JP2024025853A - washing method - Google Patents

Abstract

[Problem] To exhibit a good cleaning effect with fewer steps and to increase flexibility after washing. [Solution] The cleaning solution includes a cleaning step of bringing a cleaning liquid into contact with an object to be washed, and a dehydration step of dehydrating the object to be washed without rinsing after the cleaning step, and the cleaning liquid has the following (A): A washing method comprising the following components: (B) component below; and (C) component below. (A) Component: Non-soap surfactant. Component (B): one or more selected from the group consisting of enzymes (B1), polymeric organic dispersants (B2), and chelating agents (B3). Component (C): fatty acid having 12 to 18 carbon atoms or a salt thereof. [Selection diagram] None

Description

The present invention relates to a washing method.

When washing clothes, it is desirable to remove stains from the clothes while also making the clothes feel soft after washing and drying.
For example, Patent Document 1 describes a washing method in which, after washing textile products in a washing liquid containing a surfactant, a softening agent is added to the rinse water in the final rinsing step.

Japanese Patent Application Publication No. 2017-145546

In recent years, there has been a demand for washing methods that save resources, save energy, and reduce environmental impact.
Therefore, an object of the present invention is to provide a washing method that exhibits a good cleaning effect and increases flexibility after washing with fewer steps.

As a result of intensive studies by the present inventors, it has been found that after washing in a cleaning solution containing a specific component (C), dehydration and drying without rinsing improves flexibility. The present invention was completed based on the finding that the cleaning effect can be enhanced by combining component A) and a specific component (B).
The present invention has the following aspects.

[1] It has a cleaning step of bringing a cleaning liquid into contact with the object to be washed, and a dehydration step of dehydrating the object to be washed without rinsing after the washing step,
In the washing method, the washing liquid contains the following (A) component, the following (B) component, and the following (C) component.
(A) Component: Non-soap surfactant.
Component (B): one or more selected from the group consisting of enzymes (B1), polymeric organic dispersants (B2), and chelating agents (B3).
Component (C): fatty acid having 12 to 18 carbon atoms or a salt thereof.
[2] The washing method according to [1], wherein the content of the component (C) is 1 to 100 ppm by mass based on the total mass of the cleaning liquid.
[3] The washing method according to [1] or [2], wherein the content of the component (A) is 40 to 200 ppm by mass based on the total mass of the cleaning liquid.
[4] The washing method according to any one of [1] to [3], wherein the enzyme (B1) contains one or more selected from protease, lipase, amylase, and cellulase.
[5] The washing method according to any one of [1] to [4], wherein the component (A) contains one or both of a nonionic surfactant (A1) and an anionic surfactant (A2).
[6] The component (A) contains a nonionic surfactant (A1),
In the cleaning liquid, A1/(A1+A2) representing the mass ratio of the nonionic surfactant (A1) to the total of the nonionic surfactant (A1) and the anionic surfactant (A2) is 0.2/1 or more. The washing method according to [5].

According to the washing method of the present invention, a good washing effect can be achieved with a smaller number of steps, and flexibility after washing can be 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. Further, the material of the textile product is not particularly limited, and examples thereof 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, the following (B) component, and the following (C) component. The cleaning liquid may be an aqueous solution or an aqueous dispersion.

The cleaning liquid may be an aqueous solution in which an integrated cleaning composition containing components (A), (B), and (C) is dispersed in water, or a solution containing components (A), (B), and (C). It may be an aqueous solution in which each of the components and other components as required are dispersed in water. As the cleaning composition, a liquid cleaning composition is preferred.

[(A) Component]
Component (A) is a non-soap surfactant.
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 (A1), anionic surfactants (A2), cationic surfactants, amphoteric surfactants, semipolar surfactants, and the like.
As component (A), one type of surfactant may be used, or two or more types of surfactants may be combined.
From the viewpoint of further increasing detergency, component (A) preferably contains one or both of a nonionic surfactant (A1) and an anionic surfactant (A2), and more preferably contains both.
By using the nonionic surfactant (A1) and the anionic surfactant (A2) together, the cleaning effect can be enhanced and recontamination can be suppressed.
In addition, the nonionic surfactant (A1) is preferable because it causes less foaming and is suitable for a washing method that does not involve rinsing. From this point of view, it is more preferable that component (A) contains at least the nonionic surfactant (A1).

[(A1) Component: Nonionic surfactant]
Examples of the nonionic surfactant (A1) include polyoxyalkylene type nonionic surfactants, alkylphenols, alkylene oxide adducts such as fatty acids having 8 to 22 carbon atoms or amines having 8 to 22 carbon atoms, and polyoxyethylene polyoxypropylene. Block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or their alkylene oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, Examples include N-alkyl polyhydroxy fatty acid amide and alkyl glycoside.

Among these, polyoxyalkylene type nonionic surfactants are preferred. As polyoxyalkylene type nonionic surfactants, compounds represented by the following general formula (a1) (hereinafter also referred to as "compound (a1)"), compounds represented by the following general formula (a2) (hereinafter, (also referred to as "compound (a2)"), and a compound represented by the following general formula (a3) (hereinafter also referred to as "compound (a3)").
Among these, it is preferable that the component (A1) contains one or both of the compound (a1) and the compound (a2), since it has low foaming and is suitable for a washing method that does not involve rinsing. It is more preferable.

[Compound (a1)]
R ¹¹ -O-[(EO) _s / (A ¹¹ O) _t ]-(EO) _u -R ¹² ...(a1)
In the general formula (a1), R ¹¹ is a linear hydrocarbon group having 8 to 22 carbon atoms. R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. s is a number from 3 to 25 indicating the average number of EO repetitions. A ¹¹ O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). t is a number from 0 to 6 indicating the average number of repetitions of A ¹¹ O. u is a number from 0 to 20 representing the average number of EO repetitions.

In the general formula (a1), the hydrocarbon group of R ¹¹ has 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and more preferably 12 to 18 carbon atoms. The hydrocarbon group of R ¹¹ is linear. The hydrocarbon group of R ¹¹ may or may not have an unsaturated bond. The carbon atom of R ¹¹ bonded to -O- may be a primary carbon atom or a secondary carbon atom.

