Washing instructions

Abstract

DEPCT67 A washing method that produces less foam during rinsing, has good rinsing properties, and is capable of... Demonstrating sufficient cleaning power even though the rinsing step is omitted for simplified operation, this invention is... Washing methods for fiber products that involve washing steps that expose the fiber product to detergents, including: There is no need for a rinsing step after the washing process; the detergents included are... Component (A): Surfactant, and Component (B): Organic dispersant. Polymer, and the concentration of component (A) is 30-200 ppm per total mass of The laundry detergent mentioned;

Description

Washing Instructions

[0001] The present invention relates to a washing method. This application claims priority based on Japanese Patent Application No. 2021-162976, filed on October 1, 2021, the contents of which are incorporated herein by reference.

[0002] In recent years, from the viewpoints of resource conservation, energy conservation, and reduction of the environmental load, there has been a demand for simplification of the rinsing step, such as by reducing the number of rinsing cycles after cleaning with a cleaning liquid prepared by diluting a detergent composition with water or by reducing the amount of rinsing water required for rinsing.

[0003] In a typical detergent solution, a high level of foaming during washing leads to a good feel when used, and the absence of foam during rinsing is an indication of completion of rinsing. For example, Patent Document 1 discloses a washing method using a liquid detergent composition for textile products containing a specific anionic surfactant, a specific amount of an alkylene oxide adduct of a polyalkyleneamine, a specific fatty acid or its salt, and a specific nonionic surfactant. According to the invention described in Patent Document 1, the function of preventing soiling adhering to textile products from being removed by the detergent solution and adhering to other textile products (anti-redeposition ability) and the function of suppressing foaming of the detergent solution and shortening the rinsing time (foam suppression ability, rinsability) are improved.

[0004] Japanese Patent Application Publication No. 2020-050839

[0005] However, it is desirable to simplify the rinsing step in a washing method. Simplifying the rinsing step here means that at least one of the amount of rinsing water and the number of rinses can be reduced, and preferably means that the rinsing step can be eliminated.

[0006] While studying ways to simplify the rinsing process, the inventors discovered the following problems. For example, in a washing machine that is set to automatically start water injection and proceed to the rinsing process when it detects foam after spin-drying, if it detects foam even after the rinsing process, the rinsing process is automatically extended. Therefore, in order to simplify or eliminate the rinsing process, it is necessary to reduce the amount of foam. Furthermore, if the number of rinses or the amount of rinse water is reduced, dirt that has been removed from the washed items may re-adhere to the washed items, resulting in insufficient detergency. Therefore, it is also necessary for the washing method to be able to obtain sufficient detergency even when the number of rinses or the amount of rinse water required for rinsing are reduced.

[0007] Therefore, an object of the present invention is to provide a washing method that produces less foam during washing and has good rinsing properties, and that can exert sufficient detergency even when the rinsing step is simplified.

[0008] The present invention has the following aspects. [1] A method for washing textile products, comprising a washing step of contacting a washing solution with textile products and not requiring a rinsing step after the washing step, wherein the washing solution contains component (A): a surfactant and component (B): a polymeric organic dispersant, and the concentration of component (A) is 30 to 200 ppm relative to the total mass of the washing solution. [2] The method according to [1], wherein the concentration of component (A) in the washing solution is 30 to 150 ppm relative to the total mass of the washing solution. [3] The method according to [1] or [2], wherein the mass ratio of component (B) / component (A) in the washing solution is 0.01 to 10. [4] The method according to any one of [1] to [3], wherein component (B) is one or more selected from alkoxylated polyalkyleneimine, polyacrylic acid-based polymer, and carboxymethyl cellulose-based polymer.

[0009] According to the washing method of the present invention, there is little foaming during washing, rinsing is good, and sufficient detergency can be exerted even when the rinsing step is simplified.

[0010] [Washing liquid] The washing liquid used in the washing method of the present invention is an aqueous liquid containing component (A) and component (B). The aqueous liquid conceptually includes at least one of an aqueous solution and an aqueous dispersion.

[0011] <<Component (A)>> Component (A) is a non-soap surfactant. A "non-soap surfactant" is a surfactant excluding higher fatty acids or their salts (so-called soaps). A "higher fatty acid" is a saturated or unsaturated fatty acid 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 their salts. Component (A) is a component that imparts detergency to the cleaning liquid. Component (A) may be used alone or in combination of two or more. Examples of component (A) include nonionic surfactants, non-soap anionic surfactants, cationic surfactants, amphoteric surfactants, and semi-polar surfactants. It is preferable that component (A) include one or both of components (A1) and (A2) described below.

[0012] <Component (A1)> Component (A1) is a nonionic surfactant. Component (A1) may be any nonionic surfactant conventionally used in detergent compositions for clothing, etc. Examples of component (A1) include polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts of higher amines, etc., 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, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides. In this specification, "higher" refers to organic compounds having 8 to 24 carbon atoms. As component (A1), polyoxyalkylene-type nonionic surfactants are preferred due to their excellent detergency. Component (A1) may be used alone or in combination of two or more.

[0013] Examples of polyoxyalkylene-type nonionic surfactants include compounds represented by the following formula (a1) (hereinafter also referred to as "compound (a1)"). １ -X-[(EO) ｍ / (PO) ｎ ]-R ２ ...(a1) In formula (a1), R １ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, and R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; EO represents an oxyethylene group; PO represents an oxypropylene group; m represents the average number of repeating EOs and is a number from 3 to 20; and n represents the average number of repeating POs and is a number from 0 to 6. [(EO) ｍ / (PO) ｎ The symbol "-" indicates that the EO and PO may be random chains or block chains. The average number of repeating units can be measured by gas chromatography or the like.

[0014] In formula (a1), R １ The hydrocarbon group of R may be linear or branched. It may have an unsaturated bond. １ has 6 to 22 carbon atoms, preferably 8 to 20, and more preferably 10 to 18. １ Examples of -X- include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides. In formula (a1), -X- includes -O-, -COO-, and -CONH-. -X- is preferably -O- or -COO- from the viewpoint of excellent effect of improving detergency. ２ When is an alkyl group, R ２ The carbon number of R is 1 to 6, preferably 1 to 3. ２ When is an alkenyl group, R ２ The carbon number of R is 2 to 6, preferably 2 to 3. ２ is preferably a hydrogen atom.

[0015] In formula (a1), m represents the average number of repeating EO units (i.e., the average number of moles of ethylene oxide added), and is a number from 3 to 20, preferably from 5 to 18, and more preferably from 7 to 16. When m is at least the above lower limit, deterioration of the raw material odor of component (A) itself can be suppressed. When m is at most the above upper limit, the detergency against sebum can be enhanced.

[0016] In formula (a1), n ​​represents the average number of PO repeats (i.e., the average number of moles of propylene oxide added), and is a number from 0 to 6, preferably 0 to 3. When n is equal to or less than the above upper limit, solution stability at high temperatures (e.g., 50°C) can be further improved. When n is 1 or more, that is, when compound (a1) has EO and PO, the method for adding EO and PO is not particularly limited, and may be, for example, a random addition method or a block addition method. Examples of block addition methods include a method of adding EO and then adding PO, a method of adding PO and then adding EO, and a method of adding EO, adding PO, and then adding EO.

[0017] The distribution of the number of moles of EO or PO added is not particularly limited. The distribution of the number of moles of EO or PO added is likely to vary depending on the reaction method used in producing the nonionic surfactant. For example, when EO or PO is added to a hydrophobic raw material using an alkali catalyst such as sodium hydroxide or potassium hydroxide, the distribution of the number of moles of EO or PO added tends to be relatively wide. ３＋ , Ga ３＋ , In ３＋ , Co ３＋ , Sc ３＋ , La ３＋ , Mn ２＋ When EO or PO is added to a hydrophobic raw material using a specific alkoxylation catalyst such as magnesium oxide to which a metal ion such as ethylene glycol or propylene glycol has been added, the distribution of the number of moles of EO or PO added tends to be a relatively narrow distribution.

