulfate ion preferably has an alkyl group having 1 to 3 carbon atoms, such as methyl sulfate ion, ethyl sulfate ion, and the like.
Examples of amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidobetaines, imidazolinium betaines, and the like.
Examples of the semipolar surfactant include amine oxide type surfactants such as lauryl dimethyl amine oxide and lauric acid amidopropyl dimethyl amine oxide.
These may be manufactured by conventional methods, or commercially available products may be used.

The content of component (A) in the cleaning solution is preferably 50 to 300 mass ppm, more preferably 70 to 270 mass ppm, and even more preferably 100 to 200 mass ppm, based on the total mass of the cleaning solution. When the content of component (A) is at least the above lower limit, the cleaning effect on the items to be washed can be further enhanced. When the content of component (A) is below the above upper limit, foaming of the cleaning solution can be further suppressed, the amount of component (A) remaining on the items to be washed is reduced, and the texture of the items to be washed can be further enhanced. .

The content of the (Ax) component in the cleaning solution is preferably 10 to 200 mass ppm, more preferably 20 to 150 mass ppm, and even more preferably 30 to 60 mass ppm, based on the total mass of the cleaning solution. When the content of component (A) is at least the above lower limit, the cleaning effect on the items to be washed can be further enhanced. When the content of component (A) is below the above upper limit, foaming of the cleaning liquid can be further suppressed.
The mass ratio of the content of surfactants other than the (Ax) component to the content of the (Ax) component, and the ratio of surfactants other than (Ax)/Ax is preferably 0.1 to 10, and 0.5 to 7. is more preferred, and 1 to 5 are even more preferred. When it is above the lower limit value, good detergency can be obtained, and when it is below the upper limit value, the texture of the items to be washed can be further improved.

[(B) Component]
Component (B) is cellulase. Component (B) can cut the fluff of the fibers and suppress the formation of pilling. In addition, when component (B) is used in combination with component (Ax), it penetrates into the fibers and cuts the fluff inside the fibers, making it easier to take air into the fibers and increasing flexibility. That is, when the cleaning liquid contains the component (B), the texture of the item to be washed can be improved.
Component (B) is not particularly limited and can be appropriately selected from known components.
As component (B), an endoglucanase having a molecular weight of 30 to 50 kDa and an isoelectric point of 4.5 to 6.0 is particularly preferable because it has excellent dirt removal performance from fibers. This endoglucanase is thought to have the effect of removing dirt adsorbed to the amorphous portion inside the fiber. It is particularly preferred that the endoglucanase is derived from a Humicola insolens strain.
The molecular weight (unit: kDa) of endoglucanase is a value obtained by SDS-PAGE using a precast gel (Atto) with a gel concentration of 12.5% total acrylamide (mass/volume) and BenchiMark Proteim Ladder (Invitrogen).
Endoglucanases are commercially available, such as Endolase 5000L (trade name, manufactured by Novozyme) and Carezyme Premium 4500L (trade name, manufactured by Novozyme).

The content of component (B) in the cleaning solution is preferably 0.1 to 50 mass ppm, more preferably 0.5 to 30 mass ppm, and even more preferably 2 to 20 mass ppm, based on the total mass of the cleaning solution. When the content of component (B) is equal to or higher than the above lower limit, the occurrence of pilling in the laundry can be further suppressed, and the texture of the laundry after washing can be improved. When the content of component (B) is below the above upper limit, deterioration in strength of the object to be washed can be further suppressed. Note that the content of component (B) is the content as an enzyme preparation.

In the cleaning liquid, the mass ratio expressed by component (B)/component (Ax) (mass ratio of component (B) to component (ax), B/ax ratio) is preferably 0.01 to 5% by mass, and 0. More preferably .05 to 2, and even more preferably 0.1 to 1. When the B/Ax ratio in the cleaning liquid is equal to or higher than the above lower limit value, the texture of the item to be washed can be further improved. The cleaning effect can be further enhanced when the B/Ax ratio in the cleaning liquid is below the above upper limit.

[(C) Component]
The cleaning liquid may contain component (C). Component (C) is a modified silicone. Component (C) contributes to improving the flexibility of the object to be washed.
Examples of component (C) include amino-modified silicones, aminopolyether-modified silicones, amide-modified silicones, amide-polyether-modified silicones, alkyl-modified silicones, alkyl-polyether-modified silicones, and polyether-modified silicones. Among these, polyether-modified silicones and amino-modified silicones are preferred, and polyether-modified silicones are more preferred, from the viewpoint of further increasing the flexibility of textile products and the appearance stability of cleaning liquids.
Component (C) may be used alone or in combination of two or more.

The polyether-modified silicone is a compound ((C1) component) represented by the following formula (c1).

In formula (c1), R ²⁴ is a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom. R ²³ is a linear or branched alkylene group having 1 to 4 carbon atoms, or a linear or branched alkenylene group having 2 to 4 carbon atoms.
^Y3 represents a polyoxyalkylene group.
p is a number from 10 to 10,000, and q is a number from 1 to 1,000. The order of each structural unit to which p and q are attached may be different.

The specific gravity of component (C1) at 25°C is preferably 1.00 to 1.09, more preferably 1.04 to 1.09. Note that the specific gravity is a value measured using a pycnometer at 25° C. according to the specific gravity measurement method of the Japanese Pharmacopoeia General Test Methods.

Commercially available products of (C1) include, for example, CF1188N (trade name) manufactured by Dow Corning Toray Co., Ltd., KF-6011 (specific gravity: 1.06) and KF-6012 (specific gravity: 1.06) manufactured by Shin-Etsu Chemical Co., Ltd. 03), KF-6015 (specific gravity 1.00), KF-6017 (specific gravity 1.01), etc.
These (C1) components may be used alone or in combination of two or more.