When R ¹² is an alkyl group, it may be linear or branched. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
When R ¹² is an alkenyl group, it may be linear or branched. The alkenyl group has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.
R ¹² is particularly preferably a hydrogen atom.

s is 3 to 25, preferably 5 to 25, more preferably 7 to 20, even more preferably 7 to 18, particularly preferably 9 to 18, and most preferably 11 to 18.
t is 0 to 6, preferably 0 to 3.
u is 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
s+u is preferably 3 to 30, more preferably 5 to 25, even more preferably 5 to 20, particularly preferably 7 to 20, most preferably 9 to 18, and very preferably 11 to 18.

When t is not 0, that is, when compound (a1) has EO and PO, EO and BO, or EO, PO and BO, EO and PO, EO in [(EO) _s / (A ¹¹ O) _t ] There is no particular limitation on the distribution (order of arrangement) of and BO, or EO, PO, and BO, and these may be arranged in a block shape or randomly. Furthermore, EO may be bonded to "R ¹¹ -O-", and PO or BO may be bonded to "R ¹¹ -O-".
When t is not 0, compound (a1) preferably has EO and PO or EO and BO.

[Compound (a2)]
R ¹³ -O- [(EO) _v / (A ¹² O) _w ] - (EO) _x -R ¹⁴ ... (a2)
In the general formula (a2), R ¹³ is a branched hydrocarbon group having 8 to 22 carbon atoms. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. v is a number from 3 to 25 indicating the average number of EO repetitions. A ¹² O represents at least one of PO (oxypropylene group) and BO (oxybutylene group). w is a number from 0 to 6 indicating the average number of repetitions of A ¹² O. x is a number from 0 to 20 representing the average number of EO repetitions.

In general formula (a2), the number of carbon atoms in the hydrocarbon group of R ¹³ is 8 to 22, preferably 10 to 18, and more preferably 12 to 18. The hydrocarbon group of R ¹³ is branched. Further, the hydrocarbon group of R ¹³ may or may not have an unsaturated bond. The carbon atom of R ¹³ bonded to -O- may be a primary carbon atom or a secondary carbon atom.

When R ¹⁴ is an alkyl group, it may be linear or branched. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
When R ¹⁴ is an alkenyl group, it may be linear or branched. The alkenyl group has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.
R ¹⁴ is particularly preferably a hydrogen atom.

v is 3 to 25, preferably 5 to 18, more preferably 5 to 15, even more preferably 5 to 10, particularly preferably 5 to 8.
w is 0 to 6, preferably 0 to 3.
x is from 0 to 20, preferably from 0 to 15, and more preferably from 0 to 10.
v+x is preferably 3 to 30, more preferably 5 to 25, even more preferably 5 to 20, particularly preferably 5 to 15, most preferably 5 to 10, and very preferably 5 to 8.

When w is not 0, that is, when compound (a2) has EO and PO, EO and BO, or EO, PO and BO, EO and PO, EO in [(EO) _v / (A ¹² O) _w ] There is no particular limitation on the distribution (order of arrangement) of and BO, or EO, PO, and BO, and these may be arranged in a block shape or randomly. Further, EO may be bonded to "R ¹³ -O-", and PO or BO may be bonded to "R ¹³ -O-".
When w is not 0, compound (a2) preferably has EO and PO or EO and BO.

Commercially available products of compound (a2) 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), Neodol manufactured by Shell (registered trademark) (mixture of C12 and C13), Sasol (registered trademark) 23 (mixture of C12 and C13), EXXAL (registered trademark) 13 (C13), etc. Added with 10 moles of 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 C13 alcohol obtained by subjecting a C12 alkene obtained by trimerizing butene to the oxo method, to which ethylene oxide equivalent to 12 moles or 15 moles is added (Lutensol (registered trademark) TO12, Lutensol TO15, etc., 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);
Examples include those 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).
Among these, Sasol's product name Safol 23 (branching rate: 50% by mass) (an alcohol obtained from olefin obtained from coal gasification by the oxo method and further hydrogenated), Shell Chemicals As in the product name Neodol 23 (branching rate: 20% by mass) (produced from n-olefin by the improved oxo method and rectified) manufactured by the company, the hydrocarbon group of R ¹³ in the general formula (a2) is In the case of a "mixture" of a branched compound and a compound in which the hydrocarbon group of R ¹¹ in general formula (a1) is linear, the compound having a branched chain is defined as compound (a2), and on the other hand, Those having a straight chain are defined separately from compound (a1). Note that "branching rate" refers to the ratio (mass %) of higher alcohols having branched chains to all higher alcohols.

[Compound (a3)]
R ¹⁵ -X-[(EO) _p /(A ¹³ O) _q ]-(EO) _r -R ¹⁶ ...(a3)
In the general formula (a3), R ¹⁵ is a hydrocarbon group having 7 to 21 carbon atoms. -X- is -COO- or -CONH-. R ¹⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. EO is an oxyethylene group. p is a number from 3 to 25 indicating the average number of EO repetitions. A ¹³ represents at least one of PO (oxypropylene group) and BO (oxybutylene group). q is a number from 0 to 6 indicating the average number of repetitions of A ¹³ O. r is a number from 0 to 20 representing the average number of EO repetitions.

In the general formula (a3), the number of carbon atoms in the hydrocarbon group of R ¹⁵ is 7 to 21, preferably 9 to 19, and more preferably 11 to 19. The hydrocarbon group of R ¹⁵ may be linear or branched. Further, the hydrocarbon group of R ¹⁵ may or may not have an unsaturated bond.
The carbon atom of R ¹⁵ bonded to -X- may be a primary carbon atom or a secondary carbon atom.

