Washing Instructions

Abstract

To provide a laundry method materializing little foaming in washing and preferable rinsing property, enabling sufficient washing force to be exhibited even when a rinsing step is simplified, and enabling excellent flexibility to be imparted to a textile product.SOLUTION: A laundry method of a fiber product is provided, having a washing step of bringing washing fluid into contact with the fiber product, and requiring no rinsing step after the washing step, the washing fluid comprises a component (A): a surfactant except for components (B) and (C), a component (B): a fatty acid having C12-C18 or a salt thereof, and a component (C): at least one kind of a compound selected from a group comprised of an amine compound which has in a molecule, 1-3 hydrocarbon groups having C10-26 and which may be divided by one or more kinds of groups selected from an ester group, an ether group and an amide group, a salt of the amine compound or a quaternary compound thereof, and a modified silicone, wherein density of the component (A) is 30-150 ppm with respect to total mass of the washing fluid.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a washing method. [Background technology]

[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] With general cleaning solutions, a lot of foaming during cleaning leads to a good feeling when used, and the disappearance of foam during rinsing is an indication that rinsing is complete. 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 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 dirt adhering to textile products from being removed by the cleaning solution and adhering to other textile products (anti-redeposition property) and the function of suppressing foaming of the cleaning solution and shortening the rinsing time (foam suppression property, rinsing property) are improved. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-050839 Summary of the Invention [Problem to be solved by the invention]

[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] The present inventors have found the following problems while studying methods for further simplifying the rinsing step. For example, in a washing machine that is set to automatically start water injection and move on to the rinse cycle when it detects foam after spin-drying, if it detects foam even after the rinse cycle, it will automatically extend the rinse cycle. Therefore, in order to simplify or eliminate the rinse cycle, it is necessary to reduce the amount of foam. Furthermore, if the number of rinses or the amount of rinse water is reduced, the dirt that was once removed from the washed item (textile product) may adhere to the washed item again, 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 is reduced.

[0007] Furthermore, in conventional washing methods, the detergent composition adhering to the textile product is washed away in the rinsing step, and then a softener is added to the textile product to impart softness to the textile product.

[0008] Therefore, an object of the present invention is to provide a washing method that produces little foam during washing, has good rinsing properties, and can exert sufficient detergency even when the rinsing step is simplified, and can also impart excellent softness. [Means for solving the problem]

[0009] The present invention has the following aspects. [1] A method for washing textile products, comprising a washing step of contacting a washing liquid with textile products, and not requiring a rinsing step after the washing step, The cleaning solution comprises: component (A): a surfactant other than the following component (B) and the following component (C); (B) component: a fatty acid having 12 to 18 carbon atoms or a salt thereof, Component (C): at least one selected from the following component (C1) and the following component (C2), The washing method, wherein the concentration of the component (A) is 30 to 150 ppm relative to the total mass of the washing liquid. Component (C1): At least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be interrupted by one or more groups selected from the group consisting of ester groups, ether groups, and amide groups, salts thereof, and quaternized products thereof. (C2) Ingredient: Modified silicone. [2] The washing method according to [1], wherein the washing liquid further contains component (D): a polymeric organic dispersant. [3] The washing method according to [1] or [2], wherein the concentration of the component (C) is 10 to 100 ppm relative to the total mass of the washing liquid. [4] The washing method according to any one of [1] to [3], wherein the mass ratio of the component (C) to the component (A) in the washing liquid is 0.06 to 3.3. [Effects of the Invention]

[0010] According to the washing method of the present invention, there is little foaming during washing and rinsing is good, and even when the rinsing step is simplified, sufficient detergency can be exerted and excellent softness can be imparted. DETAILED DESCRIPTION OF THE INVENTION

[0011] [Cleaning solution] The washing liquid used in the washing method of the present invention is an aqueous liquid containing components (A), (B), and (C). The aqueous liquid conceptually includes at least one of an aqueous solution and an aqueous dispersion.

[0012] Component (A) Component (A) is a surfactant excluding components (B) and (C) described below. 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 the component (A) include nonionic surfactants, non-soap anionic surfactants, cationic surfactants other than the component (C), amphoteric surfactants, and semi-polar surfactants. Component (A) preferably contains a nonionic surfactant because it provides superior rinsing properties. When component (A) contains a nonionic surfactant, the content of the nonionic surfactant is preferably 50 mass% or more relative to the total mass of component (A). It is more preferable to use a nonionic surfactant in combination with a non-soap anionic surfactant as component (A) because this further enhances detergency.

[0013] <Component (A1)> The component (A1) is a nonionic surfactant. The component (A1) may be any nonionic surfactant that has been conventionally used in detergent compositions for clothing and the like. 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, the term "higher" refers to organic compounds having 8 to 26 carbon atoms. As the component (A1), a polyoxyalkylene-type nonionic surfactant is preferred because of its excellent detergency. The component (A1) may be used alone or in combination of two or more types.

[0014] An example of the polyoxyalkylene nonionic surfactant is a compound represented by the following formula (a1) (hereinafter also referred to as "compound (a1)"). R 1 -X-[(EO) m / (PO) n ]-R 2 (a1) In formula (a1), R 1is 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 repetitions of EO and is a number from 3 to 20; and n represents the average number of repetitions of PO and is a number from 0 to 6. [(EO) m / (PO) n The symbol "-" indicates that the EO and PO chains may be random or block chains. The average repeat number can be measured by gas chromatography or the like.

[0015] In formula (a1), R 1 The hydrocarbon group R may be linear or branched. It may have an unsaturated bond. 1 The number of carbon atoms in R is 6 to 22, preferably 8 to 20, and more preferably 10 to 18. 1 Examples of the fatty acids include those derived from raw materials such as primary or secondary higher alcohols, higher fatty acids, and higher fatty acid amides. In the formula (a1), examples of -X- include -O-, -COO-, -CONH-, etc. -X- is preferably -O- or -COO- because it has an excellent effect of improving detergency. R in formula (a1) 2 When is an alkyl group, R 2 The number of carbon atoms in R is 1 to 6, preferably 1 to 3. 2 When is an alkenyl group, R 2 The number of carbon atoms in R is 2 to 6, preferably 2 to 3. 2 is preferably a hydrogen atom.

[0016] In formula (a1), m represents the average repeat number of EO (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 cleansing power against sebum can be enhanced.

[0017] In formula (a1), n ​​represents the average number of repeating PO units (i.e., the average number of moles of propylene oxide added) and is a number of 0 to 6, preferably 0 to 3. When n is equal to or less than the above upper limit, the liquid stability at high temperatures (for example, 50°C) can be further improved. When n is 1 or more, that is, when compound (a1) has EO and PO, the method of adding EO and PO is not particularly limited, and may be, for example, a random addition method or a block addition method. Examples of the block addition method 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, then adding PO, and then adding EO.

[0018] The distribution of the number of moles of EO or PO added is not particularly limited. The mole distribution of added EO or PO tends to vary depending on the reaction method used to produce nonionic surfactants. For example, when EO or PO is added to a hydrophobic raw material using an alkaline catalyst such as sodium hydroxide or potassium hydroxide, the mole distribution of added EO or PO tends to be relatively broad. Al described in Japanese Patent Publication No. 6-15038 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 metal ions such as EO or PO have been added, the mole number distribution of EO or PO added tends to be a relatively narrow distribution.

[0019] 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 2 is an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms (fatty acid alkyl(alkenyl) esters) are particularly preferred. When -X- is -O-, R 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. 2is 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.

[0020] <(A2) component> Component (A2) is a non-soap anionic surfactant. "Non-soap anionic surfactant" refers to an anionic surfactant excluding higher fatty acids or their salts (so-called soaps). "Higher fatty acids" refer to saturated or unsaturated fatty acids having 8 to 24 carbon atoms. In other words, 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, and glycerin fatty acid ester monophosphate ester or its salt. 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; and alkanolamine salts such as monoethanolamine salts and diethanolamine salts. The component (A2) may be used alone or in combination of two or more types.

[0021] As the component (A2), one or more selected from the group consisting of linear alkylbenzenesulfonic acid or a salt thereof, α-olefinsulfonic acid or a salt thereof, internal olefinsulfonic acid or a salt thereof, and polyoxyalkylene alkenyl ether sulfate or a salt thereof are preferred, in terms of their excellent effect of improving rinsing performance.