[0018] The compound (a1) is a compound in which —X— is —O— (alcohol-type nonionic surfactant) or a compound in which —X— is —COO— and R ２is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (fatty acid alkyl(alkenyl) ester) is particularly preferred. １ The number of carbon atoms in R is preferably 10 to 22, more preferably 10 to 20, and even more preferably 10 to 18. ２ is preferably a hydrogen atom. When —X— is —COO—, R １ The number of carbon atoms in R is preferably 9 to 21, and more preferably 11 to 21. ２ is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

[0019] <Component (A2)> The component (A2) is a non-soap anionic surfactant. A "non-soap anionic surfactant" is an anionic surfactant excluding higher fatty acids or their salts (so-called soaps). A "higher fatty acid" is a saturated or unsaturated fatty acid having 8 to 24 carbon atoms. In other words, the component (A2) is an anionic surfactant excluding saturated or unsaturated fatty acids having 8 to 24 carbon atoms and their salts. Examples of component (A2) include linear alkylbenzenesulfonic acid or its salt (LAS), α-olefinsulfonic acid or its salt (AOS), internal olefinsulfonic acid or its salt (IOS), hydroxyalkanesulfonic acid or its salt, polyoxyalkylene alkenyl ether sulfate ester or its salt, alkyl group-containing alkane sulfonic acid or its salt, α-sulfofatty acid ester or its salt (MES), alkyl ether carboxylic acid or its salt, polyoxyalkylene ether carboxylic acid or its salt, alkylamide ether carboxylic acid or its salt, alkenylamide 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 alkylphenyl phosphate ester or its salt, glycerin fatty acid ester monophosphate ester or its salt, dialkyl sulfosuccinic acid or its salt, monoalkyl sulfosuccinic acid or its salt, and the like. Examples of salts in component (A2) include alkali metal salts such as sodium salts and potassium salts; alkaline earth metal salts such as magnesium salts; alkanolamine salts such as monoethanolamine salts and diethanolamine salts; and the like. One type of component (A2) may be used alone, or two or more types may be used in combination.

[0020] As component (A2), one or more selected from the group consisting of linear alkylbenzenesulfonic acid or its salt, α-olefinsulfonic acid or its salt, internal olefinsulfonic acid or its salt, and polyoxyalkylene alkenyl ether sulfate or its salt are preferred, in terms of their excellent effect of improving rinsing performance. One type of component (A2) may be used alone, or two or more types may be used in combination.

[0021] As the linear alkylbenzenesulfonic acid or a salt thereof, one in which the linear alkyl group has 8 to 16 carbon atoms is preferred, and one in which the linear alkyl group has 10 to 14 carbon atoms is particularly preferred. As the α-olefin sulfonate or internal olefin sulfonate, one in which the carbon number is 10 to 20 is preferred. As the polyoxyalkylene alkyl ether sulfate or a salt thereof, an alkenyl ether sulfate having a linear or branched alkenyl group having 10 to 20 carbon atoms and to which an average of 1 to 10 moles of ethylene oxide have been added (i.e., a polyoxyethylene alkenyl ether sulfate) is preferred. The component (A2) may be produced by a conventional method, or a commercially available product may be used.

[0022] Other examples of component (A) include cationic surfactants, amphoteric surfactants, and semi-polar surfactants. Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. Examples of counter ions of these salts include halogen ions and alkyl sulfate ions. Examples of halogen ions include fluoride ions, chloride ions, bromide ions, and iodide ions. Examples of alkyl sulfate ions include those having an alkyl group containing 1 to 3 carbon atoms, such as methyl sulfate ions and ethyl sulfate ions. Examples of amphoteric surfactants include alkylcarboxybetaines, alkylsulfobetaines, alkylhydroxysulfobetaines, alkylamidobetaines, and imidazolinium betaines. Examples of semi-polar surfactants include amine oxide surfactants such as lauryldimethylamine oxide and lauric acid amidopropyldimethylamine oxide. These surfactants may be produced by conventional methods, or commercially available products may be used.

[0023] The concentration of component (A) in the cleaning solution is 30 to 200 ppm by mass (relative to the total mass of the cleaning solution), preferably 30 to 150 ppm, more preferably 40 to 140 ppm, and even more preferably 50 to 120 ppm. When the concentration of component (A) is equal to or greater than the above-mentioned lower limit, detergency can be further enhanced. In addition, when the concentration of component (A) is equal to or greater than the above-mentioned lower limit, anti-redeposition properties can be further enhanced. When the concentration of component (A) is equal to or less than the above-mentioned upper limit, foaming can be suppressed and rinsing properties can be further improved.

[0024] When the cleaning solution contains the component (A1), the concentration of the component (A1) in the cleaning solution is preferably 10 to 200 ppm by mass, more preferably 10 to 150 ppm, even more preferably 15 to 120 ppm, and even more preferably 20 to 100 ppm. When the concentration of the component (A1) is equal to or greater than the above-mentioned lower limit, the detergency can be further improved. When the concentration of the component (A1) is equal to or less than the above-mentioned upper limit, the rinsing performance can be further improved.

[0025] When the cleaning solution contains component (A2), the concentration of component (A2) in the cleaning solution is preferably 10 to 150 ppm by mass, more preferably 15 to 120 ppm, even more preferably 20 to 100 ppm, and even more preferably 20 to 50 ppm. When the concentration of component (A2) is at least the above lower limit, the anti-redeposition properties can be further improved. When the concentration of component (A2) is at most the above upper limit, the rinsing properties can be further improved. Component (A1) and component (A2) may be used alone or in combination. It is preferable to use component (A1) alone, or component (A1) and component (A2) in combination.

[0026] The mass ratio of component (A1) to component (A) in the cleaning solution (hereinafter also referred to as the "A1 / A ratio") is preferably 0.1 to 1, more preferably 0.3 to 1, and even more preferably 0.5 to 1. When the A1 / A ratio is equal to or greater than the above-mentioned lower limit, the detergency can be further enhanced. When component (A1) and component (A2) are used in combination, the mass ratio of component (A1) to component (A2) (hereinafter also referred to as the "A1 / A2 ratio") is preferably 0.1 to 10, more preferably 0.3 to 5, and even more preferably 1 to 3. When the A1 / A2 ratio is equal to or greater than the above-mentioned lower limit, rinsability is good and detergency can be further enhanced, and when it is equal to or less than the above-mentioned upper limit, anti-redeposition properties are good.

[0027] <<Component (B)>> Component (B) is a polymeric organic dispersant. The cleaning solution of this embodiment contains component (B), which enhances the cleaning action. Therefore, the cleaning solution of this embodiment can exhibit sufficient cleaning power even when the concentration of component (A) is lower than that of conventional cleaning agents. Here, the term "polymeric organic dispersant" refers to an organic compound with a molecular weight of 1,000 or more that exhibits cleaning power when used in combination with component (A). Component (B) preferably includes one or more selected from the group consisting of component (B1), component (B2), and component (B3), which will be described later.

[0028] <Component (B1)> The component (B1) is an alkoxylated polyalkyleneimine. That is, the component (B1) is an alkylene oxide adduct of a polyalkyleneimine. The polyalkyleneimine is represented, for example, by the following formula (b1): NH ２ -R ３ -[N(A １ )-R ３ ] ｎ -NH ２ ...(b1) In formula (b1), R ３ are each independently an alkylene group having 2 to 6 carbon atoms, １ is a hydrogen atom or another branched polyamine chain, and n is a number of 1 or more. １ are not all hydrogen atoms. That is, the polyalkyleneimine represented by formula (b1) has a branched polyamine chain in its structure. ３Examples of R include a linear alkylene group having 2 to 6 carbon atoms and a branched alkylene group having 3 to 6 carbon atoms. ３ As the alkylene group, an alkylene group having 2 to 4 carbon atoms is preferred, and an alkylene group having 2 carbon atoms is more preferred.

