Washing method

Abstract

To provide washing methods that can enhance the amount of phenolic antibacterial compounds with antibacterial effects remaining in fiber products.SOLUTION: The present invention provides a washing method for washing a fiber product and rinsing the fiber product after washing. The rinsing is performed by bringing a rinse solution with a pH of 6.5 or less, containing water, into contact with the fiber product, in the presence of components (a) and (b) defined below. (a) A phenolic antibacterial compound. (b): At least one surfactant selected from specific anionic surfactants or nonionic surfactants.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Regarding the washing of textile products, for example, washing and rinsing using an aqueous medium are known. In recent years, due to the increasing awareness of hygiene among consumers, there has been an increasing interest in keeping things around us clean. In particular, textile products around the kitchen, such as clothing, linens, and dishcloths, may affect the human body if bacteria are attached to them, so it is desirable to sterilize, disinfect, and treat antibacterial properties of textile products. In addition, with the spread of information linking unpleasant odors to the proliferation of microorganisms, there has been an increasing interest in removing odors by sterilizing, disinfecting, and treating antibacterial properties of textile products. As a means for suppressing the proliferation of bacteria attached to textile products such as clothing, it is known to use quaternary ammonium surfactants, phenolic antibacterial agents, biguanide compounds, and the like. In addition, aromatic chlorine compounds such as diclosan are also known as compounds having antibacterial and bactericidal properties. These compounds can be applied, for example, to detergents when washing textile products.

[0003] For example, Patent Document 1 discloses a liquid detergent composition for clothing that contains component (A): a hydroxycarboxylic acid, component (B): (b-1) a specific quaternary ammonium salt, (b-2) at least one antibacterial agent selected from the group consisting of phenolic antibacterial agents and (b-3) biguanide compounds, and component (C): a nonionic surfactant, in which the content of component (A) is 5 mass% or more relative to the total mass of the liquid detergent composition for clothing and the pH at 25°C is 2 to 6.

[0004] Patent Document 2 also describes a method for cleaning a fabric comprising the steps of: a) contacting a fabric with an aqueous cleaning solution containing at least one detersive surfactant, the aqueous cleaning solution being characterized by a first pH in the range of 7.0 to 9.0; b) increasing the pH of the aqueous cleaning solution to a second pH in the range of 10.0 to 13.0, while continuing to contact the fabric with such aqueous cleaning solution for a duration in the range of 5 minutes to 30 minutes; and c) contacting the fabric with an aqueous cleaning solution characterized by a third pH in the range of 3.0 to 6.0. and contacting the fabric with a rinse liquor, further comprising a step (b1) after step (b) and before step (c) of lowering the pH of the aqueous wash liquor back to a fourth pH in the range of 7.0 to 9.0, wherein in step (b1), the fabric is contacted with the aqueous wash liquor for a duration in the range of 1 minute to 60 minutes, and further disclosed that 5-chloro-2-(4-chlorophenoxy)phenol can be dispensed into the aqueous rinse liquor during step (c). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-188641 A [Patent Document 2] Special Publication No. 2022-511731 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention provides a washing method capable of increasing the amount of a phenolic antibacterial compound having an antibacterial effect remaining on a textile product. [Means for solving the problem]

[0007] The present invention relates to a washing method for washing a textile product and rinsing the washed textile product, in which the rinsing is carried out by contacting the textile product with a rinsing liquid containing water and having a pH of 6.5 or less in the presence of the following components (a) and (b): (a) Phenolic antibacterial compounds Component (b): one or more surfactants selected from the following components (b1) and (b2): Component (b1): one or more anionic surfactants selected from the following components (b1-1) and (b1-2): Component (b1-1): Anionic surfactant represented by general formula (b1-1) R 1 -O-[(PO) q (EO) r ]-SO3M (b1-1) [In general formula (b1-1), R 1 is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, PO and EO are block bonds or random bonds, q is the average number of moles of PO added and is a number of 1 to 5, r is the average number of moles of EO added and is a number of 0.1 to 10, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium or an organic ammonium. (b1-2) component: internal olefin sulfonate having 14 to 20 carbon atoms Component (b2): one or more nonionic surfactants selected from the following components (b2-1) and (b2-2): Component (b2-1): a nonionic surfactant represented by the general formula (b2-1) R 2 COO-(AO) m -R 3 (b2-1) [In general formula (b2-1), R 2 is a hydrocarbon group having 9 to 24 carbon atoms, AO is an alkyleneoxy group, m is the average number of moles of AO added and is a number of 3 to 50, R 3 is a hydrogen atom or a methyl group. Component (b2-2): a nonionic surfactant represented by the general formula (b2-2) R 4 -O-(PO) s -(EO) t -R 5 (b2-2) [In general formula (b2-2), R 4is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, PO and EO are block-bonded in this order, s is the average number of moles of PO added and is a number of 0.1 to 20, t is the average number of moles of EO added and is a number of 4 to 25, R 5 is a hydrogen atom or a methyl group. Effect of the Invention