When R ¹⁶ is an alkyl group, it may be linear or branched. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.
When R ¹⁶ is an alkenyl group, it may be linear or branched. The alkenyl group has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.
R ¹⁶ is particularly preferably an alkyl group.

p is 3 to 25, preferably 5 to 20, more preferably 10 to 18, even more preferably 12 to 18.
q is 0 to 6, preferably 0 to 3.
r is 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
p+r is preferably from 5 to 30, more preferably from 5 to 25, even more preferably from 5 to 20, particularly preferably from 10 to 20.

When q is not 0, that is, when compound (a3) has EO and PO, EO and BO, or EO, PO and BO, EO and PO, EO in [(EO) _p / (A ¹³ O) _q ] There is no particular limitation on the distribution (order of arrangement) of and BO, or EO, PO, and BO, and these may be arranged in a block shape or randomly. Furthermore, EO may be bonded to "R ¹⁵ -X-", and PO or BO may be bonded to "R ¹⁵ -X-".
When q is not 0, compound (a3) preferably has EO and PO or EO and BO.

[Component (A2): Anionic surfactant]
Examples of anionic surfactants include linear alkylbenzenesulfonic acids or salts thereof (LAS), α-olefin sulfonic acids or salts thereof (AOS), linear or branched alkyl sulfates or salts thereof (AS), Polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt (AES), alkanesulfonic acid having an alkyl group or its salt, α-sulfo fatty acid ester or its salt, internal olefin sulfonic acid or its salt (IOS), hydroxyalkane Sulfonic acid or its salt (HAS), 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 Carboxylic acid type anionic surfactants such as salts thereof; alkyl phosphates or salts thereof, polyoxyalkylene alkyl phosphates or salts thereof, polyoxyalkylene alkylphenyl phosphates or salts thereof, glycerin fatty acid ester monophosphates or Examples include phosphate ester type anionic surfactants such as salts thereof.
Examples of the salt forms of anionic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Can be mentioned.
These anionic surfactants may be used alone or in combination of two or more.
As the anionic surfactant, LAS, AOS, AS, and AES are preferable, and among them, LAS and AES are more preferable from the viewpoint of further increasing the detergency. Preferably, the liquid cleaning agent contains at least AES, more preferably both LAS and AES.

Polyoxyalkylene alkyl (alkenyl) ether sulfate or its salt (AES) is represented by the following general formula (a4).
R ¹⁷ -O- [(EO) _j / (PO) _k ]-SO ₃ ^- M ⁺ ... (a4)
In the general formula (a4), R ¹⁷ 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. EO is an oxyethylene group. PO is an oxypropylene group. j is a number of 0.1 or more representing the average number of EO repetitions. k is a number from 0 to 6 representing the average number of PO repetitions. [(EO) _j /(PO) _k ] indicates that there is no restriction on the arrangement order of EO and PO, and M ⁺ is a counter cation.

The AES preferably has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms, to which an average of 1 to 5 moles of alkylene oxide is added. The number of carbon atoms in the alkyl group or alkenyl group is preferably 10 to 20, more preferably 12 to 14. In particular, linear alkyl groups having 10 to 20 carbon atoms are preferred, and linear alkyl groups having 12 to 14 carbon atoms are more preferred. Specific examples include dodecyl group, tridecyl group, and tetradecyl group.

j is preferably 0.1 to 5, more preferably 0.1 to 3, even more preferably 0.5 to 2, particularly preferably 0.5 to 1.5.
k is 0 to 6, preferably 0 to 3, and more preferably 0.
j+k is preferably greater than 0, more preferably 1 to 5.

When k is not 0, that is, when AES has EO and PO, there is no particular limitation on the distribution (order of arrangement) of EO and PO in [(EO) _j / (PO) _k ], and these are arranged in a block. They may be arranged in a random manner. Further, EO may be bonded to "R ¹⁷ -O-", and PO may be bonded to "R ¹⁷ -O-".
Examples of methods for arranging EO and PO in a block include a method of introducing ethylene oxide and then propylene oxide, a method of introducing ethylene oxide after introducing propylene oxide, and a method of introducing ethylene oxide and then introducing propylene oxide. Further examples include a method of introducing ethylene oxide.
Note that the compound with j=0 and k=0 in the above formula (a4) is preferably contained in an amount of 35 to 55% by mass based on the total mass of the compound represented by formula (a4).

[Cationic surfactant]
Examples of cationic surfactants include caprylic acid dimethylaminopropylamide, capric acid dimethylaminopropylamide, lauric acid dimethylaminopropylamide, myristate dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, Long chain aliphatic amide alkyl tertiary amines such as behenic acid dimethylaminopropylamide and oleic acid dimethylaminopropylamide or their salts; aliphatic ester alkyl tertiary amines such as palmitate ester propyl dimethylamine and stearate ester propyl dimethylamine or salts thereof; palmitic acid diethanolaminopropylamide, stearic acid diethanolaminopropylamide; quaternized products such as alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, alkylpyridinium salts, and the like.
Examples of the salt forms of cationic surfactants include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), and alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.). Can be mentioned.
These cationic surfactants may be used alone or in combination of two or more.

[Ampholytic surfactant]
Examples of amphoteric surfactants include alkyl betaine type, alkylamide betaine type, imidazoline type, alkylaminosulfone type, alkylaminocarboxylic acid type, alkylamidocarboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactants. Can be mentioned.
These amphoteric surfactants may be used alone or in combination of two or more.

[Semipolar surfactant]
Examples of semipolar surfactants include alkylamine oxides and alkylamidopropyl dimethylamine oxides.
These semipolar surfactants may be used alone or in combination of two or more.

[(B) Component]
Component (B) is one or more selected from the group consisting of enzymes (B1), polymeric organic dispersants (B2), and chelating agents (B3).
When used in combination with component (A), (B1) to (B3) contribute to improvement in detergency without hindering improvement in flexibility.
Two or more types of component (B) may be used in combination.