Amino-modified silicone is a compound formed by introducing amino-modified groups into both ends or side chains of a dimethyl silicone skeleton.
Commercially available amino-modified silicones can be used. For example, DOWSIL SF8417 Fluid, DOWSIL BY16-849 DOWSIL, DOWSIL BY16-892, DOWSIL FZ-3785 (all product names) from Dow Corning Toray Co., Ltd., KF-864, KF-860, KF- from Shin-Etsu Chemical Co., Ltd. Examples thereof include 880, KF-8004, KF-8002, KF-867, KF-869, and KF-861 (the above are trade names).
These amino-modified silicones may be used alone or in combination of two or more.

Aminopolyether-modified silicone is a silicone that has at least one amino-modified group and a polyether-modified group in its structure. More specifically, at least one amino-modified group selected from a side chain modified with an amino group and a terminal modified with an amino group, and a side chain modified with a polyether group or modified with a polyether group. It is a silicone compound that has both terminal ends within its structure. Among these, silicones having modified side chains are preferred.
Commercially available aminopolyether-modified silicones include, for example, DOWSIL BY16-891 and DOWSIL Silstyle 104 manufactured by Dow Corning Toray Co., Ltd., and KF-877, KF-889, and X-22-3939A manufactured by Shin-Etsu Chemical Co., Ltd. , X-52-8369A, etc., and "WETSOFT CTA", "WETSOFT AE200", "WETSOFT NE810", "WETSOFT NE820", and "WETSOFT WP201" manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
These aminopolyether-modified silicones may be used alone or in combination of two or more.

Commercially available products containing component (C) other than those listed above include, for example, DOWSIL 2501 Cosmetic Wax, DOWSIL 2503 Cosmetic Wax, DOWSIL 580 Wax, DOWSIL AMS-C30 Cosmetic Wax, BY16-89 manufactured by Dow Corning Toray Co., Ltd. 1. DOWSIL FZ -2203, DOWSIL FZ-3789, DOWSIL FZ-2222 (all product names), etc.

When the cleaning liquid contains component (C), the content of component (C) is preferably 0.1 to 50 mass ppm, more preferably 0.5 to 30 mass ppm, and 1 to 30 mass ppm, based on the total mass of the cleaning fluid. More preferably, it is 10 mass ppm. When the content of component (C) is at least the above lower limit, the flexibility of the washed item after washing can be further improved. When the content of component (C) is below the above upper limit, the content of component (C) can be reduced while fully exhibiting the effect of component (C).

[(D) Component]
The cleaning liquid may contain component (D). Component (D) is a soil release agent. Component (D) contributes to improving the flexibility of the item to be washed.
It is preferable that the cleaning liquid contains one or more selected from the above-mentioned (C) component and (D) component.
Component (D) is an aqueous solution having at least one unit ((d1) unit) selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units and (poly)oxyalkylene units ((d2) units). (D1) component).
Further, examples of the soil release agent include cationized cellulose described in JP-A No. 2019-90057.

The unit (d1) is at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units.
The alkylene terephthalate unit is a unit represented by the following formula (d1-1).

In formula (d1-1), R ³¹ is an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ³¹ is preferably 2 to 4.
Examples of the alkylene terephthalate unit include ethylene terephthalate unit, n-propylene terephthalate unit, isopropylene terephthalate unit, n-butylene terephthalate unit, isobutylene terephthalate unit, sec-butylene terephthalate unit, tert-butylene terephthalate unit, and the like. Among these, isopropylene terephthalate units are preferred.
Component (D1) may contain one type of these alkylene terephthalate units alone, or two or more types of these alkylene terephthalate units.

The alkylene isophthalate unit is a unit represented by the following formula (d1-2).

In formula (d1-2), R ⁴¹ is an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ⁴¹ is preferably 2 to 4.
Examples of alkylene isophthalate units include ethylene isophthalate units, n-propylene isophthalate units, isopropylene isophthalate units, n-butylene isophthalate units, sec-butylene isophthalate units, and tert-butylene isophthalate units. It will be done. Among these, isopropylene isophthalate units are preferred.
Component (D1) may contain one type of these alkylene isophthalate units alone, or two or more types of these alkylene isophthalate units.

Component (D1) may have both an alkylene terephthalate unit and an alkylene isophthalate unit as the (d1) unit, or may have only one of an alkylene terephthalate unit and an alkylene isophthalate unit. . It is more preferable that the component (D1) contains both alkylene terephthalate units and alkylene isophthalate units.

The (poly)oxyalkylene unit ((d2) unit) is a general term for monooxyalkylene units and polyoxyalkylene units.
The (d2) unit is represented by the following formula (d2-1).

-(R ⁵¹ O) _w - ... (d2-1)

In formula (d2-1), R ⁵¹ represents an alkylene group having 1 to 4 carbon atoms. The number of carbon atoms in R ⁵¹ is preferably 2 to 4.
w represents the average number of repetitions of (R ⁵¹ O). w is 1 to 100, preferably 1 to 80, and more preferably 1 to 50.

Examples of the (d2) unit include oxyethylene units, polyoxyethylene units, oxypropylene units, polyoxypropylene units, and polyoxyethylene polyoxypropylene units, with oxyethylene units or polyoxyethylene units being preferred.
The component (D1) may contain one kind of these (d2) units alone, or two or more kinds thereof.

The component (D1) may be anything as long as it has a (d1) unit and a (d2) unit, and may be a random copolymer or a block copolymer. Among these, block copolymers are preferred as component (D).
Component (D1) is a unit other than the (d1) unit and the (d2) unit (for example, a unit derived from a polymerization initiator, a polymerization terminator, etc., or another unit that can be polymerized with the (d1) unit or (d2) unit). ) may be included. However, the total amount of units (d1) and (d2) is preferably 80 mol% or more, more preferably 90 mol% or more, based on the total amount of repeating units in component (C).