[0029] The polyalkyleneimine can be obtained, for example, by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms by a conventional method. Examples of alkyleneimines having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Preferred polyalkyleneimines are polyethyleneimine (hereinafter also referred to as "PEI") and polypropyleneimine, with PEI being more preferred. PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms in its structure.

[0030] The weight 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 hydrogen atoms per molecule, more preferably 7 to 25 active hydrogen atoms, and even more preferably 10 to 20 active hydrogen atoms. In this specification, the weight average molecular weight refers to a value determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

[0031] Component (B1) can be obtained by adding an alkylene oxide to a polyalkyleneimine, for example, by adding an alkylene oxide such as ethylene oxide to a polyalkyleneimine starting material at 100 to 180°C in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate.

[0032] 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.

[0033] Examples of the component (B1) include an ethylene oxide adduct of a polyalkyleneimine, a propylene oxide adduct of a polyalkyleneimine, and an ethylene oxide-propylene oxide adduct of a polyalkyleneimine. The ethylene oxide-propylene oxide adduct of a polyalkyleneimine is obtained by adding ethylene oxide and propylene oxide to a polyalkyleneimine, and the order of addition of ethylene oxide and propylene oxide to the polyalkyleneimine and the addition form (block, random) are optional. From the viewpoint of deodorizing effect, the component (B1) is preferably an ethylene oxide adduct of a polyalkyleneimine or an ethylene oxide-propylene oxide adduct of a polyalkyleneimine, and more preferably an ethylene oxide adduct of a polyalkyleneimine.

[0034] The component (B1) is preferably one in which an average of 5 to 40 moles of alkylene oxide is added per mole of active hydrogen contained in the raw material polyalkyleneimine, more preferably one in which an average of 5 to 30 moles of alkylene oxide is added, even more preferably one in which an average of 8 to 25 moles of alkylene oxide is added, and particularly preferably one in which an average of 8 to 15 moles of alkylene oxide is added.

[0035] Examples of the component (B1) include compounds represented by the following formula (b1-1):

[0036]

[0037] In formula (b1-1), R ２２ are each independently an alkylene group having 2 to 6 carbon atoms, and each m is independently a number of 1 or more. ２２ is preferably an alkylene group having 2 or 3 carbon atoms, more preferably an alkylene group having 2 carbon atoms. m is (R ２２ Each m is independently preferably a number from 5 to 40, more preferably a number from 5 to 30, even more preferably a number from 8 to 25, and particularly preferably a number from 8 to 15.

[0038] The mass average molecular weight of the component (B1) is preferably from 1,000 to 80,000, more preferably from 2,000 to 50,000, even more preferably from 3,000 to 30,000, and particularly preferably from 5,000 to 20,000.

[0039] The component (B1) may be a synthetic product or a commercially available product. An example of a commercially available product is "Sokalan (registered trademark) HP20." The component (B1) may be used alone or in combination of two or more types.

[0040] <Component (B2)> Component (B2) is a polyacrylic acid-based polymer. By including component (B2), the cleaning solution of this embodiment can further enhance its detergency against sebum stains. Examples of component (B2) include one or more selected from polyacrylic acid and its salts, polymaleic acid and its salts, acrylic acid-maleic acid copolymers and their salts, copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and their salts, and acrylic acid-methacrylic acid copolymers and their salts. Component (B2) is preferably one or more selected from acrylic acid-maleic acid copolymers and their salts, or one or more selected from copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and their salts. The salt may be a partial or complete salt, and alkali metal salts such as sodium or potassium salts, or organic amine salts such as alkanolamines, are preferred.

[0041] The hydrocarbon having 4 to 12 carbon atoms in component (B2) may be any hydrocarbon copolymerizable with maleic acid, and from the viewpoint of raw material handleability, hydrocarbons having 10 or less carbon atoms are preferred, and hydrocarbons having 5 to 9 carbon atoms are more preferred. Examples of such hydrocarbons include unsaturated chain hydrocarbons having a double bond.

[0042] The copolymer of component (B2) may be a polymer having one or more repeating units 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):

[0043]

[0044] 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, or (AO)nX. A is an oxyalkylene group having 2 to 4 carbon atoms, n is an integer of 2 to 300, and X is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. In formula (b2-2), R ７ is a hydrogen atom or a methyl group, and 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. ９ When is a hydrogen atom, R ８ is an alkyl group having 10 to 30 carbon atoms, and R ９ is a carboxyl group, R ８ is a hydrogen atom.

[0045] In formula (b2-1), R ６ The alkyl group of R may be linear or branched. It may also contain a cyclic structure. ６ The number of carbon atoms in the alkyl group is preferably 1 to 8, and 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; acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and n-butyl acrylate; methacrylic acid; and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and n-butyl methacrylate. One type of monomer (b2-1) may be used alone, or two or more types may be used in combination.

[0046] In formula (b2-2), R ８ The alkyl group of R may be linear or branched. It may also contain a cyclic structure. ８ The number of carbon atoms in the alkyl group is preferably 10 to 25, and more preferably 10 to 20. Among the monomers represented by formula (b2-2) (hereinafter also referred to as monomer (b2-2)), in formula (b2-2), ９ is a hydrogen atom, R ８Examples of the monomer (b2-2) in which R is an alkyl group having 10 to 30 carbon atoms include decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, and octadecyl methacrylate. ９ is a carboxyl group, R ８ Examples of the monomer (b2-2) in which R is a hydrogen atom include maleic acid and fumaric acid. ９ is a carboxyl group, R ８ The monomer (b2-2) in which is a hydrogen atom is preferably maleic acid. The monomer (b2-2) may be used alone or in combination of two or more.

[0047] The component (B2) may be a crosslinked polymer or a non-crosslinked polymer. Examples of the crosslinked polymer include a polymer crosslinked by a crosslinking agent. Examples of the crosslinking agent include an allyl ether compound. Examples of the allyl ether compound include allyl ether, allyl ether of a sugar, and allyl ether of a sugar alcohol. Examples of the sugar include sucrose. Examples of the sugar alcohol include pentaerythritol.

[0048] The component (B2) may have a repeating unit (another repeating unit) other than the repeating unit derived from the monomer represented by formula (b2-1) and the repeating unit derived from the monomer represented by formula (b2-2). Examples of the other repeating unit include a repeating unit derived from another monomer. The other monomer is not particularly limited as long as it is copolymerizable with the monomer (b2-1) and the monomer (b2-2), and examples include methyl acrylate, ethyl acrylate, methacrylic acid, and methyl methacrylate. One type of other monomer may be used alone, or two or more types may be used in combination.

[0049] The mass average molecular weight of component (B2) is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 5,000 to 50,000. When the mass average molecular weight of component (B2) is at least the above lower limit, detergency can be further improved. When the mass average molecular weight of component (B2) is at most the above upper limit, liquid stability can be further improved.

[0050] The component (B2) may be used alone or in combination of two or more types.

[0051] <Component (B3)> The component (B3) is a carboxymethyl cellulose-based polymer. By including the component (B3), the cleaning solution of this embodiment can further enhance the anti-redeposition properties. Examples of the component (B3) include carboxymethyl cellulose (CMC) or a salt thereof. Examples of CMC salts include alkali metal salts such as sodium salt and potassium salt, and ammonium salt, and mixtures of these salts are also possible. As the CMC salt, the sodium salt is preferred.

[0052] Examples of CMC include anionic water-soluble or water-insoluble cellulose ethers obtained by treating pulp as a raw material with an aqueous sodium hydroxide solution and then reacting the treated cellulose with monochloroacetic acid. Specific examples include polymer compounds having a repeating unit represented by the following formula (b3-1):

[0053]

[0054] In formula (b3-1), n ​​represents the number of repeating units; １１ ~R １３ are each independently a hydroxyl group or a carboxymethyl group (—CH ２ COO-Z+; Z+ is a counter ion).

[0055] 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 1,200,000 or less, more preferably 1,000,000 or less. When the mass average molecular weight of CMC is equal to or greater than the lower limit, the anti-redeposition property can be further improved. When the mass average molecular weight of CMC is equal to or less than the upper limit, the solubility is improved and the liquid stability can be further improved.