[(B1) component]
(B1) Component is an enzyme.
Examples of enzymes include protease, lipase, amylase, cellulase, mannanase, and pectinase.
Protease, lipase, amylase, and cellulase are preferable, and protease and lipase are more preferable from the viewpoint of their excellent effect of improving detergency.
Cellulase is preferred because it has an excellent effect of improving flexibility.
The protease is preferably a protease having serine, histidine, and aspartic acid in the molecule, such as serine protease.
Enzymes are generally commercially available as enzyme-containing preparations (enzyme preparations). As component (B1), a commercially available enzyme preparation can be used.
In this specification, the enzyme content is the mass as an enzyme preparation.

[(B2) component]
Component (B2) is a polymeric organic dispersant. When the cleaning liquid contains the component (B2), it exhibits the effect of assisting the cleaning action. Therefore, sufficient cleaning power can be exhibited even if the concentration of component (A) in the cleaning liquid is low. Here, the term "polymer organic dispersant" refers to an organic compound with a molecular weight of 1000 or more that exhibits detergency when used in combination with component (A).
The component (B2) preferably includes one or more selected from the components (B21), (B22), and (B23) described below.

[(B21) component]
Component (B21) is an alkoxylated polyalkylene imine. That is, component (B21) is an alkylene oxide adduct of polyalkylene imine.
The polyalkyleneimine is represented by the following formula (b1), for example.
NH ₂ -R ³ -[N(A ¹ )-R ³ ] _n -NH ₂ ...(b1)
In formula (b1), R ³ is each independently an alkylene group having 2 to 6 carbon atoms, A ¹ is a hydrogen atom or another branched polyamine chain, and n is a number of 1 or more. However, not all of the above A ¹ are hydrogen atoms. That is, the polyalkyleneimine represented by formula (b1) has a branched polyamine chain in its structure.
Examples of R ³ include a linear alkylene group having 2 to 6 carbon atoms and a branched alkylene group having 3 to 6 carbon atoms. R ³ is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 carbon atoms.

The polyalkylene imine can be obtained, for example, by polymerizing one or more alkylene imines 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, and 1,1-dimethylethyleneimine.
As the polyalkylene imine, polyethylene imine (hereinafter also referred to as "PEI") and polypropylene imine are preferred, and PEI is more preferred. PEI is obtained by polymerizing ethyleneimine, and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms.

The mass average molecular weight of the polyalkyleneimine is preferably 200 to 2,000, more preferably 300 to 1,500, even more preferably 400 to 1,000, and particularly preferably 500 to 800.
The polyalkyleneimine preferably has 5 to 30 active hydrogens in one molecule, more preferably 7 to 25, and even more preferably 10 to 20.
In addition, the mass average molecular weight in this specification means the value calculated|required by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

Component (B21) is obtained by adding alkylene oxide to polyalkylene imine. In this method, for example, an alkylene oxide such as ethylene oxide is added to a polyalkylene imine as a starting material at 100 to 180°C in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate. For example, the method of

Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide, with ethylene oxide and propylene oxide being preferred, and ethylene oxide being more preferred.

Examples of the component (B21) include ethylene oxide adducts of polyalkylene imine, propylene oxide adducts of polyalkylene imine, and ethylene oxide-propylene oxide adducts of polyalkylene imine. The ethylene oxide-propylene oxide adduct of polyalkylene imine is obtained by adding ethylene oxide and propylene oxide to polyalkylene imine, and the order and form of addition (block, random) of ethylene oxide and propylene oxide to polyalkylene imine are arbitrary. It is.
As component (B21), from the viewpoint of deodorizing effect, ethylene oxide adducts of polyalkylene imine, ethylene oxide-propylene oxide adducts of polyalkylene imine are preferable, and ethylene oxide adducts of polyalkylene imine are more preferable.

As the component (B21), it is preferable that an average of 5 to 40 moles of alkylene oxide is added to each mole of active hydrogen possessed by the raw material polyalkylene imine, and an average of 5 to 30 moles of alkylene oxide is added. It is more preferable that an alkylene oxide is added thereto in an average amount of 8 to 25 moles.

As the component (B21), for example, a compound represented by the following formula (b1-1) can be mentioned.

In formula (b1-1), R ²² is each independently an alkylene group having 2 to 6 carbon atoms, and m is each independently a number of 1 or more.
R ²² is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms.
m represents the average number of repetitions of (R ²² O). m is each independently preferably a number from 5 to 40, more preferably from 5 to 30, even more preferably from 8 to 25, particularly preferably from 8 to 15.

The mass average molecular weight of component (B21) is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 20,000.

As the component (B21), a synthetic product or a commercially available product may be used. Examples of commercially available products include "Sokalan (registered trademark) HP20" and the like.
Component (B21) may be used alone or in combination of two or more.

[(B22) component]
Component (B22) is a polyacrylic acid polymer. When the cleaning liquid contains component (B22), the cleaning power against sebum stains can be further enhanced.
(B22) Components include, for example, polyacrylic acid and its salts, polymaleic acid and its salts, acrylic acid-maleic acid copolymers and their salts, and copolymers of a hydrocarbon having 4 to 12 carbon atoms and maleic acid. and salts thereof, and acrylic acid-methacrylic acid copolymers and salts thereof. (B22) The component is selected from one or more selected from acrylic acid-maleic acid copolymers and salts thereof, or copolymers of maleic acid and hydrocarbons having 4 to 12 carbon atoms and salts thereof. One or more types are preferred.
The salt may be used in part or in whole, and preferred salts include alkali metal salts such as sodium and potassium salts and organic amine salts such as alkanolamines.

The hydrocarbon having 4 to 12 carbon atoms in component (B22) may be any hydrocarbon that can be copolymerized with maleic acid, preferably a hydrocarbon having 10 or less carbon atoms from the viewpoint of handling of raw materials, and 5 to 5 carbon atoms. -9 hydrocarbons are more preferred. Examples of such hydrocarbons include unsaturated chain hydrocarbons having double bonds.

The copolymer of component (B22) is selected from a repeating unit derived from a monomer represented by the following formula (b2-1) and a repeating unit derived from a monomer represented by the following formula (b2-2). It may be a polymer having one or more types of repeating units.