[0008] According to the present invention, there is provided a washing method capable of increasing the amount of a phenolic antibacterial compound having an antibacterial effect remaining on a textile product. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In the washing method of the present invention, washing of textile products and rinsing of the washed textile products are carried out under predetermined conditions. The textile products can be washed according to known washing methods. For example, the textile products can be washed by contacting them with a cleaning solution prepared from a cleaning agent containing a surfactant, a builder, etc. More specifically, for example, a method of mixing a detergent containing a surfactant, builder, etc., with a textile product and water, and preferably applying an external force to the textile product to wash it can be mentioned. Alternatively, the detergent can be brought into contact with the textile product by a method such as immersing the textile product in a cleaning liquid in which the detergent is dissolved in water in advance, or directly applying the detergent to the textile product, and then leaving it for a certain period of time, and then performing normal washing. Washing, preferably washing with application of an external force, is usually carried out once. The method of applying an external force to the textile product may be, for example, a method of applying mechanical force using a washing machine, or a method of hand washing such as rubbing, pressing, beating, grabbing, pinching, or shaking. Usually, the laundry process includes a rinsing process after the washing process. In general, the rinsing process is carried out by supplying a liquid medium not containing a detergent, preferably water, and preferably applying an external force to the textile product to remove detergent components such as surfactants remaining on the textile product. The liquid medium used for rinsing may contain a fabric softener. In the present invention, rinsing can be carried out in accordance with a known rinsing method, except that a rinsing liquid having a pH of 6.5 or less is used. The rinsing process may be carried out once or twice or more. In the present invention, unless otherwise specified, the term "fiber retention" means an improvement in the retention of the phenolic antibacterial compound of component (a) on fibers.

[0010] In the washing method of the present invention, the washed textile product is rinsed by contacting the textile product with a rinsing liquid containing water and having a pH of 6.5 or less in the presence of the following components (a) and (b). (a) Phenolic antibacterial compounds Component (b): one or more surfactants selected from the following components (b1) and (b2): Component (b1): one or more anionic surfactants selected from the following components (b1-1) and (b1-2): Component (b1-1): Anionic surfactant represented by general formula (b1-1) R 1 -O-(PO)q(EO)r-SO3M (b1-1) [In general formula (b1-1), R 1 is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, EO and PO may be bonded in a block or random manner, q is the average number of moles of PO added and is a number of 1 to 5, r is the average number of moles of EO added and is a number of 0.1 to 10, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium or an organic ammonium. (b1-2) component: internal olefin sulfonate having 14 to 20 carbon atoms Component (b2): one or more nonionic surfactants selected from the following components (b2-1) and (b2-2): Component (b2-1): a nonionic surfactant represented by the general formula (b2-1) R 2 COO-(AO) m -R 3 (b2-1) [In general formula (b2-1), R 2 is a hydrocarbon group having 9 to 24 carbon atoms, AO is an alkyleneoxy group, m is the average number of moles of AO added and is a number of 3 to 50, R 3 is a hydrogen atom or a methyl group. Component (b2-2): a nonionic surfactant represented by the general formula (b2-2) R 4 -O-(PO) s -(EO) t -R 5 (b2-2) [In general formula (b2-4), R 4 is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, EO and PO are block bonded in this order, s is the average number of moles of PO added and is a number of 0.1 to 20, t is the average number of moles of EO added and is a number of 4 to 25, R 5 is a hydrogen atom or a methyl group.

[0011] As the component (a), a phenol-based antibacterial compound is used from the viewpoint of fiber residue. The phenol-based antibacterial compound is an antibacterial compound having a phenol structure. Specific examples of the (a) component include phenol, cresol, thymol, carvacrol, eugenol, paraben, isopropylmethylphenol (common name: IPMP), chloroxylenol (common name: PCMX), o-benzyl-p-chlorophenol (common name: chlorophene), 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan), and benzylchlorophenol.