[0022] The linear alkylbenzenesulfonic acid or salt thereof is preferably one in which the linear alkyl group has 8 to 16 carbon atoms, and particularly preferably one in which the linear alkyl group has 10 to 14 carbon atoms. The α-olefin sulfonate and internal olefin sulfonate preferably have 10 to 20 carbon atoms. The polyoxyalkylene alkenyl ether sulfate or a salt thereof is preferably an alkenyl ether sulfate having a linear or branched alkenyl group having 10 to 20 carbon atoms and having an average of 1 to 10 moles of ethylene oxide added thereto (i.e., a polyoxyethylene alkenyl ether sulfate). The component (A2) may be produced by a conventional method, or a commercially available product may be used.

[0023] Examples of component (A) other than those mentioned above include cationic surfactants, amphoteric surfactants, and semi-polar surfactants excluding component (C) described below. Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salts. 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. Preferred alkyl sulfate ions have an alkyl group having 1 to 3 carbon atoms, such as methyl sulfate ions and ethyl sulfate ions. Examples of amphoteric surfactants include alkylcarboxybetaine, alkylsulfobetaine, alkylhydroxysulfobetaine, alkylamidobetaine, and imidazolinium betaine. Examples of the semi-polar surfactant include amine oxide surfactants such as lauryl dimethylamine oxide and lauric acid amide propyl dimethylamine oxide. These may be produced by conventional methods, or commercially available products may be used.

[0024] The concentration of component (A) in the cleaning solution is 30 to 150 ppm by mass (relative to the total mass of the cleaning solution), preferably 40 to 140 ppm, and more preferably 50 to 120 ppm. When the concentration of component (A) is at least the lower limit, cleaning power can be further enhanced. When the concentration of component (A) is at most the upper limit, foaming can be suppressed and rinsing performance can be further enhanced.

[0025] When the cleaning solution contains the component (A1), the concentration of the component (A1) in the cleaning solution is preferably 15 to 150 ppm by mass, more preferably 20 to 140 ppm, and even more preferably 25 to 120 ppm. When the concentration of the component (A1) is at least the above lower limit, detergency can be further improved. When the concentration of the component (A1) is at most the above upper limit, rinsing performance can be further improved.

[0026] When the cleaning solution contains the (A2) component, the concentration of the (A2) component in the cleaning solution is preferably 5 to 75 ppm by mass, more preferably 10 to 70 ppm, and even more preferably 15 to 60 ppm. When the concentration of the (A2) component is at least the above lower limit, the anti-soil redeposition properties can be further improved. When the concentration of the (A2) component is at most the above upper limit, the rinsing properties can be further improved. In addition, when the concentration of the (A2) component is at most the above upper limit, the detergency can be further improved. The components (A1) and (A2) may be used either alone or in combination.

[0027] The mass ratio of component (A1) to component (A) in the cleaning liquid (hereinafter also referred to as "(A1) / (A) ratio") is preferably from 0.5 to 1, more preferably from 0.6 to 1, and even more preferably from 0.8 to 1. When the (A1) / (A) ratio is at least the above lower limit, the cleaning power can be further improved.

[0028] ≪(B) Component≫ Component (B) is a fatty acid having 12 to 18 carbon atoms or a salt thereof. Component (B) is a so-called soap. By including component (B), the cleaning liquid of this embodiment can further improve rinsing properties and softness. Examples of component (B) include simple 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. The component (B) may be used alone or in appropriate combination of two or more types.

[0029] As a combination of components (B), a combination of a fatty acid having 12 carbon atoms in the hydrocarbon group and a fatty acid having 14 to 18 carbon atoms in the hydrocarbon group is preferred, and a combination of a fatty acid having 12 carbon atoms and two or more fatty acids having 14 to 18 carbon atoms in the hydrocarbon group is more preferred. The ratio of the mass of fatty acids having 14 to 18 carbon atoms to the mass of fatty acids having 12 carbon atoms, [fatty acids having 14 to 18 carbon atoms] / [fatty acids 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.

[0030] Examples of salt forms of fatty acids having 12 to 18 carbon atoms include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; and alkanolamine salts such as monoethanolammonium and diethanolammonium. Commercially available products of component (B) include, for example, 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., Ltd.)), etc.

[0031] The concentration of component (B) in the cleaning solution is preferably 1 to 50 ppm by mass (relative to the total mass of the cleaning solution), more preferably 5 to 40 ppm, and even more preferably 10 to 30 ppm. When the concentration of component (B) is equal to or greater than the above-mentioned lower limit, rinsing performance can be further improved. In addition, when the concentration of component (B) is equal to or greater than the above-mentioned lower limit, softness can be further improved. When the concentration of component (B) is equal to or less than the above-mentioned upper limit, solution stability can be further improved.

[0032] The mass ratio of component (B) to component (A) in the cleaning solution (hereinafter also referred to as "(B) / (A) ratio") is preferably 0.006 to 1.0, more preferably 0.03 to 0.5, and even more preferably 0.06 to 0.3. When the (B) / (A) ratio is equal to or greater than the above lower limit, rinsing performance can be further improved. When the (B) / (A) ratio is equal to or less than the above upper limit, solution stability can be further improved.

[0033] ≪(C) Component≫ Component (C) is a compound that functions as a softening base material and is at least one selected from components (C1) and (C2). By containing component (C), the cleaning liquid of this embodiment can impart softness to textile products after washing.

[0034] <(C1) component> The component (C1) is at least one compound selected from the group consisting of amine compounds having 1 to 3 hydrocarbon groups of 10 to 26 carbon atoms in the molecule, their salts, and their quaternized products. The hydrocarbon group of 10 to 26 carbon atoms may be interrupted by one or more groups selected from the group consisting of ester groups, ether groups, and amide groups. The component (C1) is at least one compound selected from the group consisting of amine compounds having one or more hydrocarbon groups of 10 to 26 carbon atoms in the molecule, their neutralized products, and their quaternized products. The component (C1) is a soft base material and functions as a cationic surfactant.

[0035] The hydrocarbon group has a carbon number of 10 to 26, preferably 12 to 22, and more preferably 14 to 18. When the carbon number is 10 or more, flexibility can be further improved. When the carbon number is 26 or less, handleability can be further improved. The hydrocarbon group may be saturated or unsaturated. When the hydrocarbon group is unsaturated, the double bond may be located anywhere. When there is one double bond, the double bond is preferably located at the center or near the center of the hydrocarbon group. The hydrocarbon group may be a chain or may be a hydrocarbon group containing a ring in its structure. The hydrocarbon group is preferably a chain. The chain hydrocarbon group may be a linear or branched chain. The chain hydrocarbon group is preferably an alkyl group or an alkenyl group. An alkyl group is more preferred.

[0036] The hydrocarbon group may be interrupted by one or more groups selected from the group consisting of an ester group (-COO-), an ether group, and an amide group (-NHCO-). That is, the hydrocarbon group may have at least one interrupting group selected from the group consisting of an ester group, an ether group, and an amide group in its carbon chain, and the carbon chain may be interrupted by the interrupting group. It is preferable for the hydrocarbon group to have an interrupting group in view of improving rinsing performance, etc. When the hydrocarbon group has a splitting group, the number of splitting groups that one hydrocarbon group has may be one or two or more. That is, the hydrocarbon group may be split at one location by a splitting group, or at two or more locations. When two or more splitting groups are present, the respective splitting groups may be the same or different. As the splitting group, an ester group is particularly preferred. When a separating group is present in the carbon chain, the carbon atoms of the separating group are counted in the number of carbon atoms of the hydrocarbon group. The hydrocarbon group is usually introduced by using an industrially used unhydrogenated fatty acid derived from beef tallow, a fatty acid obtained by hydrogenating or partially hydrogenating the unsaturated moiety, an unhydrogenated fatty acid or fatty acid ester derived from a plant such as palm or oil palm, or a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating the unsaturated moiety. The amine compound of component (C1) is preferably a secondary amine compound or a tertiary amine compound, and more preferably a tertiary amine compound.

[0037] More specifically, the amine compound of the component (C1) includes the compound represented by the following formula (C1).

[0038] [ka]

[0039] In formula (C1), R 11 ~R 13 are each independently a hydrocarbon group having 10 to 26 carbon atoms, -CH2CH(Y)OCOR 4 (Y is a hydrogen atom or CH3, and R 4 is a hydrocarbon group having 7 to 21 carbon atoms.) -CH2CH(Y)OR 5 (Y is a hydrogen atom or CH3, and R 5 is a hydrocarbon group having 7 to 21 carbon atoms.) or -(CH2) n NHCOR 6 (n is 2 or 3, and R 6 is a hydrocarbon group having 7 to 21 carbon atoms, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, -CH2CH(Y)OH, or -(CH2) n NH2 and R 11 ~R 13 At least one of the groups is a hydrocarbon group having 10 to 26 carbon atoms, -CH2CH(Y)OCOR 4 , -CH2CH(Y)OR 5 or -(CH2) n NHCOR 6 is.