[0056] The degree of etherification of CMC is preferably 0.2 to 1.3, more preferably 0.2 to 1.0, and even more preferably 0.2 to 0.7. In this specification, the degree of etherification of CMC means the average number of hydroxyl groups substituted with carboxymethyl groups or salts thereof per glucose ring unit (indicating how many of the three hydroxyl groups on the glucose ring are substituted with carboxymethyl groups or salts thereof, up to a maximum of 3). For example, in the above formula (b3-1), -OR １１ , -OR １２ , -OR １３ Among them, R １１ ~R １３ The average number of groups substituted with carboxymethyl groups or salts thereof is the degree of etherification.

[0057] Commercially available CMC products may be used. Commercially available CMC products include those sold by Daicel Miraize Co., Ltd. under the trade names "CMC Daicel" and "HEC (hydroxyethyl cellulose) Daicel." Examples of CMC Daicel products include product numbers 1110, 1120, 1130, 1140, 1160, 1170, 1180, 1190, 1220, 1240, 1260, 1280, 1290, 1380, 2200, 2260, 2280, 2450, and 2340. Examples of HEC Daicel products include product numbers SP200, SP400, SP500, SP600, SP850, and SP900. Another commercially available CMC product is sold by Nippon Paper Industries Co., Ltd. under the trade name "Sunrose (registered trademark)." Examples of Sunrose (registered trademark) include the Sunrose F series, such as F10LC, F600LC, F1400LC, F10MC, F150MC, F350HC, F1400MC, and F1400MG; the Sunrose A series, such as A02SH, A20SH, and A200SH; and SLD-F1 (all trade names). Among the above, commercially available CMC products include CMC Daicel 1130, 1170, 1180, 1190, and 1260, HEC Daicel SP400 and SP500, Sunrose F1400LC, F1400MC, and Sunrose SLD-F1, with CMC Daicel 1260 and HEC Daicel SP500 being more preferred.

[0058] The component (B3) may be used alone or in combination of two or more types.

[0059] Other examples of component (B) include cationized cellulose, polyvinylpyrrolidone, and hydroxypropylmethylcellulose.

[0060] The concentration of component (B) in the cleaning solution is preferably 5 to 200 ppm, more preferably 10 to 150 ppm, and even more preferably 20 to 100 ppm, on a mass basis (relative to the total mass of the cleaning solution). When the concentration of component (B) is equal to or greater than the above-mentioned lower limit, the cleaning power can be further enhanced. In addition, when the concentration of component (B) is equal to or greater than the above-mentioned lower limit, the anti-redeposition properties can be further enhanced. When the concentration of component (B) is equal to or less than the above-mentioned upper limit, the solution stability can be further enhanced.

[0061] When the cleaning solution contains component (B1), the concentration of component (B1) is preferably 5 to 100 ppm by mass, more preferably 10 to 80 ppm, and even more preferably 20 to 50 ppm. When the concentration of component (B1) is at least the above-mentioned lower limit, the cleaning power and anti-soil redeposition properties can be further improved. When the concentration of component (B1) is at most the above-mentioned upper limit, the solution stability can be further improved.

[0062] When the cleaning solution contains component (B2), the concentration of component (B2) is preferably 5 to 100 ppm by mass, more preferably 10 to 80 ppm, and even more preferably 20 to 50 ppm. When the concentration of component (B2) is at least the above-mentioned lower limit, the cleaning power and anti-soil redeposition properties can be further improved. When the concentration of component (B2) is at most the above-mentioned upper limit, the solution stability can be further improved.

[0063] When the cleaning solution contains component (B3), the concentration of component (B3) is preferably 0.1 to 50 ppm, more preferably 0.5 to 30 ppm, and even more preferably 1 to 10 ppm, by mass. When the concentration of component (B3) is at least the above-mentioned lower limit, the anti-soil redeposition properties can be further improved. When the concentration of component (B3) is at most the above-mentioned upper limit, the solution stability can be further improved. Component (B1), component (B2), and component (B3) may be used alone or in combination of two or more.

[0064] The mass ratio of component (B) to component (A) in the cleaning solution (hereinafter also referred to as "B / A ratio") is preferably 0.01 to 10, more preferably 0.05 to 5, even more preferably 0.1 to 1, and particularly preferably 0.3 to 1. When the B / A ratio is equal to or greater than the above lower limit, the cleaning power and anti-soil redeposition properties can be further improved. When the B / A ratio is equal to or less than the above upper limit, the solution stability can be further improved.

[0065] The cleaning solution of this embodiment contains a solvent. Water is preferably used as the solvent from the viewpoints of ease of preparation, ease of use, ease of availability, and the like. The water used is preferably ion-exchanged water, distilled water, or purified water, from which metal ions such as heavy metals dissolved in water have been removed, from the viewpoint of the stability of the cleaning solution over time. The water content in the cleaning solution is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the cleaning solution. When the water content is equal to or greater than the above-mentioned lower limit, the solution stability of the cleaning solution over time becomes better.

[0066] <<Optional Components>> The cleaning liquid of this embodiment may contain other components (optional components) in addition to the component (A) and the component (B). Examples of optional components include components typically used in detergent compositions, such as higher fatty acids or salts thereof, water-miscible organic solvents, chelating agents, enzymes, hydrotropes, antifoaming silicones, soil release agents, stabilizers, alkali agents, texture improvers, preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, thickeners, UV absorbers, general-purpose dyes or pigments as colorants, emulsifiers, fragrances, insoluble particles, pH adjusters, and extracts of natural products. These optional components may be used alone or in combination of two or more.

[0067] The cleaning solution can further improve rinsing properties by containing a higher fatty acid or a salt thereof. For this reason, the cleaning solution preferably contains a higher fatty acid or a salt thereof. As the higher fatty acid, a fatty acid having 8 to 18 carbon atoms is preferred. Examples of fatty acids having 8 to 18 carbon atoms include single fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, hydroxystearic acid, and oleic acid; and mixed fatty acids such as coconut oil fatty acid and beef tallow fatty acid.

[0068] The fatty acids having 8 to 18 carbon atoms may be used singly or in appropriate combination of two or more. A preferred combination is a combination of a fatty acid having 12 carbon atoms in the hydrocarbon group with a fatty acid having 14 to 18 carbon atoms in the hydrocarbon group, and a more preferred combination is a combination of a fatty acid having 12 carbon atoms with two or more fatty acids having 14 to 18 carbon atoms in the hydrocarbon group. The ratio of the mass of the fatty acid having 14 to 18 carbon atoms to the mass of the fatty acid having 12 carbon atoms, [fatty acid having 14 to 18 carbon atoms] / [fatty acid having 12 carbon atoms], is preferably 0.03 or more and 1 or less, more preferably 0.05 or more and 0.8 or less, and even more preferably 0.06 or more and 0.5 or less.

[0069] Examples of salt forms of higher fatty acids include alkali metal salts such as sodium and potassium salts, alkaline earth metal salts such as magnesium salts, and alkanolamine salts such as monoethanolammonium and diethanolammonium salts. Commercially available products of higher fatty acids or salts thereof include sodium coconut fatty acid (coconut fatty acid (manufactured by NOF Corporation) neutralized with sodium hydroxide, a pH adjuster), C16 soap (sodium palmitate (manufactured by Kanto Chemical Co., Inc.)), and the like.

[0070] When the cleaning solution contains a higher fatty acid or a salt thereof, the concentration of the higher fatty acid or a salt thereof in the cleaning solution is preferably 20 to 115 ppm, more preferably 30 to 80 ppm, by mass. When the concentration of the higher fatty acid or a salt thereof is equal to or higher than the above-mentioned lower limit, rinsing performance can be further improved. When the concentration of the higher fatty acid or a salt thereof is equal to or lower than the above-mentioned upper limit, detergency can be further improved.