Examples of the component (D1) include compounds represented by the following formula (D1-1) or the following general formula (D1-2).

In formula (D1-1), Z ¹ is each independently a hydrogen atom or a methyl group, preferably both are methyl groups.
R ⁶¹ and R ⁶² are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
x ¹ is a number from 0 to 10 representing the average repeating number of the structural unit, preferably from 0.5 to 5, and more preferably from 0.5 to 2.5. When x ¹ is equal to or greater than the above lower limit value, the effect of improving flexibility is excellent. When x ¹ is less than or equal to the above upper limit value, a liquid cleaning agent with excellent appearance stability is likely to be obtained.
y ¹ is a number representing the average repeating number of (R ⁶¹ O), each independently preferably from 1 to 100, more preferably from 1 to 80, even more preferably from 1 to 50, particularly preferably from 10 to 50, 20-30 is most preferred. When ^y1 is equal to or greater than the above lower limit, the effect of improving permeability is excellent. When ^y1 is less than or equal to the above upper limit, the effect of improving flexibility is excellent.
In formula (D1-1), the ratio of x ¹ to y ¹ (x ¹ :y ¹ ) is preferably 1:5 to 1:20, more preferably 1:8 to 1:18. When (x ¹ :y ¹ ) is within the above range, the effect of improving flexibility is excellent and the effect of improving permeability is excellent.

In formula (D1-2), Z ² is each independently a hydrogen atom or a methyl group, preferably both are methyl groups.
R ⁶³ and R ⁶⁴ are each independently an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms.
x ² is a number from 0 to 10 representing the average repeating number of the structural unit, preferably from 0.5 to 5, more preferably from 0.5 to 2.5. When x ² is equal to or greater than the above lower limit value, the effect of improving flexibility is excellent. When x ² is less than the above upper limit, a liquid cleaning agent with excellent appearance stability is likely to be produced.
y ² is a number representing the average repeating number of (R ⁶³ O), each independently preferably from 1 to 100, more preferably from 1 to 80, even more preferably from 1 to 50, particularly preferably from 10 to 50, 20-30 is most preferred. When ^y2 is equal to or greater than the above lower limit, the effect of improving permeability is excellent. When y ² is less than or equal to the above upper limit value, the effect of improving flexibility is excellent.
In formula (D1-2), the ratio between x2 and y2 (x ² :y ² ) is preferably 1:5 to 1:20, more preferably 1:8 to 1:18. When (x ² :y ² ) is within the above range, the effect of improving flexibility is excellent and the effect of improving permeability is excellent.

The mass average molecular weight of component (D1) is preferably 500 to 10,000. When the mass average molecular weight is within the above range, dissolution and dispersibility in water is excellent. In addition, it is easy to improve the water absorption of hydrophobic fibers such as animal fiber products.
The lower limit of the mass average molecular weight of component (D1) is more preferably 800 or more, and even more preferably 1000 or more.
The upper limit of the mass average molecular weight of component (D1) is more preferably 9,000 or less, and even more preferably 8,000 or less.
Therefore, the mass average molecular weight of component (D1) is more preferably from 800 to 9,000, even more preferably from 1,000 to 8,000.

The mass average molecular weight of component (D1) is a value measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent, and converted using PEG (polyethylene glycol) as a calibration curve.

Component (D1) is easily available on the market. In addition, component (C) may be synthesized by methods described in various publications. Publications describing the method for producing component (C) include, for example, Journal of Polymer Science, Volume 3, pages 609-630 (1948); Journal of Polymer Science, Volume 8, pages 1-22 (1948); (1951) and Japanese Patent Application Laid-Open No. 61-218699.
Commercially available products of component (D1) include, for example, TexCare (registered trademark) SRN-100 (trade name, manufactured by Clariant Japan Co., Ltd., mass average molecular weight: 2000-3000) and TexCare SRN-300 (trade name, manufactured by Clariant Japan Co., Ltd.). Co., Ltd., mass average molecular weight: 7000), Repel-O-Tex (registered trademark) Crystal (trade name, manufactured by Rhodia, mass average molecular weight: undetermined), Repel-O-Tex QCL (trade name, manufactured by Rhodia, mass average molecular weight: undetermined). Among these, TexCare SRN-100 is preferred because it has high solubility in water and shows little deterioration in cleaning performance after storage. Particularly preferred is a 70% by mass aqueous solution of TexCare SRN-100, and a commercially available product thereof includes TexCare SRN-170C (trade name, manufactured by Clariant Japan Co., Ltd.).

When the cleaning liquid contains component (D), the content of component (D) is preferably 1 to 100 mass ppm, more preferably 3 to 70 mass ppm, and 5 to 50 mass ppm based on the total mass of the cleaning fluid. More preferred. When the content of the component (D) is at least the above lower limit, the flexibility of the laundry object after washing can be further improved. When the content of component (D) is below the above upper limit, the content of component (D) can be reduced while the effects of component (D) are fully exhibited.

[(E) component]
The cleaning liquid may contain component (E). Component (E) is an antifoaming silicone. Component (E) contributes to suppressing foaming of the cleaning liquid in the cleaning process.