In formula (b2-1), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. In formula (b2-2), R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a hydrogen atom or an alkyl group having 10 to 30 carbon atoms, and R ⁹ is a hydrogen atom or a carboxyl group. However, in formula (b2-2), when R ⁹ is a hydrogen atom, R ⁸ is an alkyl group having 10 to 30 carbon atoms, and when R ⁹ is a carboxyl group, R ⁸ is a hydrogen atom.

In formula (b2-1), the alkyl group of R ⁶ may be linear or branched. Further, it may include a cyclic structure. The number of carbon atoms in the alkyl group of R ⁶ is preferably 1 to 8, more preferably 1 to 4.
Examples of the monomer represented by formula (b2-1) (hereinafter also referred to as monomer (b2-1)) include acrylic acid; methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate. Methacrylic acid; methacrylic esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and n-butyl methacrylate.
Monomer (b2-1) may be used alone or in combination of two or more.

In formula (b2-2), the alkyl group of R ⁸ may be linear or branched. Moreover, it may contain a cyclic structure. The number of carbon atoms in the alkyl group of R ⁸ is preferably 10 to 25, more preferably 10 to 20.
Among the monomers represented by formula (b2-2) (hereinafter also referred to as monomers (b2-2)), in formula (b2-2), R ⁹ is a hydrogen atom, and R ⁸ is an alkyl having 10 to 30 carbon atoms. Examples of the monomer (b2-2) which is a group include decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, Examples include octadecyl methacrylate. In formula (b2-2), examples of the monomer (b2-2) in which R ⁹ is a carboxyl group and R ⁸ is a hydrogen atom include maleic acid and fumaric acid. The monomer (b2-2) in which R ⁹ is a carboxyl group and R ⁸ is a hydrogen atom is preferably maleic acid.
Monomer (b2-2) may be used alone or in combination of two or more.

Component (B22) may be a crosslinked polymer or a non-crosslinked polymer.
Examples of the crosslinked polymer include crosslinked polymers crosslinked with a crosslinking agent. Examples of the crosslinking agent include allyl ether compounds. Examples of the allyl ether compound include allyl ether, sugar allyl ether, sugar alcohol allyl ether, and the like. Examples of the sugar include sucrose and the like. Examples of the sugar alcohol include pentaerythritol.

Component (B22) is a repeating unit derived from the monomer represented by formula (b2-1) and a repeating unit other than the repeating unit derived from the monomer represented by formula (b2-2) (other repeating units). ).
Other repeating units include repeating units derived from other monomers.
Other monomers are not particularly limited as long as they can be copolymerized with monomer (b2-1) and monomer (b2-2), and include methyl acrylate, ethyl acrylate, methacrylic acid, methyl methacrylate, and the like.
One type of other monomers may be used alone, or two or more types may be used in combination.

The mass average molecular weight of the component (B22) is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, even more preferably 5,000 to 50,000. When the mass average molecular weight of the component (B22) is at least the above lower limit, the detergency can be further enhanced. When the mass average molecular weight of the component (B22) is below the above upper limit, the liquid stability of the liquid cleaning composition can be further improved.

Component (B22) may be used alone or in combination of two or more.

[(B23) component]
Component (B23) is a carboxymethyl cellulose polymer. When the cleaning liquid contains the component (B23), the function of preventing dirt adhering to textile products from being removed by the cleaning liquid and adhering to other textile products (recontamination prevention property) can be further enhanced.
As the component (B23), for example, carboxymethyl cellulose (CMC) or a salt thereof can be mentioned. Examples of the salts of CMC include alkali metal salts such as sodium salts and potassium salts, ammonium salts, etc., and mixtures of these salts may be used. As the salt of CMC, sodium salt is preferred.

Examples of CMC include anionic water-soluble cellulose ether or water-insoluble cellulose ether obtained by treating pulp as a raw material with an aqueous sodium hydroxide solution and then reacting it with monochloroacetic acid.
Specifically, a polymer compound having a repeating unit represented by the following formula (b3-1) is exemplified.

In formula (b3-1), n represents the repeating number of the repeating unit, and R ³¹ to R ³³ are each independently a hydroxyl group or a carboxymethyl group (-CH ₂ COO ⁻ Z ⁺ ; Z ⁺ is a counter ion ) is shown.

The mass average molecular weight of CMC is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 800,000 or more. The upper limit of the mass average molecular weight of CMC is preferably 1.2 million or less, more preferably 1 million or less. When the mass average molecular weight of CMC is equal to or higher than the above lower limit, the recontamination prevention property can be further improved. When the mass average molecular weight of CMC is less than or equal to the above upper limit, the solubility becomes good and the liquid stability of the liquid cleaning composition can be further improved.

The degree of etherification of CMC is preferably from 0.2 to 1.3, more preferably from 0.2 to 1.0, even more preferably from 0.2 to 0.7.
In this specification, the degree of etherification of CMC refers to the average number of hydroxyl groups substituted with a carboxymethyl group or its salt per glucose ring unit (out of the three hydroxyl groups of the glucose ring, how many are carboxymethyl groups or its salts)? This indicates whether the salt has been substituted with a salt (up to 3). For example, in the above formula (b3-1), among -OR ³¹ , -OR ³² , and -OR ³³ , the average number of R ³¹ to R ³³ substituted with a carboxymethyl group or a salt thereof is the degree of etherification. becomes.

A commercially available product may be used as CMC. Commercial products of CMC are, for example, sold by Daicel Millize Co., Ltd. under the trade names "CMC Daicel" and "HEC (Hydroxyethyl Cellulose) Daicel". For CMC Daicel, for example, all product numbers are 1110, 1120, 1130, 1140, 1160, 1170, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380, 2200, 2260, 2280, 2450, 2340, etc. can be mentioned. Examples of HEC Daicel include product numbers such as SP200, SP400, SP500, SP600, SP850, and SP900.
Other commercial products of CMC are sold by Nippon Paper Industries Co., Ltd. under the trade name "Sunrose (registered trademark)." Sunrose (registered trademark) includes, for example, Sunrose F series such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, F1400MG; Sunrose A series such as A02SH, A20SH, A200SH; SLD-F1 (and above); product name).
Among the above, commercially available CMC products are preferably CMC Daicel 1130, 1170, 1180, 1190, 1260, HEC Daicel SP400, SP500, Sunrose F1400LC, F1400MC, and Sunrose SLD-F1, and CMC Daicel 1260, HEC Daicel SP500. is more preferable.