[0040] In formula (C1), R 11 ~R 13 The hydrocarbon group having 10 to 26 carbon atoms preferably has 12 to 22 carbon atoms, more preferably 14 to 18 carbon atoms. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group. -CH2CH(Y)OCOR 4 In R, Y is a hydrogen atom or CH3, and a hydrogen atom is particularly preferred. 4is a hydrocarbon group having 7 to 21 carbon atoms, and R 4 The number of carbon atoms in R is preferably 15 to 19. 4 When there are multiple R 4 may be the same as each other or may be different from each other.

[0041] R 4 The hydrocarbon group is a fatty acid having 8 to 22 carbon atoms (R 4 It is a residue (fatty acid residue) obtained by removing the carboxyl group from a fatty acid (COOH). 4 The fatty acids that form the base of 4 COOH) may be a saturated or unsaturated fatty acid, and may be a straight-chain or branched fatty acid. 4 As the COOH, saturated or unsaturated straight-chain fatty acids are preferred. 4 The saturated / unsaturated ratio (mass ratio) of COOH is preferably from 90 / 10 to 0 / 100, more preferably from 80 / 20 to 0 / 100. R 4 When R is an unsaturated fatty acid residue, it exists in cis and trans forms. 4 The mass ratio of cis isomer / trans isomer in the formula (I) is preferably 40 / 60 to 100 / 0, more preferably 70 / 30 to 90 / 10.

[0042] R 4 Specific examples of COOH include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated beef tallow fatty acid (iodine value 10 to 60), etc. Among these, it is preferable to use a fatty acid composition prepared by combining predetermined amounts of two or more acids selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid so as to satisfy the following conditions (a) to (c): (a) The ratio (mass ratio) of saturated fatty acids to unsaturated fatty acids is 90 / 10 to 0 / 100, and more preferably 80 / 20 to 0 / 100. (b) The cis / trans ratio (mass ratio) is 40 / 60 to 100 / 0, more preferably 70 / 30 to 90 / 10. (c) The fatty acids having 18 carbon atoms are 60% by mass or more, preferably 80% by mass or more, the fatty acids having 20 carbon atoms are less than 2% by mass, and the fatty acids having 21 to 22 carbon atoms are less than 1% by mass.

[0043] -CH2CH(Y)OR 5 In R, Y is a hydrogen atom or CH3, and a hydrogen atom is particularly preferred. 5 is a hydrocarbon group having 7 to 21 carbon atoms, and R 5 The number of carbon atoms in R is preferably 15 to 19. 5 When there are multiple R 5 may be the same as each other or may be different from each other. 5 As for R 4 The same can be mentioned.

[0044] -(CH2) n NHCOR 6 In the formula, n is 2 or 3, and 3 is particularly preferred. 6 is a hydrocarbon group having 7 to 21 carbon atoms, and R 6 The number of carbon atoms in R is preferably 15 to 19. 6 When there are multiple R 6 may be the same as each other or may be different from each other. 6 As for R 4 The same can be mentioned.

[0045] R 11 ~R 13 At least one of the groups is a long-chain hydrocarbon group (a hydrocarbon group having 10 to 26 carbon atoms, -CH2CH(Y)OCOR 4 , -CH2CH(Y)OR 5 or -(CH2) n NHCOR 6 ) and preferably two of them are long-chain hydrocarbon groups. 11 ~R 13When one or two of the groups are long-chain hydrocarbon groups, the remaining two or one of the groups are hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, -CH2CH(Y)OH, or -(CH2) n NH2, an alkyl group having 1 to 4 carbon atoms, -CH2CH(Y)OH, or -(CH2) n Of these, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or an ethyl group, and more preferably a methyl group. Y in -CH2CH(Y)OH is -CH2CH(Y)OCOR 4 Same as Y in -(CH2) n n in NH2 is -(CH2) n NHCOR 6 It is the same as n in

[0046] Preferred examples of the compound represented by formula (C1) include compounds represented by the following formulae (c1-1) to (c1-8).

[0047] [ka]

[0048] In the formula, R 7 and R 8 are each independently a hydrocarbon group having 10 to 26 carbon atoms. 9 and R 10 are each independently a hydrocarbon group having 7 to 21 carbon atoms.

[0049] R 7 and R 8 The hydrocarbon group in R 11 ~R 13 Examples of the hydrocarbon group include those having 10 to 26 carbon atoms. R 9 , R 10 The hydrocarbon group having 7 to 21 carbon atoms in the R 4 In the formula, R 9 When there are multiple R 9may be the same as each other or may be different from each other. The component (C1) may be a salt of an amine compound. The component (C1) may be used alone or in combination of two or more types.

[0050] The salt of an amine compound can be obtained by neutralizing the amine compound with an acid. The acid used to neutralize the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. The neutralization of the amine compound can be carried out by a known method. Quaternized amine compounds can be obtained by reacting an amine compound with a quaternizing agent. Examples of quaternizing agents used for quaternizing amine compounds include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced to the nitrogen atom of the amine compound, forming a salt of a quaternary ammonium ion with a halogen ion or a monoalkyl sulfate ion. The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of an amine compound can be carried out by known methods.

[0051] The component (C1) is preferably at least one selected from the group consisting of compounds represented by the formula (C1), salts thereof, and quaternized products thereof, more preferably at least one selected from the group consisting of the formulae (c1-1) to (c1-8), salts thereof, and quaternized products thereof, and even more preferably at least one selected from the group consisting of the formulae (c1-1) to (c1-6), salts thereof, and quaternized products thereof. The compound represented by formula (C1), its salt and its quaternary derivative may be commercially available or may be produced by a known method.

[0052] For example, the compound represented by formula (c1-2) (hereinafter also referred to as "compound (c1-2)." The same applies to the compounds represented by formulas (c1-3) to (c1-8)) and compound (c1-3) can be synthesized by a condensation reaction between the above-mentioned fatty acid composition or a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is replaced with a fatty acid methyl ester, and methyldiethanolamine. From the viewpoint of improving flexibility, the synthesis is preferably carried out so that the abundance ratio represented by "compound (c1-2) / compound (c1-3)" is 99 / 1 to 50 / 50 by mass. Furthermore, when using quaternized compounds (c1-2) to (c1-3), it is more preferable to use dimethyl sulfate as a quaternizing agent. In this case, from the viewpoint of flexibility, it is preferable to synthesize the compounds so that the abundance ratio represented by "quaternized compound (c1-2) / quaternized compound (c1-3)" is 99 / 1 to 50 / 50 by mass ratio.

[0053] Compounds (c1-4) to (c1-6) can be synthesized by a condensation reaction between the above-mentioned fatty acid composition or fatty acid methyl ester composition and triethanolamine. In this case, from the viewpoint of flexibility, the content ratio of each component relative to the total mass of compounds (c1-4) to (c1-6) is preferably 1 to 60 mass% for compound (c1-4), 5 to 98 mass% for compound (c1-5), and 0.1 to 40 mass% for compound (c1-6), and more preferably 30 to 60 mass% for compound (c1-4), 10 to 55 mass% for compound (c1-5), and 5 to 35 mass% for compound (c1-6). Furthermore, when using quaternized compounds (c1-4) to (c1-6), it is more preferable to use dimethyl sulfate as the quaternizing agent in order to ensure sufficient progress of the quaternization reaction. From the viewpoint of flexibility, the abundance ratios of the quaternized compounds (c1-4) to (c1-6) are preferably 1 to 60% by mass of the quaternized compound (c1-4), 5 to 98% by mass of the quaternized compound (c1-5), and 0.1 to 40% by mass of the quaternized compound (c1-6), and more preferably 30 to 60% by mass of the quaternized compound (c1-4), 10 to 55% by mass of the quaternized compound (c1-5), and 5 to 35% by mass of the quaternized compound (c1-6). Furthermore, when quaternizing compounds (c1-4) to (c1-6), unquaternized esteramine generally remains after the quaternization reaction. In this case, the ratio of "quaternized product / non-quaternized ester amine" is preferably within the range of a mass ratio of 70 / 30 to 99 / 1.

[0054] Compounds (c1-7) to (c1-8) can be synthesized by a condensation reaction of the above fatty acid composition with N-(2-hydroxyethyl)-N-methyl-1,3-propylenediamine, which is synthesized by a known method described in J. Org. Chem., 26, 3409 (1960) from an adduct of N-methylethanolamine and acrylonitrile. In this case, it is preferable to synthesize them so that the abundance ratio represented by "compound (c1-7) / compound (c1-8)" is 99 / 1 to 50 / 50 by mass. Furthermore, when using quaternized compounds (c1-7) to (c1-8), it is preferable to use methyl chloride as a quaternizing agent, and it is preferable to synthesize them so that the abundance ratio represented by "quaternized compound (c1-7) / quaternized compound (c1-8)" is 99 / 1 to 50 / 50 by mass.