As component (E), any of oil type, oil compound type, emulsion type, and self-emulsifying type can be used.
Oil-type antifoaming silicone is an antifoaming agent that is composed of 100% unmodified silicone oil and does not contain silica. A commercially available product is SH200 (Toray Dow Corning Co., Ltd.).
Oil compound type antifoaming silicone is an antifoaming agent made by blending water-insoluble particles such as finely powdered silica with silicone oil. Commercially available products include 8590 Additive (Toray Dow Corning Co., Ltd.), AF-8014 Anti Foam (Toray Dow Corning Co., Ltd.), AC-8066 Anti Foam (Toray Dow Corning Co., Ltd.), and ACP-3073 Anti Foam (Toray Dow Corning Co., Ltd.). (Toray/Dow Corning Co., Ltd.), KS-66 (Shin-Etsu Chemical Co., Ltd.), etc.
Solution-type antifoaming silicone is an antifoaming agent made by dissolving silicone oil in a solvent such as isoparaffin. Commercially available products include KS-602A (Shin-Etsu Chemical Co., Ltd.) and the like.
Emulsion type antifoaming silicone is an antifoaming agent made by emulsifying a silicone oil compound with a nonionic activator. Commercially available products include FS Antiform 93 (Toray Dow Corning Co., Ltd.), KM-90 (Shin-Etsu Chemical Co., Ltd.), KM-73 (Shin-Etsu Chemical Co., Ltd.), and KM-7750 (Shin-Etsu Chemical Co., Ltd.). , KM-7752 (Shin-Etsu Chemical Co., Ltd.), etc.
Self-emulsifying antifoaming silicone is an antifoaming agent composed of a hydrophilic modified silicone oil and an oil compound. Commercially available products include KS-537 (Shin-Etsu Chemical Co., Ltd.).

When the cleaning liquid contains component (E), the content of component (E) is preferably 0.01 to 10 mass ppm, more preferably 0.05 to 5 mass ppm, and 0.01 to 10 mass ppm, more preferably 0.05 to 5 mass ppm, based on the total mass of the cleaning fluid. More preferably 1 to 1 ppm by mass. When the content of component (E) is at least the above lower limit, foaming of the cleaning liquid can be further suppressed. When the content of component (E) is below the above upper limit, the content of component (E) can be reduced while fully exhibiting the effect of component (E).

[water]
The cleaning liquid contains water.
Water is not particularly limited, and examples include tap water, well water, ion exchange water, and the like.

[Other ingredients]
The cleaning liquid may contain components other than the above-mentioned components (other components).
Other components include components commonly used in cleaning compositions, such as fatty acids having 12 to 18 carbon atoms or salts thereof, water-miscible organic solvents, chelating agents, enzymes (excluding cellulases), Hydrotropes, detergent builders, stabilizers, alkali agents, preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, general-purpose dyes or pigments as coloring agents, emulsifiers, Examples include perfumes, insoluble particles, pH adjusters, and extracts of natural products. These components may be used alone or in combination of two or more.

[Physical properties of cleaning liquid]
The pH of the cleaning solution is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 8. When the pH is equal to or higher than the above lower limit, the action of the surfactant on dirt adhering to the object to be washed increases, and the cleaning effect can be further enhanced. When the pH is below the above upper limit, damage to the items to be washed can be further reduced. The pH of the cleaning solution is controlled by the composition of the cleaning composition.
The pH is a value measured using a pH meter (portable pH/ORP/ION meter D-73, manufactured by Horiba, Ltd.) with the measurement target at 25°C.

The temperature of the cleaning liquid in the cleaning step is not particularly limited, and is, for example, 0 to 60°C.

≪Cleaning conditions≫
The cleaning method in the cleaning step may be any method as long as the cleaning liquid can be brought into contact with the object to be washed for an arbitrary period of time. Examples of the cleaning method include a method in which the object to be washed is immersed in a cleaning liquid, and a method in which the object to be washed is immersed in the cleaning liquid and mechanical force is applied to the object (for example, by stirring). Methods of immersing the items to be washed in a cleaning solution and applying mechanical force to the items include a washing method using a washing machine, a method of washing the items by hand at a sink, and a method of washing the items by putting them in a bag or the like. One method is to rub and wash.

Examples of the washing machine include a two-layer washing machine, a fully automatic washing machine, a washing machine with an automatic detergent injection function, and a commercial washing machine.
Examples of the fully automatic washing machine include a washing machine with a vertical washing tub, a drum-type washing machine, and a drum-type washing machine with a dryer.
As the washing machine, a two-layer washing machine or a washing machine having a vertical washing tub is preferable because it is easy to immerse the items to be washed in the washing liquid.

The bath ratio in the washing step is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. When the bath ratio is equal to or higher than the above lower limit, the efficiency of contact between the object to be washed and the cleaning liquid can be further increased, and the cleaning effect can be further enhanced. The upper limit of the bath ratio is, for example, 50, although it is not particularly limited.
The bath ratio is a mass ratio expressed as [mass of cleaning liquid]/[mass of textile product].

The cleaning time in the cleaning step is preferably 3 minutes or more, preferably 5 minutes or more, and more preferably 10 minutes or more. When the cleaning time is equal to or longer than the above lower limit, the cleaning effect can be further enhanced. The upper limit of the washing time is not particularly limited, but from the viewpoint of washing efficiency, it is preferably 6 hours or less, more preferably 2 hours or less, even more preferably 30 minutes or less, and particularly preferably 15 minutes or less.
Note that the cleaning time is the time from when the cleaning liquid comes into contact with the object to be washed until when the dehydration process is started. The cleaning time is, for example, the time during which the cleaning liquid is in contact with the object to be washed at a bath ratio of 1 or more.

<Dehydration process>
The dehydration process is a process of separating the items to be washed and the cleaning liquid. By including the dehydration step, the items to be washed can be quickly dried.

In the dehydration step of the present invention, after the washing step, dehydration is performed without rinsing. By dehydrating without rinsing, the component (B) stays in the fibers and continues to act, further improving the texture of the items to be washed.

Examples of dehydration methods in the dehydration step include centrifugation using a washing machine, manual squeezing, and the like.

The bath ratio after dehydration is less than 1, more preferably 0.7 or less, and even more preferably 0.5 or less. If the bath ratio after dehydration is below the above upper limit, the effect of component (B) on the items to be washed will not be excessive, suppressing deterioration of the strength of the items to be washed, and enhancing the texture of the items to be washed. It will be done.