[0012] From the viewpoint of fiber residue, component (a) is preferably a compound having a halogen atom, more preferably a chlorodiphenyl ether antibacterial compound such as diclosan or triclosan, and even more preferably diclosan.

[0013] The component (a) may be used alone or in appropriate combination of two or more kinds.

[0014] The component (b) is one or more surfactants selected from the following components (b1) and (b2). Component (b1): one or more anionic surfactants selected from the following components (b1-1) and (b1-2): Component (b1-1): Anionic surfactant represented by general formula (b1-1) R 1 -O-[(PO) q (EO) r ]-SO3M (b1-1) [In general formula (b1-1), R 1 is a hydrocarbon group having 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, PO and EO are block bonds or random bonds, q is the average number of moles of PO added and is a number of 1 to 5, r is the average number of moles of EO added and is a number of 0.1 to 10, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium or an organic ammonium. (b1-2) component: internal olefin sulfonate having 14 to 20 carbon atoms Component (b2): one or more nonionic surfactants selected from the following components (b2-1) and (b2-2): Component (b2-1): a nonionic surfactant represented by the general formula (b2-1) R 2 COO-(AO) m -R 3 (b2-1) [In general formula (b2-1), R 2 is a hydrocarbon group having 9 to 24 carbon atoms, AO is an alkyleneoxy group, m is the average number of moles of AO added and is a number of 3 to 50, R3 is a hydrogen atom or a methyl group. Component (b2-2): a nonionic surfactant represented by the general formula (b2-2) R 4 -O-(PO) s -(EO) t -R 5 (b2-2) [In general formula (b2-4), R 4 is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, PO and EO are block-bonded in this order, s is the average number of moles of PO added and is a number of 0.1 to 20, t is the average number of moles of EO added and is a number of 4 to 25, R 5 is a hydrogen atom or a methyl group.

[0015] Regarding the component (b1-1), in the general formula (b1-1), R 1 From the viewpoint of fiber retention, is a hydrocarbon group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 22 or less, preferably 16 or less, more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the general formula (b1-1), PO and EO may be either block bonds or random bonds. From the viewpoint of fiber retention, however, R 1 It is a block bond in which PO and EO are bonded in that order to -O. In general formula (b1-1), q is a number that is 1 or more, preferably 1.5 or more, more preferably 1.8 or more, and 5 or less, preferably 3 or less, more preferably 2.5 or less, from the viewpoint of fiber retention. In general formula (b1-1), r is a number that is 0.1 or more, preferably 1 or more, more preferably 2 or more, and 10 or less, preferably 5 or less, more preferably 3 or less, from the viewpoint of fiber residue. In the general formula (b1-1), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. M is more preferably an alkali metal such as sodium or potassium, an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and further preferably monoethanol ammonium. The content of the component (b1-1) in the present invention is based on the amount of the compound converted into a monoethanolammonium salt.

[0016] The internal olefin sulfonate having 14 to 20 carbon atoms, which is the component (b1-2), can be obtained by sulfonating an internal olefin having 14 to 16 carbon atoms. The internal olefin refers to an olefin in which the double bond is located inside the 2-position. For example, the internal olefin can be obtained by isomerizing a 1-olefin obtained by dehydrating a 1-alcohol. When the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkanesulfonate and olefin sulfonate in the neutralization and hydrolysis process (for example, J. Am. Oil Chem. Soc. 69, 39(1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonic acid is inside the alkane chain, and the double bond of the olefin sulfonate is inside the olefin chain. The obtained product is mainly a mixture of these, and may contain a small amount of hydroxyalkanesulfonic acid having a hydroxy group at the end of the carbon chain or α-olefinsulfonic acid having a double bond at the end of the carbon chain. In this specification, these products and their mixtures are collectively called internal olefinsulfonic acid. Hydroxyalkanesulfonic acid is also called hydroxyl form of internal olefinsulfonic acid (hereinafter also called HAS), and olefinsulfonic acid is also called olefin form of internal olefinsulfonic acid (hereinafter also called IOS).

[0017] From the viewpoint of fiber residual property, the carbon number of the internal olefin sulfonate is 14 or more, preferably 16 or more, and 20 or less, preferably 18 or less. The carbon number of the internal olefin sulfonate refers to the carbon number of the internal olefin to which the sulfonic acid is covalently bonded. The salt is preferably a hydrogen atom, an alkali metal salt such as sodium or potassium, an alkaline earth metal salt (1 / 2 atom) such as magnesium or calcium, or an organic ammonium salt. The salt is more preferably an alkali metal salt such as sodium or potassium, or an alkanol ammonium salt such as monoethanol ammonium or diethanol ammonium, and further preferably a potassium salt. The content of the component (b1-2) in the present invention is based on the amount of the compound converted into a potassium salt.