[0055] The concentration of component (C1) in the cleaning solution is preferably 10 to 100 ppm by mass (relative to the total mass of the cleaning solution), more preferably 20 to 80 ppm, and even more preferably 30 to 50 ppm. When the concentration of component (C1) is at least the above lower limit, flexibility can be further improved. When the concentration of component (C1) is at most the above upper limit, solution stability can be further improved.

[0056] <(C2) component> The component (C2) is a modified silicone. Examples of component (C2) include amino-modified silicone, amino polyether-modified silicone, amide-modified silicone, amide polyether-modified silicone, alkyl-modified silicone, alkyl polyether-modified silicone, polyether-modified silicone, etc. Among these, from the viewpoint of further improving the flexibility of textile products and further improving the appearance stability of the cleaning liquid, polyether-modified silicone and amino-modified silicone are preferred, and polyether-modified silicone is more preferred. The component (C2) may be used alone or in combination of two or more types.

[0057] The polyether-modified silicone is a compound represented by the following formula (c2-1) (hereinafter also referred to as "compound (c2-1)").

[0058] [ka]

[0059] In formula (c2-1), R 24 R is either a linear or branched alkyl group having 1 to 4 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms, or a hydrogen atom. 23 Y is a linear or branched alkylene group having 1 to 4 carbon atoms or a linear or branched alkenylene group having 2 to 4 carbon atoms. 3 represents a polyoxyalkylene group, p is a number from 10 to 10,000, and q is a number from 1 to 1,000. The order of the structural units to which p and q are attached may be different. The specific gravity of compound (c2-1) is preferably 1.00 to 1.09, more preferably 1.04 to 1.09 at 25° C. The specific gravity is a value measured using a pycnometer at 25° C. in accordance with the specific gravity measurement method in the general testing methods of the Japanese Pharmacopoeia.

[0060] Examples of commercially available products of compound (c2-1) include CF1188N (trade name) manufactured by Dow Corning Toray Co., Ltd., and KF-6011 (specific gravity: 1.06), KF-6012 (specific gravity: 1.03), KF-6015 (specific gravity: 1.00), and KF-6017 (specific gravity: 1.01), all manufactured by Shin-Etsu Chemical Co., Ltd. These compounds (c2-1) may be used alone or in combination of two or more.

[0061] Amino-modified silicone is a compound in which amino-modified groups are introduced into both ends or side chains of a dimethyl silicone skeleton. Commercially available amino-modified silicones can be used, such as those sold by Dow Corning Toray Co., Ltd. under the trade names DOWSIL SF8417 Fluid, DOWSIL BY16-849, DOWSIL BY16-892, and DOWSIL FZ-3785, and those sold by Shin-Etsu Chemical Co., Ltd. under the trade names KF-864, KF-860, KF-880, KF-8004, KF-8002, KF-867, KF-869, and KF-861. These amino-modified silicones may be used alone or in combination of two or more.

[0062] Aminopolyether-modified silicone is a silicone having at least one amino-modified group and a polyether-modified group in its structure. More specifically, it is a silicone compound having at least one amino-modified group selected from a side chain modified by an amino group and an end modified by an amino group, and a side chain modified by a polyether group or an end modified by a polyether group in its structure. Among these, silicones having modified side chains are preferred. Commercially available aminopolyether-modified silicones include, for example, DOWSIL BY16-891 and DOWSIL Silstyle 104 manufactured by Dow Corning Toray Co., Ltd., KF-877, KF-889, X-22-3939A, and X-52-8369A manufactured by Shin-Etsu Chemical Co., Ltd., and WETSOFT CTA, WETSOFT AE200, WETSOFT NE810, WETSOFT NE820, and WETSOFT WP201 manufactured by Wacker Asahi Kasei Silicones Co., Ltd. These may be used alone or in combination of two or more.

[0063] Other commercially available products of component (C2) include, for example, DOWSIL 2501 Cosmetic Wax, DOWSIL 2503 Cosmetic Wax, DOWSIL 580 Wax, DOWSIL AMS-C30 Cosmetic Wax, BY16-891, DOWSIL FZ-2203, DOWSIL FZ-3789, and DOWSIL FZ-2222 (all trade names), manufactured by Dow Corning Toray Co., Ltd. These commercially available products may be used alone or in combination of two or more.

[0064] The concentration of component (C2) in the cleaning solution is preferably 0.1 to 20 ppm by mass (relative to the total mass of the cleaning solution), more preferably 0.5 to 15 ppm, and even more preferably 1 to 10 ppm. When the concentration of component (C2) is at least the lower limit, flexibility can be further improved. When the concentration of component (C2) is at most the upper limit, solution stability can be further improved.

[0065] The concentration of component (C) in the cleaning solution is preferably 1 to 100 ppm by mass (relative to the total mass of the cleaning solution), more preferably 3 to 80 ppm, and even more preferably 5 to 50 ppm. When the concentration of component (C) is at least the above lower limit, flexibility can be further improved. When the concentration of component (C) is at most the above upper limit, solution stability can be further improved.

[0066] The mass ratio of component (C) to component (A) in the cleaning solution (hereinafter also referred to as "(C) / (A) ratio") is preferably 0.01 to 2.0, more preferably 0.03 to 1.0, and even more preferably 0.05 to 0.5. When the (C) / (A) ratio is equal to or greater than the above lower limit, softness can be further improved. When the (C) / (A) ratio is equal to or less than the above upper limit, the component (C) attached to the textile product can be prevented from attracting dirt, and anti-soil redeposition properties can be further improved.

[0067] ≪(D) ​​Component≫ Component (D) is a polymeric organic dispersant. The cleaning solution of this embodiment contains component (D), which enhances the cleaning action. By containing component (D), 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. For this reason, it is preferable that the cleaning solution of this embodiment further contains component (D). 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). The component (D) preferably contains at least one selected from the components (D1), (D2), and (D3) described below.

[0068] <Component (D1)> The component (D1) is an alkoxylated polyalkyleneimine, i.e., the component (D1) is an alkylene oxide adduct of a polyalkyleneimine. The polyalkyleneimine is represented, for example, by the following formula (d1). NH2-R 3 -[N(A 1 )-R 3 ] n -NH2 (d1) In formula (d1), R 3 are each independently an alkylene group having 2 to 6 carbon atoms, and A 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 (d1) has a branched polyamine chain in its structure. R 3 Examples 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.

[0069] Polyalkyleneimine can be obtained, for example, by polymerizing, by a conventional method, one or more alkyleneimines having 2 to 6 carbon atoms. Examples of alkyleneimines having 2 to 6 carbon atoms include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. As the polyalkyleneimine, polyethyleneimine (hereinafter also referred to as "PEI") and polypropyleneimine are preferred, 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.

[0070] The mass average molecular weight of the polyalkyleneimine is preferably 200-2,000, more preferably 300-1,500, further preferably 400-1,000, and particularly preferably 500-800. The polyalkyleneimine preferably has 5 to 30 active hydrogen atoms, more preferably 7 to 25 active hydrogen atoms, and even more preferably 10 to 20 active hydrogen atoms in one molecule. The mass average molecular weight in this specification refers to a value determined by gel permeation chromatography (GPC) using polyethylene glycol (PEG) as a standard substance.

[0071] Component (D1) 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.

[0072] 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.

[0073] Examples of the component (D1) include an ethylene oxide adduct of a polyalkyleneimine, a propylene oxide adduct of a polyalkyleneimine, an ethylene oxide-propylene oxide adduct of a polyalkyleneimine, etc. 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 form of addition (block-like, random-like) are optional. As the component (D1), from the viewpoint of deodorizing effect, an ethylene oxide adduct of a polyalkyleneimine or an ethylene oxide-propylene oxide adduct of a polyalkyleneimine is preferred, with an ethylene oxide adduct of a polyalkyleneimine being more preferred.

[0074] The component (D1) 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.

[0075] Examples of the component (D1) include compounds represented by the following formula (d1-1).

[0076] [ka]

[0077] In formula (d1-1), 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. R 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, further preferably a number from 8 to 25, and particularly preferably a number from 8 to 15.

[0078] The mass average molecular weight of the component (D1) 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.

[0079] The component (D1) may be a synthetic product or a commercially available product, such as "Sokalan (registered trademark) HP20." The component (D1) may be used alone or in combination of two or more types.