<Drying process>
The washing method of the present invention may include a drying step. By including the drying process, the moisture contained in the items to be washed can be reduced.

Examples of the drying method in the drying step include a method of drying the washed items indoors or outdoors, a method of drying with a dryer, and the like.
The time required for the drying step is, for example, 10 minutes to 12 hours.

In addition, "without rinsing" means not performing the act of contacting the item to be washed after the cleaning process (rinsing process) with a rinsing liquid that has a lower content of component (A) than the cleaning liquid of the present invention. be. Examples of the rinsing liquid include water such as tap water, well water, ion exchange water, and water in which a small amount of a cleaning composition is dispersed. The content of component (A) in the rinsing liquid is, for example, less than 50 mass ppm. Further, the content of component (B) in the rinsing liquid is, for example, less than 0.1 mass ppm.

The washing method may include two or more washing steps and dehydration steps.
The washing method may include a pre-washing step of washing the items to be washed with water or a washing liquid before the washing step. The cleaning liquid in the pre-washing process may be the same as the cleaning liquid in the cleaning process, or may be different.
The washing method may include a rinsing step after the prewashing step and before the washing step.
However, it is preferable that the washing method does not include a rinsing step after the dehydration step. If a rinsing step is provided after the dehydration step, the amount of component (B) remaining in the items to be washed may be reduced, which may impair the effects of the present invention.

According to the washing method of the present invention, since the washing method includes the washing step of contacting the washing liquid containing the components (A) and (B) with the washing object, the washing method has a cleaning effect on the washing object, and also The texture can be enhanced.
In addition, according to the washing method of the present invention, since the dehydration step is performed without rinsing, the texture of the items to be washed can be further improved.
Further, according to the washing method of the present invention, since rinsing is not performed, it can contribute to resource saving, energy saving, and reduction of environmental burden.

(Cleaning composition)
The cleaning composition of the present invention contains component (A) and component (B). The cleaning composition of the present invention may further contain one or more of component (C), component (D), and component (E). The cleaning composition of the present invention may further contain the other components mentioned above.

The cleaning composition may be liquid or solid such as powder. The cleaning composition is preferably a liquid cleaning composition because it can be quickly dispersed in water and a cleaning solution can be easily prepared.

The pH of the liquid cleaning composition at 25° C. is preferably 4 to 10, more preferably 5 to 9, and even more preferably 6 to 8. When the pH is within the above range, the storage stability of the liquid cleaning composition can be further improved.

The viscosity of the liquid cleaning composition is preferably 0.5 to 50 mPa·s, more preferably 1 to 30 mPa·s.

The content of each component in the liquid cleaning composition is determined to be the content of each component in the cleaning liquid when the liquid cleaning composition is added to water to form a cleaning liquid.
When preparing a cleaning agent, for example, 1 part by volume of the liquid cleaning agent composition is added to 10 to 2000 parts by volume of water.

The content of component (A) in the liquid cleaning composition is, for example, preferably 5 to 25% by mass, more preferably 7 to 20% by mass, and even more preferably 8 to 15% by mass. When the content of component (A) in the liquid cleaning composition is at least the above lower limit, the cleaning effect can be further enhanced. When the content of component (A) in the liquid cleaning composition is below the above upper limit, the cleaning effect can be ensured, and the texture and rinsability of the items to be washed will be good.

The content of the (Ax) component in the liquid cleaning composition is, for example, preferably 1 to 15% by mass, more preferably 2 to 12% by mass, and even more preferably 3 to 7% by mass. When the content of the (Ax) component in the liquid cleaning composition is at least the above lower limit, a good texture can be imparted to the items to be washed, and the cleaning effect can be further enhanced. When the content of the (Ax) component in the liquid cleaning composition is at most the above upper limit, a sufficient cleaning effect can be ensured and rinsing properties will be good.

The content of component (Ax) relative to the total mass of component (A) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and may be 100% by mass.

The content of component (B) in the liquid cleaning composition is, for example, preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and even more preferably 0.1 to 1% by mass. When the content of component (B) in the liquid cleaning composition is at least the above lower limit, the texture of the item to be washed can be further improved. When the content of component (B) in the liquid cleaning composition is below the above upper limit, deterioration in the strength of the object to be washed can be further suppressed.

When the liquid cleaning composition contains component (C), the content of component (C) in the liquid cleaning composition is, for example, preferably 0.01 to 2% by mass, and 0.05 to 1% by mass. More preferably, 0.1 to 0.5% by mass is even more preferred. When the content of component (C) in the liquid cleaning composition is at least the above lower limit, the flexibility of the object to be washed can be further improved. When the content of component (C) in the liquid cleaning composition is below the above upper limit, storage stability can be further improved.

When the liquid cleaning composition contains component (D), the content of component (D) in the liquid cleaning composition is, for example, preferably 0.1 to 10% by mass, and 0.3 to 5% by mass. More preferably, 0.5 to 3% by mass is even more preferred. When the content of component (D) in the liquid cleaning composition is at least the above lower limit, the texture of the item to be washed can be further improved. When the content of component (D) in the liquid cleaning composition is below the above upper limit, storage stability can be further improved.

When the liquid cleaning composition contains component (E), the content of component (E) in the liquid cleaning composition is, for example, preferably 0.001 to 1% by mass, and 0.005 to 0.5% by mass. %, more preferably 0.01 to 0.2% by mass, and particularly preferably 0.01 to 0.1% by mass. When the content of component (E) in the liquid cleaning composition is at least the above lower limit, foaming of the cleaning liquid can be further suppressed. If the content of component (E) in the liquid cleaning composition is below the above upper limit, storage stability will be affected if the content of component (E) in the liquid cleaning composition is below the above upper limit. It can be further enhanced.