[0071] The cleaning solution of this embodiment can be improved in stability and antiseptic properties during storage at low temperatures (e.g., 5°C) by incorporating a water-miscible organic solvent. In this specification, a water-miscible organic solvent refers to an organic solvent that dissolves at least 50 g in 1 L of ion-exchanged water at 25°C. Examples of water-miscible organic solvents include alcohols, glycols, polyglycols, alkyl ethers, and phenoxyethanol. Examples of alcohols include ethanol, 1-propanol, 2-propanol, and 1-butanol. Examples of glycols include propylene glycol, butylene glycol, and hexylene glycol. Examples of polyglycols include dipropylene glycol. Examples of alkyl ethers include diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl ether, diethylene glycol monophenyl ether, and 3-methoxy-3-methyl-1-butanol. Among these, ethanol, propylene glycol, diethylene glycol monobutyl ether (butyl carbitol), 3-methoxy-3-methyl-1-butanol, and phenoxyethanol are preferred in terms of availability, liquid stability, flowability, and the like.

[0072] Examples of metal ion sequestrants (chelating agents) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid, methylglycine diacetate (MGDA), L-glutamic acid diacetate (GLDA), diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid, ethylenediaminesuccinic acid (EDDS), 3-hydroxy-2,2'-iminodisuccinic acid (HIDS), L-aspartic acid-N,N-diacetic acid, and salts thereof. Examples of hydrotropes include paratoluenesulfonic acid or its salts, cumenesulfonic acid or its salts, benzoates, phenoxyethanol, and urea. Examples of soil release agents include water-soluble polymers having at least one unit selected from the group consisting of alkylene terephthalate units and alkylene isophthalate units, and at least one unit selected from the group consisting of oxyalkylene units and polyoxyalkylene units, as described in International Publication No. 2014 / 109380. Specific examples include components commercially available under the trade names TexCare SRN-100 (manufactured by Clariant Japan, weight average molecular weight: 2000-3000), TexCare SRN-300 (manufactured by Clariant Japan, weight average molecular weight: 7000), Repel-O-Tex Crystal (manufactured by Rhodia), and Repel-O-Tex QCL (manufactured by Rhodia). Examples of alkaline agents include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

[0073] As the feel improver, for example, a silicone oil having a modified group can be used. Specific examples include polyether-modified silicone, aminopolyether-modified silicone, amidepolyether-modified silicone, and alkylpolyether-modified silicone. By incorporating a silicone oil having a modified group, friction of the textile product in the bath is reduced, and the feel after drying is improved. Commercially available silicone oils having a modified group include, for example, "CF1188N", "BY16-878", "BY16-891", "BY16-893", "FV2090-01", "SILSTYLE104", "SF8417", "SF8418", "BY16-837", "BY16-906", "FZ-2203", and "FZ-3789" manufactured by Toray Dow Corning Co., Ltd. , "KF-877", "KF-889", "X-22-3939A", etc. manufactured by Shin-Etsu Chemical Co., Ltd., and "WetSoft (registered trademark) CTA", "WetSoft (registered trademark) AE200", "WetSoft (registered trademark) NE810", "WetSoft (registered trademark) NE820", "WetSoft (registered trademark) WP201", etc. manufactured by Wacker Asahi Kasei Silicones Co., Ltd.

[0074] Antifoaming silicones can be any of oil type, oil compound type, emulsion type, and self-emulsifying type. Oil-type antifoaming silicones are composed of 100% unmodified silicone oil and are silica-free. Commercially available products include SH200 (Dow Corning Toray Co., Ltd.). Oil-compound type antifoaming silicones are antifoaming agents in which water-insoluble particles such as finely powdered silica are blended with silicone oil. Commercially available products include 8590 Additive, AF-8014 Antifoam, AC-8066 Antifoam, ACP-3073 Antifoam (all Dow Corning Toray Co., Ltd.), KS-66 (Shin-Etsu Chemical Co., Ltd.), etc. Solution-type antifoaming silicones are antifoaming agents in which silicone oil is dissolved in a solvent such as isoparaffin. Commercially available products include KS-602A (Shin-Etsu Chemical Co., Ltd.), etc. Emulsion-type antifoaming silicones are antifoaming agents in which a silicone oil compound is emulsified with a nonionic surfactant. Commercially available products include FS Antifoam 93 (Dow Corning Toray Co., Ltd.), KM-90, KM-73, KM-7750, and KM-7752 (all from Shin-Etsu Chemical Co., Ltd.). Self-emulsifying antifoaming silicones are antifoaming agents composed of a hydrophilic modified silicone oil and an oil compound. Commercially available products include KS-537 (Shin-Etsu Chemical Co., Ltd.).

[0075] Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan, and "NIPACIDE BIT 20" (trade name) manufactured by Clariant. Examples of antioxidants include dibutylhydroxytoluene (BHT), distyrenated cresol, sodium sulfite, and sodium hydrogen sulfite. Examples of fragrances include fragrance components described in JP-A-2002-146399. Examples of pH adjusters include sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamines.

[0076] Examples of antibacterial agents include organic antibacterial agents such as diphenyls, alcohols, phenols, aldehydes, carboxylic acids, esters, ethers, nitriles, peroxides / epoxies, halogens, pyridine / quinolines, triazines, isothiazolones, imidazole / thiazoles, anilides, biguanides, disulfides, thiocarbamates, sugars, tropolones, and organometallics; and inorganic antibacterial agents such as metal oxides and silver. Specific examples include diclosan, triclosan, bis-(2-pyridylthio-1-oxide)zinc, polyhexamethylene biguanide hydrochloride, 8-oxyquinoline, isopropylmethylphenol, and polylysine.

[0077] Examples of extracts of natural products include sophora japonica, uva-ursi, echinacea, scutellaria, phellodendron amurense, coptis japonica, allspice, oregano, sophora japonica, chamomile, honeysuckle, sophora floribunda, cinnamon, laurel, bay laurel, magnolia, burdock, comfrey, Japanese pepper, burnet, peony, ginger, goldenrod, elderberry, sage, mistletoe, narrow-leaved holly, thyme, anemone, clove, satsuma mandarin, tea tree, and basil. Examples of plants that can be used include berry, Houttuynia cordata, Nandina, Chinese laurel, army laurel, white grass, garnet, Dutch amaranth, hops, rosewood, mountain grape, purple jasmine, common mint, bean jasmine, Japanese perilla, eucalyptus, lavender, rose, rosemary, Balsam, Japanese cedar, Gilead balsam, Chinese laurel, Japanese holly, willow, Jingzhou, water chestnut, Japanese angelica, wild jasmine, Cabbage, Cabbage, Cabbage, licorice, and St. John's wort.

[0078] The total content of the optional components relative to the total mass of the cleaning solution is preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, by mass, and may be 0 ppm.

[0079] <<pH>> The cleaning solution preferably has a pH of 4 to 10 at 25°C, more preferably 5 to 9, and even more preferably 6 to 8. When the pH is within the above range, the solution stability can be maintained well. The pH is measured at 25°C using a pH meter (for example, "HM-30G" (product name) manufactured by DKK-TOA Corporation).

[0080] <<Viscosity>> The viscosity of the cleaning liquid at 25°C is preferably 10 mPa·s or less. When the viscosity of the cleaning liquid is equal to or less than the above upper limit, the cleaning liquid can easily come into contact with the entire textile product. In this specification, viscosity refers to a value measured at 25°C using a Brookfield type viscometer.

[0081] [Method for Producing Cleaning Solution] The cleaning solution of this embodiment can be obtained by dispersing component (A), component (B), and optional components, as necessary, in water so that the concentration of component (A) is a predetermined concentration. Alternatively, a cleaning composition containing component (A) and component (B) and having a higher concentration of component (A) than the concentration in the cleaning solution can be prepared, and this cleaning composition can be diluted 200 to 3000 times to produce a cleaning solution having a predetermined concentration of component (A). From the viewpoint of practicality, it is preferable to prepare the cleaning solution by diluting the above-mentioned cleaning composition with water. The cleaning composition may be a liquid cleaning composition or a powder cleaning composition.