Component (B23) may be used alone or in combination of two or more.

In addition to the above, the component (B2) includes cationized cellulose, polyvinylpyrrolidone, and the like.

[(B3) component]
Component (B3) is a chelating agent.
Examples of chelating agents include citric acid and aminocarboxylic acid type chelating agents.
Examples of the aminocarboxylic acid type chelating agent include ethylenediaminetetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), and the like.

[(C) Component]
Component (C) is a fatty acid having 12 to 18 carbon atoms or a salt thereof. Component (C) may be used alone or in combination of two or more.
Component (C) contributes to improving the flexibility of the items to be washed. In addition, component (C) suppresses foaming and is suitable for washing methods that do not involve rinsing.
It is thought that component (C) combines with calcium ions derived from water or the like in the washing liquid to produce calcium salts, and such fatty acid calcium remains in the washed items to increase flexibility. Furthermore, it is thought that the presence of fatty acid calcium in the cleaning solution makes the foam film unstable and makes defoaming easier.

The fatty acid constituting component (C) may be a saturated fatty acid, an unsaturated fatty acid, or a mixture of a saturated fatty acid and an unsaturated fatty acid.
Specific examples of the fatty acid constituting component (C) include lauric acid, myristic acid, palmitic acid, stearic acid, linoleic acid, oleic acid, and coconut fatty acid.
Examples of the salt form of fatty acids include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, etc.), alkanolamine salts (monoethanolamine salts, diethanolamine salts, etc.).
Component (C) may be a fatty acid, a fatty acid salt, or a combination of these. It is preferable that the component (C) contains a fatty acid because fatty acid calcium is more easily produced.

[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 ingredients include those commonly used in cleaning compositions, such as water-miscible organic solvents, hydrotropes, stabilizers, antifoaming agents, alkalis, preservatives, fluorescent agents, and stain transfer agents. Examples of inhibitors, texture improvers, pearlescent agents, antioxidants, and coloring agents include general-purpose dyes or pigments, fragrances, emulsifiers, insoluble particles, pH adjusters, and extracts of natural products.
These components may be used alone or in combination of two or more.

[Content]
The content of component (A) is 40 to 200 mass ppm, preferably 50 to 180 mass ppm, and more preferably 50 to 150 mass ppm, based on the total mass of the cleaning liquid. 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 the component (A) is below the above upper limit, the flexibility of the laundry object after washing can be further improved. This is thought to be because the amount of component (A) remaining in the items to be washed is reduced, making it difficult for the items to be washed to become stiff.

The total content of nonionic surfactant (A1) and anionic surfactant (A2) is preferably 80% by mass or more, more preferably 85% by mass or more, based on the total mass of component (A) contained in the cleaning liquid. It is preferably 90% by mass or more, and more preferably 90% by mass or more. It may be 100% by mass.

When the anionic surfactant (A2) binds to calcium ions in the cleaning liquid, the amount of calcium ions that can bind to the component (C) decreases, so it is preferable that the anionic surfactant (A2) is not too large.
A1/(A1+A2) representing the mass ratio of the nonionic surfactant (A1) to the total of the nonionic surfactant (A1) and the anionic surfactant (A2) is preferably 0.2/1 or more, and 0.4 /1 or more is more preferable, 0.5/1 or more is even more preferable, 0.6/1 or more is even more preferable, and 0.7/1 or more is particularly preferable. It may be 1/1, and preferably 0.9/1 or less.
When A1/(A1+A2) is within the above range, good detergency and flexibility can be obtained and recontamination can be suppressed.

The content of component (B) is preferably 5 to 100 mass ppm, more preferably 7 to 80 mass ppm, and even more preferably 10 to 50 mass ppm, based on the total mass of the cleaning liquid. When the content of component (B) is above the lower limit of the above range, it has an excellent effect of improving detergency, and when it is below the upper limit, it has a good balance with components other than component (B), and increases in cost can be suppressed. .
The content of component (B1) is preferably 0.1 to 50 mass ppm, more preferably 0.5 to 30 mass ppm, and even more preferably 1 to 10 mass ppm, based on the total mass of the cleaning liquid.
The content of component (B2) is preferably 5 to 100 ppm, more preferably 7 to 80 ppm, and even more preferably 10 to 50 ppm, based on the total mass of the cleaning liquid.
The content of component (B21) is preferably 5 to 100 ppm, more preferably 7 to 80 ppm, and even more preferably 10 to 50 ppm, based on the total mass of the cleaning liquid.
The content of component (B22) is preferably 5 to 100 ppm, more preferably 7 to 80 ppm, and even more preferably 10 to 50 ppm, based on the total mass of the cleaning liquid.
The content of component (B23) is preferably 0.1 to 50 ppm, more preferably 0.5 to 30 ppm, and even more preferably 1 to 10 ppm, based on the total mass of the cleaning liquid.
The content of component (B3) is preferably 0.1 to 50 mass ppm, more preferably 0.5 to 30 mass ppm, and even more preferably 1 to 10 mass ppm, based on the total mass of the cleaning liquid.

The content of component (C) is preferably 3 to 70 mass ppm, more preferably 5 to 50 mass ppm, and even more preferably 10 to 30 mass ppm, based on the total mass of the cleaning liquid. When the content of component (C) is at least the lower limit of the above range, the effect of improving flexibility is excellent. In addition, it has an excellent foaming suppressing effect. When it is below the upper limit, the balance with components other than component (C) is good, and an increase in cost can be suppressed.

In the cleaning liquid, C/A, which represents the mass ratio of the content of component (C) to the content of component (A), is preferably from 0.05/1 to 0.5/1, and preferably from 0.1/1 to 0.3/1 is more preferable. When C/A is within the above range, the effect of improving detergency and flexibility is excellent.