The content of water in the liquid cleaning composition is, for example, preferably 30 to 95% by mass, more preferably 50 to 90% by mass, and even more preferably 70 to 85% by mass.
The content of other components in the liquid cleaning composition is, for example, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.
Note that the total content of each component in the liquid cleaning composition does not exceed 100% by mass.

In the liquid cleaning composition, the mass ratio expressed by component (B)/component (Ax) (mass ratio of component (B) to component (ax), B/ax ratio) is 0.01 to 5% by mass. is preferable, 0.05 to 2 is more preferable, and 0.1 to 1 is even more preferable. When the B/Ax ratio in the liquid detergent composition is at least the above lower limit, the texture of the object to be washed can be further improved. When the B/Ax ratio in the liquid cleaning composition is below the above upper limit, the cleaning effect can be further enhanced.

<Method for producing liquid cleaning composition>
Liquid cleaning compositions are manufactured according to conventional methods. As a manufacturing method, for example, the (A) component, the (B) component, and if necessary, the (C) component, the (D) component, the (E) component, or other components are added to a part of the water, An example of this method is to add the remainder of the water after adjusting the pH.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following description.

(Raw materials used)
<(A) component>
≪(Ax) component≫
・Ax-1: EXAL (trade name "RHA-234 TAG-90", manufactured by Lion Chemical Co., Ltd. In the formula (ax1), R ¹¹ is a branched alkyl group with 13 carbon atoms, R ¹² is an alkylene group with 2 carbon atoms, Compounds where n is 7).
・Ax-2: Lutensol (trade name "Lutensol TO-7", manufactured by BASF. In the formula (ax1), R ¹¹ is a branched alkyl group with 13 carbon atoms, R ¹² is an alkylene group with 2 carbon atoms, and n is 7 ).
・Ax-3: Softanol (trade name "Softanol 30" manufactured by Nippon Shokubai Co., Ltd.) In formula (ax1), R ¹¹ is a straight-chain alkyl group having 12 to 14 carbon atoms (O is bonded to the secondary carbon), R ¹² is an alkylene group having 2 carbon atoms, and n is a compound having 3 carbon atoms.
・Ax ^- 4: Lutensol (trade ^name "Lutensol compound.

≪(A1) Component≫
・A1-1: Linear AE, polyoxyethylene alkyl ether (15EO), natural alcohol added with ethylene oxide equivalent to 15 moles. A compound in which R ² in formula (a1) is a linear alkyl group having 12 to 14 carbon atoms, X is O, R ³ is a hydrogen atom, s is 15, t is 0, and u is 0.
・A1-2: Linear AE, polyoxyethylene alkyl ether (12EO), natural alcohol added with 12 moles of ethylene oxide. A compound in which R ² is a linear alkyl group having 12 to 14 carbon atoms, R ³ is a hydrogen atom, s is 12, t is 0, and u is 0.
・A1-3: Linear AE, polyoxyethylene alkyl ether (6EO), natural alcohol with 6 moles of ethylene oxide added. A compound in which R ² is a linear alkyl group having 12 to 14 carbon atoms, R ³ is a hydrogen atom, s is 6, t is 0, and u is 0.
・A1-4: MEE (trade name "MEE", manufactured by Lion Corporation. Polyoxyethylene fatty acid methyl ester (fatty acid carbon number 12 to 14, average number of added moles of ethylene oxide 15), in formula (a1), R ² is one or more alkyl groups selected from an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms, X is COO, ^R3 is a methyl group, and s=15, t=0, u=0.) .
・A1-5: EOPO (natural alcohol (mass ratio of primary alcohol with 12 carbon atoms/primary alcohol with 14 carbon atoms = 7/3), 8 mol of ethylene oxide, 2 mol of propylene oxide, 8 mol In the formula (a1), R ² is an alkyl group having 12 carbon atoms/an alkyl group having 14 carbon atoms = 7/3, X is O, R ³ is a hydrogen atom, and s = 8 , t=2, u=8.

≪(A2) Component≫
- A2-1: LAS (linear sodium alkylbenzene sulfonate (LAS), trade name "Lipon LS-250", manufactured by Lion Corporation).
- A2-2: AES (1EO) (manufactured by PT. Kao Indonesia Chemicals. Sodium oxyethylene alkyl sulfate having an alkyl group having 12 to 14 carbon atoms and an average repeating number of oxyethylene groups of 1.).
- A2-3: AEPS (monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate).
- A2-4: IOS (inner olefin sulfonate synthesized by the method described in Example 7 of JP-A-2001-247534).

<(B) component>
・B-1: Carezyme Premium 4500L (product name, manufactured by Novozymes).
- B-2: Cell Clean 4500T (trade name, manufactured by Novozymes).

<(C) component>
- C-1: POE modified silicone (trade name "CF1188N", manufactured by Dow Corning Toray Co., Ltd.).
- C-2: Amino-modified silicone (trade name "KF-864", manufactured by Shin-Etsu Chemical Co., Ltd.).

<(D) component>
・D-1: SR (trade name "TexCare SRN-170C", manufactured by Clariant Japan Co., Ltd., mass average molecular weight = 2000 to 3000, pH (5% by mass aqueous solution at 20 ° C.) = 4, viscosity (20 ° C.) = 300 mPa. s). TexCare SRN-170C is a 70% by mass aqueous solution of TexCare SRN-100 (trade name, manufactured by Clariant Japan, mass average molecular weight = 2000 to 3000). TexCare SRN-100 corresponds to a compound represented by formula (D1-1). ).

<(E) component>
- E-1: KM-90 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).
・E-2: SH200 (product name, manufactured by Dow Corning Toray Co., Ltd.).
- E-3: AF-8014 Antiform (trade name, manufactured by Dow Corning Toray Industries).
- E-4: FS Antiform 93 (trade name, manufactured by Dow Corning Toray Industries).

<Water>
- Ion exchange water: Balance (amount required to make the total amount of the liquid cleaning composition 100% by mass).