[0082] The content of component (A) in the detergent composition is preferably 3 to 20 mass%, more preferably 5 to 15 mass%, even more preferably 5 to 12 mass%, and particularly preferably 5 to 10 mass%, relative to the total mass of the detergent composition. When the content of component (A) is equal to or greater than the above-mentioned lower limit, detergency can be further enhanced. When the content of component (A) is equal to or less than the above-mentioned upper limit, foaming of a cleaning liquid obtained by dissolving the detergent composition in water can be further reduced, thereby further improving rinsing performance.

[0083] The content of component (B) in the detergent composition is preferably 1 to 15 mass%, more preferably 2 to 10 mass%, and even more preferably 3 to 5 mass%, based on the total mass of the detergent composition. When the content of component (B) is equal to or greater than the above-mentioned lower limit, the anti-soil redeposition properties can be further improved. In addition, when the content of component (B) is equal to or greater than the above-mentioned lower limit, the detergency can be further improved. When the content of component (B) is equal to or less than the above-mentioned upper limit, the liquid stability can be further improved.

[0084] The content of water in the detergent composition is not particularly limited, but is preferably 30 to 95 mass%, more preferably 50 to 90 mass%, and even more preferably 70 to 85 mass%, relative to the total mass of the detergent composition. The content of optional components in the detergent composition is preferably 20 mass% or less, more preferably 10 mass% or less, and may be 0 mass%, relative to the total mass of the detergent composition. The total content of each component in the detergent composition does not exceed 100 mass%.

[0085] [Washing method] The washing method of the present invention is a washing method that does not require a rinsing step after washing textile products with the above-mentioned cleaning solution. Since the washing method of the present invention does not require a rinsing step, it reduces the environmental burden and can wash textile products in a short time. In addition, since the washing method of the present invention does not require a rinsing step, it is possible to maintain the fragrance and antibacterial effect attached to the textile products and reduce damage to the textile products.

[0086] The washing method of this embodiment is the same as a normal washing method except that it does not require a rinsing step. For example, the washing method of this embodiment has a washing step and a spin-drying step. An example of the washing method of this embodiment is a method of washing textile products using a washing machine. In addition, the washing method of this embodiment also includes hand washing in a sink and washing outdoors by placing textile products in a bag or the like and rubbing them.

[0087] The washing step is a step of bringing the washing liquid of this embodiment into contact with the textile product to wash the textile product. In the washing step, the washing liquid may be sprinkled onto the textile product, or the textile product may be immersed in the washing liquid. Since this increases the contact efficiency and the cleaning effect, the washing step preferably includes an operation of immersing the textile product in the washing liquid (immersion operation). The washing step may include only the immersion operation, or may include a dropping operation and a stirring operation in addition to the immersion operation. The dropping operation is an operation of dropping the washing liquid of this embodiment onto the textile product. The amount of washing liquid to be dropped is determined appropriately depending on the type and amount of the textile product.

[0088] When the washing step includes a immersion operation, the liquor ratio in the immersion operation, expressed as [mass of washing liquid] / [mass of textile product], is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more. When the liquor ratio is equal to or greater than the above lower limit, the contact efficiency between the textile product and the washing liquid can be further increased. Therefore, the washing effect can be further improved. The upper limit of the liquor ratio is not particularly limited, but is, for example, 50. The stirring operation is performed by stirring the washing liquid in which the items to be washed are immersed, thereby applying shear force to the items to be washed. The stirring operation is performed, for example, by rotating or turning the washing tub of the washing machine. The rotation speed and rotation time of the washing tub in the stirring operation are determined appropriately depending on the type and amount of textile products.

[0089] In the washing step, the time (contact time) for which the washing liquid is brought into contact with the textile product is preferably 3 minutes or more, more preferably 5 minutes or more, and more preferably 10 minutes or more. When the contact time is equal to or greater than the above-mentioned lower limit, the washing effect can be further improved. There is no particular upper limit to the contact time, 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. In this specification, "contact time" refers to the time from when the washing liquid is brought into contact with the textile product until the textile product is removed from the washing liquid, or the time until the spin-drying step described below is started.

[0090] The temperature of the cleaning liquid in the cleaning step is preferably 10 to 90°C, more preferably 20 to 70°C. When the temperature of the cleaning liquid in the cleaning step is equal to or higher than the above lower limit, the cleaning effect can be further improved. When the temperature of the cleaning liquid in the cleaning step is equal to or lower than the above upper limit, deterioration of the textile product can be suppressed.

[0091] In this specification, "textile products" include, for example, clothing, dishcloths, towels, handkerchiefs, sheets, curtains, pillowcases, toilet mats, etc. The material of the textile products is not particularly limited, and examples include natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, and blends, woven products, or knitted products of these fibers. Examples of natural fibers include cotton, wool, and hemp. Examples of synthetic fibers include polyester, nylon, and acrylic. Examples of semi-synthetic fibers include acetate. Examples of regenerated fibers include rayon, Tencel, and Polynosic.

[0092] Examples of washing machines include twin-tub washing machines, fully automatic washing machines, washing machines with automatic detergent dispensing functions, commercial washing machines, etc. Examples of fully automatic washing machines include washing machines with vertical washing tubs, drum washing machines, drum washing machines with dryers, etc. As washing machines, twin-tub washing machines and washing machines with vertical washing tubs are preferred because they make it easier to immerse textile products in the cleaning solution.

[0093] In the washing step, it is preferable to apply a mechanical force such as stirring to the textile product. Applying a mechanical force to the textile product can further enhance the washing effect.

[0094] In the washing step, the textile product may be contacted with the component (A) and then with the component (B), or the textile product may be contacted with the component (B) and then with the component (A), or the textile product may be contacted with the components (A) and (B) simultaneously. In order to further improve the washing efficiency, it is preferable to contact the textile product with the components (A) and (B) simultaneously in the washing step.

[0095] In this specification, the "washing step" refers to the period from when the textile product is brought into contact with the washing liquid until the spin-drying step (i.e., the amount of washing liquid in contact with the textile product becomes less than a predetermined amount) or the start of the rinsing step (described later) (i.e., the concentration of component (A) in the washing liquid becomes less than a predetermined concentration). If the washing method of this embodiment does not have a spin-drying step, the washing step refers to the period up to when the textile product is in contact with the washing liquid at a liquor ratio of 0.1 or more.

[0096] The washing method of this embodiment does not require a rinsing step after the washing step. However, the washing method of this embodiment may include a rinsing step. The rinsing step is a step of contacting a textile product with a rinsing liquid to reduce the amount of component (A) adhering to the textile product. Here, the "rinsing liquid" refers to an aqueous liquid having a concentration of component (A) less than 30 ppm. The concentration of component (B) in the rinsing liquid is preferably less than 10 ppm. When the washing method of this embodiment includes a rinsing step, for example, a method of adding water to the washing liquid in which the textile product is immersed to prepare a rinsing liquid, contacting the textile product with the rinsing liquid, and applying mechanical force such as stirring to the textile product can be mentioned. Another example of a rinsing method is a method of separating the washing liquid from the textile product, contacting the separated textile product with water, and applying mechanical force such as stirring to the textile product. Examples of a method of separating the washing liquid from the textile product include a method of draining the washing liquid from the washing tub and a method of removing the textile product from the washing liquid. The washing method of the present embodiment may include a rinsing step, but it is preferable not to include a rinsing step in terms of resource conservation, energy conservation, reduction of environmental load, and the like.

[0097] The dehydration step is a step of removing moisture adhering to textile products. The washing method of this embodiment includes the dehydration step, which can improve the drying efficiency of textile products. Therefore, the washing method of this embodiment preferably includes the dehydration step. Examples of the dehydration method include a method of applying centrifugal force to textile products that have come into contact with the cleaning liquid, and a method of squeezing the textile products to remove the cleaning liquid. The liquor ratio after dehydration is preferably less than 1, more preferably 0.7 or less, and even more preferably 0.5 or less.