[0080] <(D2) component> The component (D2) is a polyacrylic acid polymer. By including the component (D2), the cleaning liquid of this embodiment can further enhance its detergency against sebum stains. Examples of the component (D2) include one or more selected from polyacrylic acid and salts thereof, polymaleic acid and salts thereof, acrylic acid-maleic acid copolymers and salts thereof, copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof, and acrylic acid-methacrylic acid copolymers and salts thereof. The component (D2) is preferably one or more selected from acrylic acid-maleic acid copolymers and salts thereof, or one or more selected from copolymers of hydrocarbons having 4 to 12 carbon atoms and maleic acid and salts thereof. The salt may be a partial or complete salt, and alkali metal salts such as sodium and potassium salts and organic amine salts such as alkanolamine salts are preferred.

[0081] The hydrocarbon having 4 to 12 carbon atoms in component (D2) 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.

[0082] The copolymer of component (D2) may be a polymer having one or more repeating units selected from a repeating unit derived from a monomer represented by the following formula (d2-1) and a repeating unit derived from a monomer represented by the following formula (d2-2):

[0083] [ka]

[0084] In formula (d2-1), R 15 is a hydrogen atom or a methyl group, and R 16 is a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. 17 is a hydrogen atom or a methyl group, and R 18 is a hydrogen atom or an alkyl group having 10 to 30 carbon atoms, and R 19 is a hydrogen atom or a carboxyl group. 19 When is a hydrogen atom, R 18 is an alkyl group having 10 to 30 carbon atoms, and R 19 When is a carboxyl group, R 18 is a hydrogen atom.

[0085] In formula (d2-1), R 16 The alkyl group R may be linear or branched, and may also contain a cyclic structure. 16 The alkyl group preferably has 1 to 8 carbon atoms, and more preferably has 1 to 4 carbon atoms. Examples of the monomer represented by formula (d2-1) (hereinafter also referred to as monomer (d2-1)) 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. The monomer (d2-1) may be used alone or in combination of two or more kinds.

[0086] In formula (d2-2), R 18 The alkyl group R may be linear or branched, and may also contain a cyclic structure. 18 The alkyl group preferably has 10 to 25 carbon atoms, and more preferably 10 to 20 carbon atoms. Among the monomers represented by formula (d2-2) (hereinafter also referred to as monomers (d2-2)), in formula (d2-2), R 19 is a hydrogen atom, R 18 Examples of the monomer (d2-2) 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. 19 is a carboxyl group, R 18 Examples of the monomer (d2-2) in which R is a hydrogen atom include maleic acid and fumaric acid. 19 is a carboxyl group, R 18 The monomer (d2-2) in which is a hydrogen atom is preferably maleic acid. The monomer (d2-2) may be used alone or in combination of two or more kinds.

[0087] The component (D2) may be a crosslinked or 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.

[0088] The component (D2) may have a repeating unit (other repeating unit) other than the repeating unit derived from the monomer represented by formula (d2-1) and the repeating unit derived from the monomer represented by formula (d2-2). The other repeating units include repeating units derived from other monomers. The other monomer is not particularly limited as long as it is copolymerizable with the monomer (d2-1) and the monomer (d2-2), and examples thereof include methyl acrylate, ethyl acrylate, methacrylic acid, and methyl methacrylate. The other monomers may be used alone or in combination of two or more.

[0089] The mass average molecular weight of component (D2) 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 (D2) is at least the above lower limit, detergency can be further improved. When the mass average molecular weight of component (D2) is at most the above upper limit, liquid stability can be further improved.

[0090] The component (D2) may be used alone or in combination of two or more types.

[0091] <Component (D3)> The component (D3) is a carboxymethyl cellulose-based polymer. By including the component (D3), the cleaning liquid of this embodiment can further enhance the anti-soil redeposition properties. Examples of component (D3) include carboxymethyl cellulose (CMC) and its salts. Examples of CMC salts include alkali metal salts such as sodium salt and potassium salt, and ammonium salt, and may also be mixtures of these salts. As the CMC salt, sodium salt is preferred.

[0092] 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 it with monochloroacetic acid. Specifically, a polymer compound having a repeating unit represented by the following formula (d3-1) can be exemplified.

[0093] [ka]

[0094] In formula (d3-1), n ​​represents the number of repeating units, R 31 ~R 33 each independently represents a hydroxyl group or a carboxymethyl group (-CH2COO-Z+; Z+ is a counter ion).

[0095] The mass average molecular weight of the 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 the CMC is preferably 1,200,000 or less, more preferably 1,000,000 or less. When the mass average molecular weight of the CMC is equal to or greater than the lower limit, the anti-redeposition properties can be further improved. When the mass average molecular weight of the CMC is equal to or less than the upper limit, the solubility is improved and the liquid stability can be further improved.

[0096] The degree of etherification of CMC is preferably from 0.2 to 1.3, more preferably from 0.2 to 1.0, and even more preferably from 0.2 to 0.7. The degree of etherification of CMC in this specification means the average number of hydroxyl groups substituted with carboxymethyl groups or salts thereof per glucose ring unit (which indicates how many of the three hydroxyl groups on the glucose ring are substituted with carboxymethyl groups or salts thereof, and the maximum number is 3). For example, in the above formula (d3-1), -OR 31 , -OR 32 , -OR 33 Among them, R 31 ~R 33 The average number of groups substituted with carboxymethyl groups or salts thereof is the degree of etherification.

[0097] Commercially available CMC may be used. Examples of 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 under the trade name "Sunrose (registered trademark)" by Nippon Paper Industries Co., Ltd. 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, and more preferably CMC Daicel 1260 and HEC Daicel SP500.

[0098] The component (D3) may be used alone or in combination of two or more types.

[0099] Other examples of component (D) include cationized cellulose and polyvinylpyrrolidone.

[0100] The concentration of component (D) in the cleaning solution is preferably 5 to 200 ppm by mass (relative to the total mass of the cleaning solution), more preferably 10 to 150 ppm, and even more preferably 20 to 100 ppm. When the concentration of component (D) is at least the above lower limit, cleaning power can be further enhanced. In addition, when the concentration of component (D) is at least the above lower limit, anti-soil redeposition properties can be further enhanced. When the concentration of component (D) is at most the above upper limit, solution stability can be further enhanced.

[0101] When the cleaning solution contains the component (D1), the concentration of the component (D1) 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 the component (D1) is at least the above lower limit, cleaning power and anti-soil redeposition properties can be further improved. When the concentration of the component (D1) is at most the above upper limit, solution stability can be further improved.

[0102] When the cleaning solution contains the component (D2), the concentration of the component (D2) 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 the component (D2) is at least the above lower limit, cleaning power and anti-soil redeposition properties can be further improved. When the concentration of the component (D2) is at most the above upper limit, solution stability can be further improved.

[0103] When the cleaning solution contains the component (D3), the concentration of the component (D3) is preferably 0.1 to 50 ppm by mass, more preferably 0.5 to 30 ppm, and even more preferably 1 to 10 ppm. When the concentration of the component (D3) is at least the above lower limit, the anti-soil redeposition properties can be further improved. When the concentration of the component (D3) is at most the above upper limit, the solution stability can be further improved. The components (D1), (D2) and (D3) may be used either alone or in combination of two or more.

[0104] The mass ratio of component (D) to component (A) in the cleaning solution (hereinafter also referred to as "(D) / (A) ratio") is preferably 0.01 to 10, more preferably 0.05 to 5, and even more preferably 0.1 to 1. When the (D) / (A) ratio is at least the above lower limit, the cleaning power and anti-soil redeposition properties can be further improved. When the (D) / (A) ratio is at most the above upper limit, the solution stability can be further improved.

[0105] The cleaning liquid of this embodiment contains a solvent. As the solvent, it is preferable to use water from the viewpoints of ease of preparation, ease of use, ease of availability, etc. From the viewpoint of the stability of the cleaning solution over time, it is preferable to use ion-exchanged water, distilled water, or purified water from which metal ions such as heavy metals dissolved in water have been removed. 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 lower limit, the stability of the cleaning solution over time becomes better.

[0106] ≪Optional ingredients≫ The cleaning liquid of the present embodiment may contain other components (optional components) in addition to the components (A), (B), (C), and (D). Optional components include components that are commonly used in detergent compositions, such as water-miscible organic solvents, chelating agents, enzymes, hydrotropes, antifoaming silicones, soil release agents, stabilizers, alkali agents, preservatives, fluorescent agents, dye transfer inhibitors, pearlescent agents, antioxidants, antibacterial agents, general-purpose dyes or pigments as colorants, emulsifiers, fragrances, insoluble particles, pH adjusters, and extracts of natural products, etc. These optional components may be used alone or in combination of two or more.