[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 (textile products) 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 by [mass of cleaning liquid]/[mass of object to be washed].

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 fatty acid calcium produced in the cleaning solution stays on the fiber surface and continues to act, further increasing the flexibility of the item 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, fatty acid calcium in the cleaning liquid is easily adsorbed on the fiber surface, and the flexibility of the object to be washed can be further improved.

<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 40 mass ppm. Further, the content of component (C) in the rinsing liquid is, for example, less than 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 fatty acid calcium 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), (B), and (C) with the washing material, it has a cleaning effect on the washing material. At the same time, the flexibility of the items to be washed can be increased.
In addition, according to the washing method of the present invention, since the dehydration step is performed without rinsing, the fatty acid calcium produced in the washing liquid tends to remain on the items to be washed, and the flexibility 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)
A preferred embodiment of the cleaning composition used in the laundry method of the present invention contains component (A), component (B), and component (C). The cleaning composition of this embodiment may further contain the other components described 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 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 20% by mass, more preferably 8 to 18% by mass, and even more preferably 10 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 flexibility of the object to be washed can be further improved.

The content of component (B) in the liquid cleaning composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass. When the content of component (B) in the liquid cleaning composition is at least the above lower limit, the cleaning effect can be further enhanced. When the content of component (B) in the liquid cleaning composition is below the above upper limit, the balance with components other than component (B) is good, and an increase in cost can be suppressed.

The content of component (C) in the liquid cleaning composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, and even more preferably 1 to 3% by mass. 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, the balance with components other than component (C) is good and an increase in cost can be suppressed. In addition, the liquid stability of the liquid cleaning composition is further improved.

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 15% by mass or less, and even more preferably 10% 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, C/A, which represents the mass ratio of the content of component (C) to the content of component (A), is preferably 0.05/1 to 0.5/1, and preferably 0.05/1 to 0.5/1. More preferably 1/1 to 0.3/1. When C/A is within the above range, the effect of improving detergency and flexibility is excellent.

<Method for producing liquid cleaning composition>
Liquid cleaning compositions are manufactured according to conventional methods. As a manufacturing method, for example, component (A), component (B), component (C), and other components as necessary are added to a portion of water, the pH is adjusted, and then the remainder of the water is added. There are several methods.

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>
≪(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 ¹¹ in formula (a1) is a linear alkyl group having 12 to 14 carbon atoms, R ¹² 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 ¹¹ in formula (a1) is a linear alkyl group having 12 to 14 carbon atoms, R ¹² is a hydrogen atom, s is 12, t is 0, and u is 0.)
・A1-3: Linear AE, polyoxyethylene alkyl ether (20EO), natural alcohol with 20 moles of ethylene oxide added. (A compound in which R ¹¹ in formula (a1) is a linear alkyl group having 12 to 14 carbon atoms, R ¹² is a hydrogen atom, s is 20, t is 0, and u is 0.)
・A1-4: EXAL (trade name "RHA-234 TAG-90", manufactured by Lion Chemical Co., Ltd. In formula (a2), R ¹³ is a branched alkyl group having 13 carbon atoms, R ¹⁴ is a hydrogen atom, v is 7, A compound in which w is 0 and x is 0.).
・A1-5: Softal (trade name "Softanol 30", manufactured by Nippon Shokubai Co., Ltd.) In formula (a1), R ¹¹ is a straight-chain alkyl group having 12 to 14 carbon atoms (O is bonded to the secondary carbon), R ¹² is a hydrogen atom, s is 3, t is 0, and u is 0.)
・A1-6: 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 ¹¹ is an alkyl group having 12 carbon atoms/an alkyl group having 14 carbon atoms = 7/3, R ¹² is a hydrogen atom, s is 8, and A ¹¹ O is PO, t is 2, and u is 8.).

≪(A2) Component≫
- A2-1: LAS (linear sodium alkylbenzene sulfonate (LAS), trade name "Lipon LS-250", manufactured by Lion Corporation).
・A2-2: AES (1EO) (PT. Manufactured by Kao Indonesia Chemicals. Sodium oxyethylene alkyl sulfate having an alkyl group with 12 to 14 carbon atoms and an average repeating number of oxyethylene groups of 1. Formula (a4) A compound in which R ¹⁷ is a straight-chain alkyl group having 12 to 14 carbon atoms, j is 1, and k is 0.)
- A2-3: IOS (inner olefin sulfonate synthesized by the method described in Example 7 of JP-A-2001-247534).

<(B) component>
・B-1: Protease preparation, trade name "Progress Uno", manufactured by Novozymes.
・B-2: Lipase preparation, trade name "Lipex 100T", manufactured by Novozymes.
- B-3: Amylase preparation, trade name "Amplify Prime", manufactured by Novozymes Japan.
・B-4: Cellulase preparation, trade name "Carezyme Premium 4500L", manufactured by Novozymes.
・B-5: Citric acid.

<(C) component>
・C-1: Coconut fatty acid, trade name "coconut fatty acid", manufactured by NOF Corporation.

<Other ingredients and water>
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.
・Silicone emulsion (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KM-90"): 0.0125% by mass
・Ethanol: 2% by mass
・PEG (polyethylene glycol): 3% by mass
・Sodium benzoate: 0.5% by mass
・BHT (dibutylhydroxytoluene): 0.03% by mass
・Pigment: 0.0002% by mass
・NaOH: 0.25% by mass
- Water (ion-exchanged water): Balance (amount required to make the total amount of the liquid cleaning composition 100% by mass).