[0098] The washing method of this embodiment may include other steps in addition to the washing step, rinsing step, and spin-drying step. Examples of such other steps include a draining step and a drying step. The draining step is a step of discharging the cleaning liquid that has been in contact with the textile product from the washing tub of the washing machine. By including the draining step, the cleaning liquid adhering to the textile product can be removed. The draining step refers to the period from the start of draining the cleaning liquid to the completion of draining the cleaning liquid. The drying step is a step of heating and drying the textile product after the spin-drying step. By including the drying step, moisture adhering to the textile product can be more reliably removed. The drying step may be performed inside the washing machine, or the textile product may be removed from the washing machine and air-dried, or may be performed in a bathroom with a dryer or outdoors.

[0099] As described above, the washing method of the present invention washes textile products with a cleaning solution containing components (A) and (B) and having a concentration of component (A) of 30 to 200 ppm, resulting in less foaming during washing and good rinsing properties, and sufficient detergency can be achieved even when the rinsing step is simplified. In addition, the washing method of the present invention has excellent anti-redeposition properties. Therefore, the washing method of the present invention can omit the rinsing step that is essential in conventional washing.

[0100] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following descriptions. The raw materials and measurement and evaluation methods used in each example and comparative example are as follows.

[0101] [Raw Materials Used] <<Component (A)>> <Component (A1)> LMAO: Polyoxyethylene alkyl ether (manufactured by Lion Chemical Co., Ltd., trade name "LMAO-90"; in formula (a1), R １ is a linear alkyl group having 12 carbon atoms (C12) and a linear alkyl group having 14 carbon atoms (C14) (mass ratio of C12:C14=75:25), -X- is -O-, and R １ The carbon atom in R is a primary carbon atom, ２is a hydrogen atom, m is 15, and n is 0. AE(7EO): Polyoxyethylene alkyl ether (7EO), a compound in which 7 moles of ethylene oxide are added to a natural alcohol. １ is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, -X- is -O-, R ２ is a hydrogen atom, m=7, and n=0. AE(6EO): Polyoxyethylene alkyl ether (6EO), a compound in which 6 moles of ethylene oxide are added to a natural alcohol. １ is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, -X- is -O-, R ２ is a hydrogen atom, m=6, and n=0. MEE: fatty acid methyl ester ethoxylate (manufactured by Lion Chemical Co., Ltd., trade name "CEAO-90", fatty acid carbon number 12 to 14, average number of EO added moles 15), a compound in which R １ is a linear alkyl group having 11 carbon atoms and a linear alkyl group having 13 carbon atoms, -X- is -COO-, and X is bonded to R １ is a secondary carbon atom, and R ２ is a methyl group, m = 15, and n = 0. EP nonionic surfactant: a nonionic surfactant obtained by block-addition of 8 moles of ethylene oxide, 2 moles of propylene oxide, and 8 moles of ethylene oxide to a natural alcohol (mass ratio of 12 carbon atoms alcohol / 14 carbon atoms alcohol = 7 / 3). １ is an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, -X- is -O-, R ２ is a hydrogen atom, m=8, n=2, and m'=8 (m' represents the average number of repeating EOs different from m). Softanol: A compound in which 12 moles of ethylene oxide are added to 1 mole of a secondary alcohol. In formula (a1), R １ is an alkyl group having 12 to 14 carbon atoms, R ２ is a hydrogen atom, -X- is -O-, and X is bonded to R １ A compound in which the carbon atom is a secondary carbon atom, m is 12, and n is 0.

[0102] <Component (A2)> LAS: linear alkylbenzenesulfonate sodium, trade name "Lipon (registered trademark) LS-250", manufactured by Lion Corporation. AES: polyoxyethylene alkyl ether sulfate (polyoxyethylene alkyl ether sulfate ester salt. A compound in which the alkyl group is a linear alkyl group having 12 or 14 carbon atoms, the average number of moles of EO added is 2, and the sulfate salt is a sodium ion. Manufactured by PT. Kao Indonesia Chemicals, trade name "EMAL 270"). AEPS: monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate ester. IOS: salt of internal olefin sulfonic acid, a compound synthesized by the method described in Example 7 of JP 2001-247534 A.

[0103] <<Component (B)>> <Component (B1)> PEI (10EO): alkoxylated polyalkyleneimine, an ethylene oxide adduct of polyethyleneimine obtained in Production Example 1 below (number of active hydrogen atoms in one polyethyleneimine molecule: 10, average number of moles of ethylene oxide added per active hydrogen atom: 10). PEI (20EO): alkoxylated polyalkyleneimine, an ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20", number of active hydrogen atoms in one polyethyleneimine molecule: 20, average number of moles of ethylene oxide added per active hydrogen atom: 20, mass average molecular weight: 14,500). PEI (30EO): alkoxylated polyalkyleneimine, an ethylene oxide adduct of polyethyleneimine obtained in Production Example 2 below (number of active hydrogen atoms in one molecule of polyethyleneimine: 30, average number of moles of ethylene oxide added per active hydrogen atom: 30).

[0104] <Component (B2)> CP7: sodium salt of a copolymer of acrylic acid and maleic acid (molar ratio of acrylic acid to maleic acid 60:40), manufactured by BASF, trade name "Sokalan CP7", mass average molecular weight 50,000. CP9: sodium salt of a copolymer of a hydrocarbon having 4 to 12 carbon atoms and maleic acid, manufactured by BASF, trade name "Sokalan CP9", mass average molecular weight 12,000. PA30CL: polyacrylic acid, manufactured by BASF, trade name "Sokalan PA30CL", mass average molecular weight 8,000.

[0105] <Component (B3)> Daicel CMC1260: Carboxymethyl cellulose, manufactured by Daicel Miraize Co., Ltd., trade name "Daicel CMC1260". Daicel SP500: Hydroxyethyl cellulose, manufactured by Daicel Miraize Co., Ltd., trade name "HEC Daicel SP500".

[0106] <Optional Ingredients> - Palm fatty acid: NOF Corporation, trade name "Palm Fatty Acid". - POE-modified silicone: Polyether-modified silicone, Dow Corning Toray Co., Ltd., trade name "CF1188N". - Silicone emulsion: Shin-Etsu Chemical Co., Ltd., trade name "KM-90". - Ethanol: Japan Alcohol Sales Co., Ltd., trade name "Specific 95% Synthetic Alcohol". - Solfit: 3-methoxy-3-methyl-1-butanol, Kuraray Co., Ltd., trade name "Solfit (registered trademark)". - Sodium benzoate: Sodium benzoate, Toagosei Co., Ltd. - Citric acid: Chelating agent, Lion Specialty Chemicals Co., Ltd., trade name "Liquid Citric Acid". - Fragrance: Fragrance composition A described in Tables 11 to 18 of JP 2002-146399 A. BHT: dibutylhydroxytoluene, manufactured by Sumitomo Chemical Co., Ltd., trade name "SUMILZER (registered trademark) BHT-R". Dye: Acid Red 138, manufactured by Nippon Kayaku Co., Ltd., trade name "Kayanol (registered trademark) Milling". NaOH: sodium hydroxide, manufactured by Toagosei Co., Ltd. pH adjuster: sulfuric acid, sodium hydroxide, both manufactured by Toagosei Co., Ltd. <Water> Water: purified water.

[0107] Preparation Example 1 Preparation of Ethylene Oxide Adduct of Polyethyleneimine (10EO) An autoclave containing polyethyleneimine (manufactured by BASF under the trade name "Lupasol FG") and water was degassed under vacuum and then purged with nitrogen. While the autoclave was heated, 10 moles of ethylene oxide per mole of nitrogen atom was added to the autoclave to ethoxylate the mixture, thereby obtaining an ethylene oxide adduct of polyethyleneimine.

[0108] Preparation Example 2 Preparation of Ethylene Oxide Adduct of Polyethyleneimine (30EO) An autoclave containing polyethyleneimine (manufactured by BASF under the trade name "Lupasol FG") and water was degassed under vacuum and then purged with nitrogen. While heating the autoclave, 30 moles of ethylene oxide per mole of nitrogen atom was added to carry out ethoxylation, thereby obtaining an ethylene oxide adduct of polyethyleneimine.