[0107] The cleaning solution of this embodiment can be blended with a water-miscible organic solvent to improve stability and antiseptic properties when stored at low temperatures (for example, 5°C). In this specification, the water-miscible organic solvent refers to an organic solvent that dissolves 50 g or more 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. An example of the polyglycols is dipropylene glycol. Examples of alkyl ethers include diethylene glycol monobutyl ether (butyl carbitol), diethylene glycol dimethyl 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.

[0108] Examples of metal ion sequestrants (chelating agents) include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, and citric acid. Examples of hydrotropic agents 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 the alkaline agent include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine.

[0109] Antifoaming silicones can be of any of the oil type, oil compound type, emulsion type and self-emulsifying type. Oil-type antifoaming silicone is a silica-free antifoaming agent that is composed of 100% unmodified silicone oil. Commercially available products include SH200 (Dow Corning Toray Co., Ltd.). Oil-compound antifoaming silicones are antifoaming agents that combine silicone oil with water-insoluble particles such as finely powdered silica. Commercially available products include 8590 Additive, AF-8014 Antifoam, AC-8066 Antifoam, and ACP-3073 Antifoam (all from Dow Corning Toray Co., Ltd.), and KS-66 (from Shin-Etsu Chemical Co., Ltd.). Solution-type antifoaming silicone is an antifoaming agent made by dissolving silicone oil in a solvent such as isoparaffin. Commercially available products include KS-602A (Shin-Etsu Chemical Co., Ltd.). Emulsion-type antifoaming silicone is an antifoaming agent made by emulsifying a silicone oil compound 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 silicone is an antifoaming agent composed of hydrophilic modified silicone oil and an oil compound. Commercially available products include KS-537 (Shin-Etsu Chemical Co., Ltd.).

[0110] Examples of preservatives include "Caisson CG" (trade name) manufactured by Dow Chemical Company, "Acticide MBS" (trade name) manufactured by Thor Japan Co., Ltd., 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 the fragrance include the fragrance components described in JP-A No. 2002-146399. Examples of pH adjusters include sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamines.

[0111] 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, and polylysine.

[0112] 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.

[0113] 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.

[0114] pH The pH of the cleaning solution 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 solution stability can be maintained well. The pH is measured at 25° C. with a pH meter (for example, "HM-30G" (product name) manufactured by DKK-Toa Corporation) or the like.

[0115] ≪Viscosity≫ The viscosity of the cleaning liquid is preferably 10 mPa·s or less at 25° C. When the viscosity of the cleaning liquid is the above upper limit or less, it is easy for the cleaning liquid to come into contact with the entire textile product. The viscosity in this specification refers to a value measured at 25°C using a Brookfield type (B) viscometer.

[0116] [Cleaning solution manufacturing method] The cleaning solution of this embodiment can be obtained by dispersing components (A) to (D) and, if necessary, optional components, in water so that the concentration of component (A) is a predetermined concentration. Alternatively, a cleaning composition containing components (A) to (D) in which the concentration of component (A) is higher than the concentration in the cleaning liquid may be prepared, and this cleaning composition may be diluted 200 to 3000 times to produce a cleaning liquid having a predetermined concentration of component (A). From the viewpoint of practicality, the cleaning liquid is preferably prepared by diluting the above-mentioned cleaning agent composition with water. The detergent composition may be a liquid detergent composition or a powder detergent composition.

[0117] The content of component (A) in the detergent composition is preferably 3 to 15 mass%, more preferably 5 to 12 mass%, and even more preferably 5 to 10 mass%, relative to the total mass of the detergent composition. When the content of component (A) is at least the above-mentioned lower limit, detergency can be further enhanced. When the content of component (A) is at most the above-mentioned upper limit, foaming of a cleaning liquid obtained by dissolving the detergent composition in water is further reduced, thereby improving rinsing performance.

[0118] The content of component (B) in the detergent composition is preferably 0.3 to 5.0 mass%, more preferably 0.5 to 4.0 mass%, and even more preferably 1.0 to 3.0 mass%, relative to the total mass of the detergent composition. When the content of component (B) is equal to or greater than the above-mentioned lower limit, rinsing performance can be further improved. In addition, when the content of component (B) is equal to or greater than the above-mentioned lower limit, softness can be further improved. When the content of component (B) is equal to or less than the above-mentioned upper limit, liquid stability can be further improved.

[0119] The content of component (C) in the detergent composition is preferably 0.5 to 8 mass%, more preferably 1 to 6 mass%, and even more preferably 2 to 5 mass%, based on the total mass of the detergent composition. When the content of component (C) is at least the above lower limit, flexibility can be further improved. When the content of component (C) is not more than the above upper limit, liquid stability can be further improved.

[0120] The content of component (D) in the detergent composition is preferably 1 to 10 mass%, more preferably 2 to 8 mass%, and even more preferably 3 to 5 mass%, based on the total mass of the detergent composition. When the content of component (D) is equal to or greater than the above-mentioned lower limit, anti-soil redeposition properties can be further improved. In addition, when the content of component (D) is equal to or greater than the above-mentioned lower limit, detergency can be further improved. When the content of component (D) is equal to or less than the above-mentioned upper limit, liquid stability can be further improved.

[0121] 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 %, based on the total mass of the detergent composition. The content of the optional components in the detergent composition is preferably 20% by mass or less, more preferably 10% by mass or less, and may be 0% by mass, relative to the total mass of the detergent composition. The total content of each component in the detergent composition does not exceed 100% by mass.

[0122] [Washing Instructions] 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 washing liquid. The washing method of the present invention does not require a rinsing step, thereby reducing the environmental impact and enabling textile products to be washed in a short time. In addition, because the washing method of the present invention does not require a rinsing step, the fragrance and antibacterial effect attached to the textile product can be maintained, and damage to the textile product can be reduced. Furthermore, because the washing method of the present invention does not require a rinsing step, components (A) to (C) can be left on the textile product, and the formation of a complex between components (A) to (B) and component (C) can impart excellent softness to the textile product without using a fabric softener in the rinsing step.

[0123] 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.

[0124] The cleaning step is a step of cleaning a textile product by bringing the cleaning liquid of this embodiment into contact with the textile product. In the washing step, the washing liquid may be sprinkled on the textile product, or the textile product may be immersed in the washing liquid. The washing step preferably includes an operation of immersing the textile product in the washing liquid (immersion operation), since this can further increase the contact efficiency and the washing effect. The washing step may include only an 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 cleaning liquid of this embodiment onto the textile product. The amount of the cleaning liquid to be dropped is determined appropriately depending on the type and amount of the textile product.

[0125] When the washing step includes a dipping operation, the bath ratio in the dipping 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 bath ratio is equal to or greater than the above-mentioned lower limit, the contact efficiency between the textile product and the washing liquid can be further increased, thereby further improving the washing effect. The upper limit of the bath ratio is not particularly limited, but is, for example, 50. The agitation operation involves agitating the cleaning solution in which the items to be washed are immersed, thereby applying shear force to the items to be washed. The agitation operation is carried out, for example, by rotating or turning the washing tub of the washing machine. The rotation speed and rotation time of the washing tub during the agitation operation are appropriately determined depending on the type and amount of textile products.

[0126] In the washing step, the time (contact time) for contacting the washing liquid 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. Although there is no particular upper limit for the contact time, 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, the term "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 dehydration step described below is started.

[0127] The temperature of the washing liquid in the washing step is preferably 10 to 50°C, more preferably 20 to 40°C. When the temperature of the washing liquid in the washing step is equal to or higher than the above lower limit, the washing effect can be further improved. When the temperature of the washing liquid in the washing step is equal to or lower than the above upper limit, deterioration of the textile product can be suppressed.

[0128] In this specification, "textile products" include, for example, clothing, dishcloths, towels, handkerchiefs, sheets, curtains, pillowcases, toilet mats, and the like. The material of the textile product is not particularly limited, and examples thereof include natural fibers, synthetic fibers, semi-synthetic fibers, regenerated fibers, and blends, woven or knitted products of these fibers. Examples of natural fibers include cotton, wool, and linen. Examples of synthetic fibers include polyester, nylon, and acrylic. An example of the semi-synthetic fiber is acetate. Examples of regenerated fibers include rayon, Tencel, and Polynosic.

[0129] Examples of washing machines include two-tier washing machines, fully automatic washing machines, washing machines with automatic detergent dispensing functions, and commercial washing machines. Examples of fully automatic washing machines include washing machines with a vertical washing tub, drum washing machines, and drum washing machines with dryers. As the washing machine, a two-layer washing machine or a washing machine having a vertical washing tub is preferred, since it makes it easier to immerse textile products in the washing liquid.