(Evaluation method)
<Cleaning effect>
Artificial dirt oil (42% oleic acid, 23% triolein, 18.5% cholesterol oleate, 3.5% squalane, 3.5% liquid paraffin, 2% cholesterol, 7% keratin, 0.5% carbon black) 1 mL of the solution was diluted with 99 mL of chloroform, and 200 μL of the resulting diluted solution was applied to a cotton knitted cloth (5 cm x 5 cm) and air-dried overnight to obtain a dirty cloth.
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 liquid" in the table.
900 mL of cleaning solution, 10 dirty cloths, and a washed knitted cloth were placed in a cleaning tester (product name "Terg-O-tometer", manufactured by UNITED STATES TESTING), and the mixture was adjusted to be 20 times the bath ratio. Thereafter, the object to be washed was washed at 120 rpm and 15° C. for 10 minutes (washing step). Thereafter, the items to be washed were transferred to a two-tank washing machine (product name "VH-30S", manufactured by Toshiba) 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 Z value ( The reflectance (unit: %) was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd., product name "SE2000 model"), and the cleaning rate (%) was determined using the following formula (i).
Cleaning rate (%) = (Z value of dirty cloth after washing - Z value of dirty cloth before washing) ÷ (Z value of unsoiled cloth - Z value of dirty cloth before washing) x 100・...(i)
The average value of the cleaning rate of 10 dirty cloths was determined. The obtained average values were evaluated according to the following criteria. Based on the following criteria, ◎ and ○ were considered to be passed.

≪Judgment criteria≫
◎: Cleaning rate is 55% or more.
○: Cleaning rate is 50% or more and less than 55%.
Δ: Cleaning rate is 45% or more and less than 50%.
×: Cleaning rate is less than 45%.

<Flexibility>
[Preparation of test cloth]
Put 5 commercially available cotton towels (100% cotton) into a fully automatic washing machine (product name "AW-8V2", manufactured by Toshiba Corporation), and then add 3 cotton skin shirts to adjust the bath ratio to 20 times. (manufactured by B.V.D. Co., Ltd.) was used. The total weight of all the washed fabrics was about 600 g.
Next, the amount of water in the fully automatic washing machine was set to a low water level (approximately 12 L of water), water was added, and the liquid detergent composition of each example was added to prepare a cleaning solution. The amount of the liquid cleaning composition added was the amount that corresponds to the "content of component (A) in the cleaning liquid" in the table.
Next, among the standard courses of the fully automatic washing machine, only the number of rinses was changed to zero, and a washing step (10 minutes) and a dehydration step (5 minutes) were performed in sequence. In Comparative Example 1, a rinsing step (10 minutes) was performed once after the washing step and before the dehydration step.
After washing, the cotton towels were taken out and left in a constant temperature and humidity room at 25° C. and 65% RH to dry and serve as test cloths.

[Preparation of control fabric]
In the preparation of the test cloth, a nonionic surfactant (15 moles of ethylene oxide added to natural alcohol CO-1270 manufactured by P&G) was used instead of the liquid detergent composition of each example. A cleaning solution was prepared by adding 10 mL of an aqueous solution containing a concentration of 20% by mass. The content of the nonionic surfactant was 167 ppm by mass based on the total mass of the cleaning solution.
A cotton towel that was otherwise subjected to the washing process, rinsing process, dehydration process, and drying in the same manner as in Comparative Example 1 was used as a control fabric.

[Evaluation of each example]
Ten expert panelists sensory-evaluated the softness of the test fabric by comparing it with a control fabric, and scored it using the following scoring criteria. The average value of 10 expert panelists was determined and evaluated using the following criteria. A case where the average value was 3 points or more was considered to be a pass.
≪Scoring criteria≫
5 points: The test fabric is much softer than the control fabric.
4 points: The test fabric is significantly softer than the control fabric.
3 points: The test fabric is softer than the control fabric.
2 points: The test fabric is slightly softer than the control fabric.
1 point: The softness of the test fabric is equivalent to that of the control fabric.
≪Judgment criteria≫
◎: Average value is 4.0 points or more.
○: Average value is 3.0 points or more and 4 points. Less than 0.
△: Average value is 2.0 points or more and 3 points. Less than 0.
×: Average value is less than 2.0 points.

(Examples 1 to 20, Comparative Examples 1 to 4)
<Preparation of liquid cleaning composition>
According to the compositions shown in Tables 1 and 2, components (A) to (C) and other components were added to water and mixed to prepare liquid cleaning compositions for each example.
Note that the blending amounts in the table are pure equivalent values. In addition, components whose blending amounts are not listed in the table are not blended.
The pH of the liquid cleaning compositions of Examples 1 to 20 and Comparative Examples 1 to 4 was within the range of 6 to 8.

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

As shown in Tables 1 and 2, Examples 1 to 20 had excellent cleaning effects and flexibility.
Comparative Example 1, which was provided with a rinsing step, had significantly lower flexibility than Example 7.
Comparative Example 2, in which the cleaning liquid did not contain component (A), had poor cleaning effects.
Comparative Example 3, in which the cleaning liquid did not contain component (B), had poor cleaning effects.
Comparative Example 4, in which the cleaning liquid did not contain component (C), had poor flexibility. Furthermore, compared to Example 7, the cleaning effect was lower.

Claims (6)

A washing step in which a cleaning 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,
In the washing method, the washing liquid contains the following (A) component, the following (B) component, and the following (C) component.
(A) Component: Non-soap surfactant.
Component (B): one or more selected from the group consisting of enzymes (B1), polymeric organic dispersants (B2), and chelating agents (B3).
Component (C): fatty acid having 12 to 18 carbon atoms or a salt thereof. The washing method according to claim 1, wherein the content of the component (C) is 1 to 100 ppm by mass based on the total mass of the cleaning liquid. The washing method according to claim 1 or 2, wherein the content of the component (A) is 40 to 200 ppm by mass based on the total mass of the cleaning liquid. The washing method according to claim 1 or 2, wherein the enzyme (B1) contains one or more selected from protease, lipase, amylase, and cellulase. The washing method according to claim 1 or 2, wherein the component (A) contains one or both of a nonionic surfactant (A1) and an anionic surfactant (A2). The component (A) contains a nonionic surfactant (A1),
In the cleaning liquid, A1/(A1+A2) representing the mass ratio of the nonionic surfactant (A1) to the total of the nonionic surfactant (A1) and the anionic surfactant (A2) is 0.2/1 or more. The washing method according to claim 5.