[0109] [Measurement and Evaluation Methods] <pH Measurement> 100 mL of each cleaning composition (liquid cleaning agent) was prepared, and the pH of each liquid cleaning agent was measured at 25°C using a pH meter (portable pH / ORP / ION meter D-73, manufactured by HORIBA, Ltd.).

[0110] <Evaluation of Rinseability (Foam Suppression)> A cleaning solution was prepared by dissolving 0.5 g of each liquid detergent in 600 mL of tap water adjusted to 25°C. 20 mL of each cleaning solution was placed in an Epton tube (volume 100 mL, body diameter 25 mm), and the Epton tube was manually shaken 20 times at 1 stroke / second. One minute after the end of shaking, the foam height (height from the boundary between the foam and the cleaning solution to the top surface of the foam) was read, and the rinsing ability was evaluated according to the following evaluation criteria. In the evaluation criteria below, S, A, and B were rated as passing. <Evaluation Criteria> S: Foam height less than 30 mm. A: Foam height 30 mm or more but less than 70 mm. B: Foam height 70 mm or more but less than 120 mm. C: Foam height 120 mm or more but less than 150 mm. D: Foam height 150 mm or more.

[0111] <Evaluation of Detergency> Detergency was evaluated without a rinsing step. A wet, artificially soiled 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, 0.5% carbon black) cut into a 5 cm x 5 cm square was used as the soiled cloth. A Terg-O-tometer (manufactured by United States Testing Co.) was used as the cleaning tester. A cleaning solution prepared by adding 750 μL (0.75 mL) of the liquid detergent of each example to 900 mL of water and stirring for 30 seconds was used. 900 mL of the cleaning solution, 10 of the soiled fabrics, and the washed knitted fabric were placed in the cleaning tester, and the bath ratio (washing water / total mass of fabrics to be washed) was adjusted to 20 times. Then, the fabrics were washed for 10 minutes at 120 rpm and 15°C. The fabrics were then transferred to a two-tub washing machine (Toshiba Corporation, product name "VH-30S"), dehydrated for 1 minute, and air-dried. The reflectance of the soiled fabrics before washing, the soiled fabrics after washing, and the unsoiled fabric (here, "unsoiled fabric" refers to the original white fabric (raw fabric) without any soiling) was measured using a color difference meter (Nippon Denshoku Co., Ltd., product name "SE200 Model"), and the cleaning rate (%) was calculated using the following formula (i): Cleaning rate (%) = (K / S of soiled cloth before cleaning - K / S of soiled cloth after cleaning) / (K / S of soiled cloth before cleaning - K / S of unsoiled cloth) x 100 (i) [In formula (i), K / S is (1 - R / 100) / (2R / 100), and R represents the reflectance (%) of the soiled cloth before cleaning, the soiled cloth after cleaning, or the unsoiled cloth. K represents the absorption coefficient, S represents the scattering coefficient, and R represents the absolute reflectance.] The average cleaning rate of 10 soiled cloths was calculated. The average value obtained was evaluated according to the following evaluation criteria. In the evaluation criteria below, A and B were rated as acceptable. Evaluation criteria A: Cleaning rate of 50% or more. B: Cleaning rate of 45% or more but less than 50%. C: Cleaning rate of 40% or more but less than 45%. D: Cleaning rate less than 40%.

[0112] <Evaluation of Anti-Resoiling Properties> Using each detergent composition, a laundry treatment was performed in which the washing step and drying step shown below were repeated three times in this order. The following cotton cloth, wet-artificially soiled cloth, and skin shirt were used as the items to be washed (textile products). Cotton cloth: Five 5 cm x 5 cm pieces of cotton knit (manufactured by Tanigashira Shoten) were used as cloths for evaluating resoiling. Wet-artificially soiled cloth: 20 pieces of soiled cloth (manufactured by the Laundry Science Association) (cloths with soiling composed of 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 (by mass)). Skin shirt: A BVD skin shirt (LL size, manufactured by Fujibo Holdings, Inc.) cut into small pieces (approximately 3 cm x 3 cm). (1) Washing Step: 900 mL of 3° DH hard water at 25°C was placed in a Terg-o-tometer (manufactured by United States Testing Co.), 750 μL of the detergent composition was added thereto, and then the items to be washed were placed therein. Subsequently, 3° DH hard water was added to adjust the bath ratio to 30, and the items were washed at 120 rpm and 25°C for 10 minutes. (2) Drying Step: The washed items were dehydrated for 1 minute, and then only the re-soiling test cloth (cotton cloth) was removed, sandwiched between filter paper, and dried with an iron. The reflectance (Z value) of the re-soiling test cloth before and after the washing treatment was measured using a reflectometer (manufactured by Nippon Denshoku Industries Co., Ltd., product name: "Spectroscopic Color Difference Meter SE2000"), and ΔZ was calculated using the following formula (ii): ΔZ = (Z value before washing) - (Z value after washing) (ii) The ΔZ of five cotton cloths used to judge re-soiling was averaged, and the ability of the detergent composition to prevent re-soiling of cotton cloth was evaluated based on the following evaluation criteria. In the following evaluation criteria, A and B were rated as passing. Evaluation Criteria A: ΔZ is less than 4. B: ΔZ is 4 or more and less than 4.8. C: ΔZ is 4.8 or more and less than 5.5. D: ΔZ is 5.5 or more.

[0113] [Examples 1 to 29, Comparative Examples 1 to 4] The amounts of each component were adjusted as shown in Tables 1 to 4, and the liquid detergents of Examples 1 to 29 and Comparative Examples 1 to 4 were prepared according to the following procedure. Component (A) and component (B) were mixed with water until homogeneous, and then optional components were added and thoroughly stirred to obtain liquid detergents. In Tables 1 to 4, the amount of each component (mass %) is the percentage relative to the total mass of the liquid detergent, and is expressed as a pure content unless otherwise specified. A "-" in the table indicates that the component is not contained. "Appropriate amount" means that a pH adjuster is added so that the pH of the liquid detergent at 25°C is the value shown in Tables 1 to 4. "Balance" means that water is added so that the total mass (mass %) of all components contained in each liquid detergent is 100 mass %. In other words, the amount of water is the remainder after subtracting the total mass (pure content) of all components other than water from the total mass of the liquid detergent. The liquid detergents of each example were evaluated for rinsability, detergency, and anti-resoiling properties by the methods described above. The results are shown in the table.

[0114]

[0115]

[0116]

[0117]

[0118] As shown in Tables 1 to 4, Examples 1 to 29, in which the present invention was applied, were excellent in rinsing properties, detergency, and anti-redeposition properties. In contrast, Comparative Example 1, which did not contain component (A), was inferior in detergency and anti-redeposition properties. Comparative Example 2, in which the concentration of component (A) in the cleaning solution was less than 30 ppm, was inferior in detergency and anti-redeposition properties. Comparative Example 3, in which the concentration of component (A) in the cleaning solution was more than 200 ppm, was inferior in rinsing properties. Comparative Example 4, which did not contain component (B), was inferior in detergency and anti-redeposition properties.

[0119] These results demonstrate that the present invention provides excellent rinsing properties with little foaming during washing, and can provide sufficient detergency even when the rinsing step is simplified.

Claims

DEPCT671. A washing method which is a washing method for textile products in which the washing step involves contact with the textile product with a detergent and does not require a post-washing rinsing step. The detergent consists of component (A): a surfactant and component (B): an organic polymer dispersant. The concentration of component (A) is 30-200 ppm relative to the total mass of the detergent.

2. A washing method according to Reputation 1 where the concentration of component (A) in the detergent is 30-150 ppm relative to the total mass of the detergent.

3. A washing method specified in Reputation 1 or 2 where the mass ratio represented by component (B) / component (A) in the detergent is 0.01-10.

4. A washing method according to Reputation 1 or 2 where component (B) is an alkoxylated polyalkyleneimine, a polyacrylic acid-based polymer, and a carboxymethylcellulose-based polymer;