[0130] 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.

[0131] In the washing step, the textile product may be contacted with components (A) and (B) and then with component (C), or may be contacted with component (C) and then with components (A) and (B), or may be contacted with components (A), (B), and (C) simultaneously. In the washing step, it is preferable to contact the textile product with component (C) after having contacted components (A) and (B), because this can further enhance the cleaning power and softness.

[0132] In this specification, the "washing process" refers to the period from when the washing liquid is brought into contact with the textile product until the dehydration process (i.e., the amount of washing liquid coming into contact with the textile product becomes less than a predetermined amount) or the rinsing process described below is started (i.e., the concentration of component (A) in the washing liquid becomes less than a predetermined concentration). When the washing method of this embodiment does not include a spin-drying step, the washing step is defined as the state in which the textile product is in contact with the washing liquid at a liquor ratio of 0.1 or more.

[0133] The washing method of this embodiment does not require a rinsing step after the washing step, but may include a rinsing step. The rinsing step is a step in which the textile product is brought into contact with a rinsing liquid to reduce the amount of component (A) adhering to the textile product. Here, "rinsing liquid" refers to an aqueous liquid in which the concentration of component (A) is less than 30 ppm. The concentration of component (B) in the rinsing liquid is preferably less than 1 ppm. The concentration of component (C) in the rinsing liquid is preferably less than 10 ppm. The concentration of component (D) in the rinsing liquid is preferably less than 10 ppm. When the washing method of this embodiment includes a rinsing step, examples of the rinsing method include a method of adding water to the cleaning liquid in which the textile product is immersed to prepare a rinsing liquid, bringing the textile product into contact with the rinsing liquid, and applying a mechanical force such as stirring to the textile product. Also, examples of the rinsing method include a method of separating the cleaning liquid from the textile product, bringing the separated textile product into contact with water, and applying a mechanical force such as stirring to the textile product. Examples of the method of separating the cleaning liquid from the textile product include a method of draining the cleaning liquid from the washing tub and a method of removing the textile product from the cleaning 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.

[0134] 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. For this reason, the washing method of this embodiment preferably includes the dehydration step. Examples of dehydration methods include a method of applying centrifugal force to textile products that have come into contact with cleaning liquid, and a method of squeezing the textile products to remove the cleaning liquid.

[0135] The washing method of the present embodiment may include steps other than the washing step, rinsing step, and spin-drying step. Other steps include, for example, a draining step and a drying step. The draining process is a process of discharging the cleaning liquid that has been in contact with the textile products from the washing tub of the washing machine. By including the draining process, the cleaning liquid adhering to the textile products can be removed. The draining process 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 dehydration 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 dried in a bathroom equipped with a dryer or outdoors.

[0136] As described above, the washing method of the present invention washes textile products with a cleaning solution containing components (A), (B), and (C), with a concentration of component (A) of 30 to 150 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 can impart excellent softness to textile products. Therefore, the washing method of the present invention can omit the rinsing step that is essential in conventional washing. [Example]

[0137] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following description. The raw materials and measurement and evaluation methods used in each example and comparative example are as follows.

[0138] [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, 2 is a hydrogen atom, m is 15, and n is 0). AE(6EO): Polyoxyethylene alkyl ether (6EO), a compound in which 6 moles of ethylene oxide are added to a natural alcohol. In the formula (a1), R 1 is a linear alkyl group having 12 carbon atoms and a linear alkyl group having 14 carbon atoms, -X- is -O-, R 2 A compound where 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 moles of EO added 15), in the formula (a1), 1is 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 The carbon atom in R is a secondary carbon atom, 2 A compound where 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 / 14 carbon atoms = 7 / 3). In formula (a1), R 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 repeats of EO different from m). TAG: polyoxyethylene alkyl ether (a compound obtained by adding 7 moles of ethylene oxide to an alcohol having 13 carbon atoms. In the formula (a1), R 1 is a branched alkyl group having 13 carbon atoms, -X- is -O-, and R 1 The carbon atom in R is a primary carbon atom, 2 is a hydrogen atom, m=7, and n=0. This compound was synthesized according to Production Example 1 below. 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. POE isotridecyl ether (60EO): Polyoxyethylene isotridecyl ether (60EO), a BASF product with Rutensol TO3 as its trade name, to which ethylene oxide (EO) has been added (60EO indicates that the average number of moles of ethylene oxide added is 60).

[0139] <(A2) component> LAS: Sodium linear alkylbenzene sulfonate, trade name "Lipon (registered trademark) LS-250", manufactured by Lion Corporation. AES: Polyoxyethylene alkyl ether sulfate (polyoxyethylene alkyl ether sulfate. 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, product name "EMAL 270"). · AEPS: Monoethanolamine salt of polyoxyethylene polyoxypropane-1,2-diyl alkyl ether sulfate. IOS: salt of internal olefin sulfonic acid, a compound synthesized by the method described in Example 7 of JP-A-2001-247534.

[0140] ≪(B) Component≫ Palm fatty acids: Manufactured by NOF Corporation, product name "Palm Fatty Acids."

[0141] ≪(C) Component≫ <(C1) component> TES: N,N-dialkanoyloxyethyl-N-methyl-N-hydroxyethylammonium methyl sulfate, manufactured by Tonan Synthetic Co., Ltd., trade name "HITEX R016E."

[0142] <(C2) component> POE-modified silicone: Polyether-modified silicone, manufactured by Toray Dow Corning Co., Ltd., product name "CF1188N". Amino-modified silicone: Shin-Etsu Chemical Co., Ltd., product name "KF-864".

[0143] ≪(D) ​​Component≫ <Component (D1)> PEI (10EO): alkoxylated polyalkyleneimine, an ethylene oxide adduct of polyethyleneimine obtained in Production Example 2 below (number of active hydrogen atoms in one molecule of polyethyleneimine: 10, average number of moles of ethylene oxide added per active hydrogen atom: 10). PEI (20EO): Alkoxylated polyalkyleneimine, ethylene oxide adduct of polyethyleneimine (manufactured by BASF, trade name "Sokalan HP20", number of active hydrogen atoms per molecule of polyethyleneimine: 20, average number of moles of ethylene oxide added per active hydrogen atom: 20, mass average molecular weight: 14,500).

[0144] <(D2) component> CP7: Sodium salt of 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 copolymer of hydrocarbons 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 8000.

[0145] <Component (D3)> Daicel CMC1260: Carboxymethyl cellulose, manufactured by Daicel Miraize Co., Ltd., product name "Daicel CMC1260".

[0146] <Optional ingredients> Silicone emulsion: Shin-Etsu Chemical Co., Ltd., product name "KM-90". Ethanol: Manufactured by Japan Alcohol Sales Co., Ltd., product name "Specific 95% synthetic alcohol". Solfit: 3-methoxy-3-methyl-1-butanol, manufactured by Kuraray Co., Ltd., trade name "Solfit (registered trademark)". Sodium benzoate: Sodium benzoate, manufactured by Toagosei Co., Ltd. Citric acid: Chelating agent, manufactured by Lion Specialty Chemicals Co., Ltd., product name "Liquid Citric Acid." Fragrance: Fragrance composition A described in Tables 11 to 18 of JP-A No. 2002-146399. ·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 and sodium hydroxide, both manufactured by Toagosei Co., Ltd. <Water> ·Water: Purified water.

[0147] <Production Example 1: Synthesis of TAG> 400 g of EXXAL (registered trademark) 13 manufactured by Sasol and 3.33 g of a 30% by mass aqueous NaOH solution were charged into a pressure-resistant reaction vessel, and the inside of the reaction vessel was purged with nitrogen. Next, after dehydration at a temperature of 100°C and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160°C. Then, while stirring the reaction solution, 1145 g of ethylene oxide (in gaseous form) was gradually added to the reaction solution. At this time, ethylene oxide was added through a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180°C. After the addition of ethylene oxide was completed, aging was carried out at a temperature of 180°C and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180°C and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100°C or less, 70% by mass p-toluenesulfonic acid was added for neutralization so that the pH of a 1% by mass aqueous solution of the reaction product became about 7, and TAG was obtained.

[0148] <Production Example 2: Production of Ethylene Oxide Adduct (10EO) of Polyethyleneimine> An autoclave containing polyethyleneimine (manufactured by BASF, trade name "Lupasol FG") and water was evacuated and then purged with nitrogen. While heating the autoclave, ethylene oxide corresponding to 10 moles per mole of nitrogen atom was added for ethoxylation to obtain an ethylene oxide adduct of polyethyleneimine.