<Other ingredients>
Other ingredients are common in each example.
The mass % written after the name of the raw material is the ratio to the total mass of the liquid cleaning composition.
- Coconut fatty acid: Coconut fatty acid (trade name, manufactured by NOF Corporation), 0.5% by mass.
- Citric acid: Liquid citric acid (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.), 0.2% by mass.
- BHT: SUMILZER BHT-R (trade name, manufactured by Sumitomo Chemical Co., Ltd.), 0.03% by mass.
- Sodium benzoate: Sodium benzoate (manufactured by Toagosei Co., Ltd.), 0.5% by mass.
-NaOH: Sodium hydroxide (manufactured by Toagosei Co., Ltd.), 0.25% by mass.
- Ethanol: Specific 95-degree synthetic alcohol (trade name, manufactured by Nippon Alcohol Sales Co., Ltd.), 2% by mass.
- Pigment: Kayanol Milling (trade name, manufactured by Nippon Kayaku Co., Ltd.) 0.0002% by mass.
- PEG: PEG #1000-L60 (trade name, manufactured by Mitsui Chemicals, Inc.), 3% by mass.
- Diclosan: Tinosan HP100 (trade name, manufactured by BASF), 0.3% by mass.
- Perfume: Perfume composition A listed in Tables 11 to 18 of JP-A No. 2002-146399, 0.3% by mass.

(Evaluation method)
<Cleaning effect>
The soiled cloth (to be washed) was a wet artificially contaminated cloth (manufactured by the Laundry Science Association, 28.3% oleic acid, 15.6% triolein, 12.2% cholesterol oleate, 2.5% liquid paraffin, 2.5% squalene, 1.6% cholesterol, 7.0% gelatin, 29.8% mud, and 0.5% carbon black) was cut into 5 cm x 5 cm squares.
As a cleaning tester, Terg-O-tometer (manufactured by UNITED STATES TESTING) was used.
A cleaning solution prepared by adding the liquid cleaning composition of each example to 900 mL of water and stirring for 30 seconds was used. The amount of the liquid cleaning composition added was determined to be the "content of component (A) in the cleaning solution" in the table.
900 mL of the cleaning solution, 10 dirty cloths, and the cleaned knitted cloth were put into a cleaning tester, and the bath ratio was adjusted to 30 times, and then the items to be washed were washed at 60 rpm and 15°C for 10 minutes ( washing process). Thereafter, the items to be washed were transferred to a two-tank washing machine (manufactured by Toshiba, product name "VH-30S") and dehydrated for 1 minute, so that the bath ratio of the items to be washed was 0.5 (dehydration step). Thereafter, the items to be washed were air-dried.
However, in Comparative Example 1, a rinsing step (tap water, 3 minutes) was provided after the washing step.
The reflectance was calculated for each of the soiled cloth before washing, the soiled cloth after washing, and the unstained cloth (here, the unstained cloth refers to the original white cloth (original cloth) without any stains). It was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name "SE200 model"), and the cleaning rate (%) was determined using the following formula (i).
Cleaning rate (%) = (K/S of soiled cloth before washing - K/S of soiled cloth after washing) / (K/S of soiled cloth before washing - K/S of unstained cloth )×100...(i)
[In formula (i), K/S is (1-R/100) ² / (2R/100), and R is soiled cloth before washing, soiled cloth after washing, or unstained cloth represents the reflectance (%) of K represents an extinction coefficient, S represents a scattering coefficient, and R represents an absolute reflectance. ]
The average value of the cleaning rate of 10 dirty cloths was determined. The obtained average values were evaluated according to the following evaluation criteria. In the following evaluation criteria, ◎ and 〇 were regarded as passing.

≪Judgment criteria≫
◎: Cleaning power is 50% or more.
○: Cleaning power is 45% or more and less than 50%.
△: Cleaning power is 40% or more and less than 45%.
×: Cleaning power is less than 40%.

<Pill prevention effect>
A fully automatic electric washing machine (AW-80VC, manufactured by Toshiba Corporation) was loaded with one commercially available wool cardigan (UNIQLO's "Extra Fine Merino V-neck Cardigan (Long Sleeves)" (100% wool)), 35× 1 piece of wool fabric cut to 20 cm (Azato Inoue's "Knit Wool Pique Weave Italy" (100% wool)), 1 piece of polyester fabric cut to 35 x 20 cm (Azato Inoue's "Polyester Fleece Knit Brushed" (100% polyester)) I put one in. The liquid detergent composition of each example was added thereto, and the number of rinses was arbitrarily changed using a weak water course setting, and a cleaning step and a dehydration step were sequentially performed. In Comparative Example 1, a rinsing step (10 minutes) was performed after the washing step and before the dehydration step.
The washing time, spin-drying time, and amount of water (set to 36 L) were not adjusted and the standard settings of the washing machine were used. The temperature of the tap water used was 25°C. This washing was repeated 10 times. After 10 washes, the laundry was laid flat to dry overnight. Thereafter, the items to be washed were left standing in a constant temperature and humidity room at 25° C. and 65% RH for 2 days (washing operation).
Two pieces of washed wool fabric and polyester fabric were each cut into circles with a diameter of 140 mm, and the pieces were placed on the top of a Martindale abrasion tester (Max-Martindale 909, manufactured by James H. Heal & Co. Ltd. Halifax, England). (test piece holder) and the lower part (pilling table).
The abrasion method was based on the J method (modified Martindale method) of JIS L1076, and 300 pilling friction was performed to generate pilling.
Regarding the anti-pilling effect, 10 expert panelists visually compared wool fabrics and polyester fabrics with a reference fabric according to the following evaluation criteria. The reference fabrics for the evaluation criteria were wool fabrics and polyester fabrics subjected to the above washing operation using the liquid detergent composition of Comparative Example 1, and subjected to pilling abrasion as described in the evaluation criteria below.
The pill prevention effect was evaluated using the average scores of 10 expert panelists as criteria.

≪Evaluation criteria≫
1 point: Equivalent to a reference cloth that has been worn by 500 pills on a Martindale abrasion tester.
2 points: Equivalent to the reference cloth that has been worn by 300 pillings using a Martindale abrasion tester.
3 points: Equivalent to the reference cloth that has been worn by 100 pills on a Martindale abrasion tester.
4 points: Equivalent to the reference cloth that has been worn by 50 pills on a Martindale abrasion tester.
5 points: Equivalent to the reference fabric with zero pilling abrasion on the Martindale abrasion tester.

≪Judgment criteria≫
◎: Pilling prevention effect is 4 points or more.
○: Pilling prevention effect is 3 points or more and less than 4 points.
△: Pilling prevention effect is 2 points or more and less than 3 points.
×: Pill prevention effect is less than 2 points.

<Flexibility>
Three commercially available cotton towels (100% cotton) were placed in a fully automatic electric washer/dryer (AW-8V2 manufactured by Toshiba Corporation), and in order to adjust the bath ratio (washing water/total mass of cloth to be washed) to 30 times, Two cotton shirts (manufactured by B.V.D., total mass of all washed fabrics approximately 400 g) were thrown in.
The liquid detergent composition of each example was put into the washing machine. The amount of the liquid cleaning composition to be added was the amount that corresponds to the "content of component (A) in the cleaning solution" in the table.
A washing step and a dehydration step were performed sequentially in a weak water flow course. The washing step was performed for 10 minutes, the dehydration step was performed for 5 minutes, and the water amount was set to a low level to give a water amount of 12 L. After washing, the removed towels were left in a constant temperature and humidity room at 25° C. and 65% RH to dry. This was used as a test cloth for flexibility evaluation.
However, in Comparative Example 1, a rinsing step (10 minutes) was provided after the washing step.
As an evaluation control fabric, 16 mL of 20% nonionic surfactant (produced by P&G, natural alcohol CO-1270 with 15 moles of ethylene oxide added) was used in the same manner as the test fabric. A treated cotton towel was used.
Six expert panelists conducted a pair-wise comparison between the washed articles of each example and the control cloth according to the following evaluation criteria based on their senses.
Flexibility was evaluated using the average scores of six expert panelists as criteria.

≪Scoring criteria≫
5 points: Much softer than the control fabric.
4 points: Much softer than the control fabric.
3 points: Softer than the control fabric.
2 points: Slightly softer than the control fabric.
1 point: Same as control fabric.

≪Judgment criteria≫
◎: Flexibility is 4 points or more.
○: Flexibility is 3 points or more and less than 4 points.
△: Flexibility is 2 points or more and less than 3 points.
×: Flexibility is less than 2 points.

(Examples 1 to 29, Comparative Examples 1 to 5)
<Preparation of liquid cleaning composition>
According to the compositions shown in Tables 1 to 3, components (A) to (E) and other components were added to water and mixed to prepare liquid cleaning compositions for each example.
In addition, the blending amounts in the table are pure equivalent values (however, component (B) is the amount as an enzyme preparation). In addition, components whose blending amounts are not listed in the table are not blended.

<Washing method>
Using the obtained liquid cleaning composition, the cleaning effect, anti-pilling effect, and flexibility were evaluated, and the results are shown in the table.

As shown in Tables 1 to 3, Examples 1 to 29 had a cleaning effect of 45% or more and a pill prevention effect of 3.7 points or more. In addition, Examples 1 to 29 had flexibility scores of 3.2 points or higher.
Comparative Example 1, which was provided with a rinsing step, had a pill prevention effect of 2.7 points.
In Comparative Example 2, which used a cleaning liquid that did not contain the (Ax) component, the anti-pilling effect was 2.9 points, and the flexibility was 2.9 points.
Comparative Example 3, which used a cleaning liquid that did not contain component (B), had a pill prevention effect of 1.9 points and a softness point of 1.8 points.
From the above results, by applying the present invention, the cleaning effect on the items to be washed is good and the texture of the items to be washed can be improved.

Claims (6)

A cleaning step of bringing a cleaning liquid containing the following (A) component and the following (B) component into contact with the object to be washed;
a dehydration step of dehydrating the object to be washed without rinsing after the washing step;
A washing method.
Component (A): A non-soap surfactant containing a nonionic surfactant (Ax) represented by the following formula (ax1).
R ¹¹ -O-(R ¹² O) _n -H...(ax1)
[In formula (ax1), R ¹¹ represents a branched alkyl group having 12 to 16 carbon atoms or a straight chain alkyl group having 12 to 16 carbon atoms, and when R ¹¹ is a straight chain alkyl group, the oxygen atom is Bonds to a secondary carbon atom in a chain alkyl group. R ¹² represents an alkylene group having 2 to 4 carbon atoms. Further, n represents the average number of repetitions of R ¹² O and is from 3 to 10. ]
(B) Component: Cellulase. The washing method according to claim 1, wherein in the washing step, the content of the component (A) based on the total weight of the washing liquid is 50 to 300 ppm by weight. The washing method according to claim 1 or 2, wherein in the washing step, the content of the (Ax) component with respect to the total weight of the washing liquid is 10 to 200 ppm by weight. The washing method according to claim 1 or 2, wherein in the washing step, the content of the component (B) based on the total weight of the washing liquid is 0.1 to 50 ppm by weight. The washing method according to claim 1 or 2, wherein the cleaning liquid further contains one or more selected from the following component (C) and component (D) below.
(C) Component: Modified silicone.
(D) Component: Soil release agent. The washing method according to claim 1 or 2, wherein the washing liquid further contains the following component (E).
(E) Component: Antifoaming silicone.