[0149] [Measurement and Evaluation Methods] <Measurement of pH> 100 mL of each cleaning composition (liquid cleaning agent) was prepared, and the pH of each liquid cleaning agent was measured using a pH meter (portable pH / ORP / ION meter D-73, manufactured by Horiba, Ltd.) in an environment of 25°C.

[0150] <Evaluation of rinsing ability (foam suppression)> 20 mL of each cleaning solution was placed in an Epton tube (volume 100 mL, body diameter 25 mm), and the Epton tube was shaken by hand 20 times at 1 stroke / second. The height of the foam (the height from the boundary between the foam and the cleaning solution to the top surface of the foam) was read one minute after the end of shaking, and the rinsing performance was evaluated according to the following evaluation criteria. In the following evaluation criteria, ⊚, ⊚, and ◯ were considered to be acceptable. Evaluation Criteria ◎◎: Bubble height is less than 30 mm. ◎: Foam height is 30mm or more but less than 70mm. ○: Foam height is 70mm or more but less than 120mm. △: Foam height is 120mm or more but less than 150mm. ×: The bubble height is 150mm or more.

[0151] <Evaluation of cleaning power> The cleaning power was evaluated without performing a rinsing step. The soiled cloth used was 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 5cm x 5cm square. The cleaning tester used was a Terg-O-tometer (manufactured by UNITED STATES TESTING). 900 mL of the cleaning solution of each example, 10 of the soiled cloths, and the washed knitted cloth were placed in the cleaning tester, and the bath ratio (washing water / total mass of the cloths to be washed) was adjusted to 20, after which a cleaning treatment was carried out for 10 minutes at 120 rpm and 15° C. Thereafter, the cloths were transferred to a twin-tub washing machine (manufactured by Toshiba Corporation, product name "VH-30S"), subjected to a spin-drying treatment for 1 minute, and then air-dried. The reflectance of each of the soiled cloth before cleaning, the soiled cloth after cleaning, and the unsoiled cloth (here, unsoiled cloth refers to the original white cloth (raw cloth) that has not been soiled) was measured using a color difference meter (manufactured by 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) × 100 (i) [In formula (i), K / S is (1-R / 100) / (2R / 100), and R represents the reflectance (%) of the soiled cloth before washing, the soiled cloth after washing, or the unsoiled cloth. K represents the absorption coefficient, S represents the scattering coefficient, and R represents the absolute reflectance.] The average value of the cleaning rate for 10 soiled cloths was calculated. The average value was evaluated according to the following evaluation criteria. In the following evaluation criteria, ⊚ and ◯ were considered to be acceptable. Evaluation Criteria ◎: Cleaning rate is 50% or more. Good: Cleaning rate is 45% or more but less than 50%. △: Cleaning rate is 40% or more but less than 45%. ×: Cleaning rate is less than 40%.

[0152] <Flexibility evaluation> Three commercially available cotton towels (100% cotton) and four cotton undershirts (manufactured by BVD, total mass of all fabrics to be washed: approximately 600 g) were placed in a fully automatic electric washer-dryer (AW-8V2, manufactured by Toshiba) to adjust the bath ratio (washing water / total mass of fabrics to be washed) to 20 times. The washing solution was prepared in the washing machine to achieve the concentration of each example, and the washing operation was carried out using the standard course, with washing and spin-drying performed in that order. The washing time (10 minutes), spin-drying time (5 minutes), and water volume (set to low water level, approximately 12 L) were adjusted, and the towels were washed. After washing, the towels were removed and left to dry in a constant temperature and humidity chamber at 25°C and 65% RH. These were used as test cloths for softness evaluation. The control cloth for evaluation was a cotton towel treated in the same manner as the test cloth, except that 10 mL of 20% nonionic surfactant (P&G natural alcohol CO-1270 to which 15 moles of ethylene oxide had been added) was used. The softness was evaluated by sensory comparison with the control fabric according to the following rating scale, and the average value of the scores of 10 expert panelists was calculated. The softness was evaluated based on the following rating scale, and an average score of 3 points or more was considered to be acceptable. <Grading criteria> 5 points: Test fabric is significantly softer than control fabric. 4 points: Test fabric is significantly softer than control fabric. 3 points: Test fabric is softer than control fabric. 2 points: Test fabric is slightly softer than control fabric. 1 point: The test fabric is as soft as the control fabric. Evaluation Criteria ◎: Average value is 4 points or more. ○: Average value is 3 points or more but less than 4 points. △: Average value is 2 points or more but less than 3 points. ×: Average value is less than 2 points.

[0153] [Examples 1 to 27, Comparative Examples 1 to 5] The concentrations of each component were adjusted as shown in Tables 1 to 6, and cleaning solutions of Examples 1 to 27 and Comparative Examples 1 to 5 were prepared according to the following procedure. Components (A), (B), and (C) were mixed with water until homogeneous, and then any optional components were added and thoroughly stirred to obtain a cleaning liquid. In Tables 1 to 6, the concentration (ppm) of each component is the percentage relative to the total mass of the cleaning solution, and unless otherwise specified, the value is shown as a pure content. In the tables, "-" indicates that the component is not contained. An appropriate amount of pH adjuster was added so that the pH of the cleaning solution at 25°C would be the value shown in Tables 1 to 6. Water was added so that the total amount (mass %) of all ingredients contained in the cleaning solution in each example was 100 mass %. In other words, the amount of water is the remainder after subtracting the total amount (in pure content) of ingredients other than water from the total mass of the cleaning solution. The cleaning solution of each example was evaluated for rinsing ability, detergency, and softness by the methods described above, and the results are shown in the table. However, Examples 20 and 21 are reference examples.

[0154] [Table 1]

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] [Table 5]

[0159] [Table 6]

[0160] As shown in Tables 1 to 6, Examples 1 to 27 to which the present invention was applied were excellent in rinsing properties, detergency, and softness. In contrast, Comparative Example 1, which did not contain component (A), exhibited poor detergency. Comparative Example 2, in which the concentration of component (A) in the cleaning solution was less than 30 ppm, exhibited poor detergency. Comparative Example 3, in which the concentration of component (A) in the cleaning solution was more than 150 ppm, exhibited poor rinsing properties and softness. Comparative Example 4, which did not contain component (B), exhibited poor rinsing properties and softness. Comparative Example 5, which did not contain component (C), exhibited poor softness.

[0161] These results demonstrate that the present invention provides excellent rinsing properties with minimal foaming during washing, and can provide sufficient cleaning power even when the rinsing process is simplified, while also imparting excellent softness.

Claims

1. A method for washing textile products, comprising a washing step of contacting a washing liquid with textile products, and not comprising a rinsing step after the washing step, The cleaning solution comprises: component (A): a surfactant other than the following component (B) and the following component (C); (B) component: 5 to 50 ppm of a fatty acid having 12 to 18 carbon atoms or a salt thereof relative to the total mass of the cleaning solution; (C) component: the cleaning solution contains 10 to 100 ppm of the following (C1) component based on the total mass of the cleaning solution, The concentration of the component (A) is 30 to 150 ppm based on the total mass of the washing liquid. Component (C1): At least one compound selected from the group consisting of amine compounds represented by the following formula (C1), their salts, and their quaternized products. 【Chemistry 1】 (In formula (C1), R １１ ~R １３ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ２ CH(Y)OCOR ４ (Y is a hydrogen atom or CH ３ and R ４ is a hydrocarbon group having 7 to 21 carbon atoms.), —CH ２ CH(Y)OR ５ (Y is a hydrogen atom or CH ３ and R ５ is a hydrocarbon group having 7 to 21 carbon atoms.) or —(CH ２ ) ｎ NHCOR ６ (n is 2 or 3, R ６ is a hydrocarbon group having 7 to 21 carbon atoms; a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH ２ CH(Y)OH, or -(CH ２ ) ｎ NH ２ and R １１ ~R １３ At least one of the groups is —CH ２ CH(Y)OCOR ４ It is.)

2. The washing method according to claim 1, wherein the washing liquid further contains component (D): a polymeric organic dispersant.

3. The washing method according to claim 2, wherein the component (D) is at least one selected from the following components (D1), (D2), and (D3): Component (D1): Alkoxylated polyalkylimine. Component (D2): polyacrylic acid polymer. Component (D3): carboxymethyl cellulose-based polymer.

4. The washing method according to claim 2 or 3, wherein the concentration of the component (D) is 5 to 200 ppm based on the total mass of the washing liquid.

5. The washing method according to any one of claims 1 to 4, wherein the mass ratio of the component (C) to the component (A) in the washing liquid is 0.06 to 3.3.

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