[0018] The internal olefin sulfonate also includes those containing a small amount of so-called alpha olefin sulfonate (hereinafter also referred to as α-olefin sulfonate) in which the sulfonic acid is at position 1 of the carbon chain. From the viewpoint of fiber residue, the upper limit of the content of α-olefin sulfonate in the internal olefin sulfonate is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, still more preferably 3% by mass or less, and preferably 0.01% by mass or more.

[0019] The internal olefin sulfonate salt (b1-2) can be obtained by sulfonating an olefin having 14 to 20 carbon atoms and a double bond at the second or higher position as the main component. When the internal olefin is sulfonated, β-sultone is quantitatively produced, and a part of the β-sultone is converted to γ-sultone and olefin sulfonic acid, which are further converted to hydroxyalkanesulfonic acid and olefin sulfonic acid in the neutralization and hydrolysis process (for example, J. Am.Oil Chem. Soc. 69, 39(1992)). Here, the hydroxy group of the obtained hydroxyalkanesulfonic acid is inside the alkane chain, and the double bond of the olefin sulfonic acid is inside the olefin chain. The obtained product is mainly a mixture of these, and some of them may contain a small amount of hydroxyalkanesulfonic acid having a hydroxy group at the end of the carbon chain or olefin sulfonic acid having a double bond at the end of the carbon chain.

[0020] In this specification, these products and mixtures thereof are collectively referred to as internal olefin sulfonates, and hydroxyalkanesulfonates are referred to as hydroxy forms of internal olefin sulfonates (HAS), and olefin sulfonates are referred to as olefin forms of internal olefin sulfonates (IOS). The mass ratio of the compounds in the internal olefin sulfonate can be measured by HPLC-MS. Specifically, for example, the mass ratio can be determined from the HPLC-MS peak area of ​​the internal olefin sulfonate by the method described in the Examples below.

[0021] The internal olefin sulfonate may contain a hydroxyl group and an olefin group. The mass ratio of the content of the olefin group in the internal olefin sulfonate to the content of the hydroxyl group in the internal olefin sulfonate (olefin group / hydroxyl group) may be 0 / 100 or more, further 5 / 95 or more, and 50 / 50 or less, further 40 / 60 or less, further 30 / 70 or less, further 25 / 75 or less.

[0022] Regarding the component (b2-1), in the general formula (b2-1), R 2 From the viewpoint of fiber retention, is a hydrocarbon group having 9 or more carbon atoms, preferably 10 or more, more preferably 11 or more, and 24 or less, preferably 20 or less, more preferably 18 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In general formula (b2-1), AO is an alkyleneoxy group, preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. In general formula (b2-1), m is a number of 3 or more, preferably 5 or more, more preferably 10 or more, and 50 or less, preferably 30 or less, more preferably 20 or less, from the viewpoint of fiber retention. In general formula (b2-1), R 2-6 is preferably a methyl group.

[0023] Regarding the component (b2-2), in the general formula (b2-2), R 4 From the viewpoint of fiber retention, represents an aliphatic hydrocarbon group having 10 or more carbon atoms, preferably 12 or more, and 24 or less, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, and still more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In general formula (b2-2), s represents the average number of moles of PO added, and from the viewpoint of fiber retention, is a number that is 0.1 or more, preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and is 20 or less, preferably 10 or less, even more preferably 8 or less, still more preferably 6 or less, and even more preferably 4 or less. In general formula (b2-2), t is the average number of moles of EO added, and from the viewpoint of fiber retention, is a number that is 4 or more, preferably 7 or more, more preferably 10 or more, and 25 or less, preferably 20 or less, more preferably 18 or less, and even more preferably 17 or less. In general formula (b2-2), R 5 is preferably a hydrogen atom.

[0024] From the viewpoint of fiber retention, the component (b) is preferably one or more surfactants selected from the components (b1-1) and (b2-1).

[0025] In the present invention, rinsing is performed by contacting a water-containing rinse solution having a pH of 6.5 or less with a textile product containing components (a) and (b). The raw material of the rinse solution may be ion-exchanged water or water containing hardness components such as tap water. When using water containing hardness components, the hardness of the water is, from the viewpoint of fiber residue, for example, 0.5° dH or more, more preferably 1° dH or more, even more preferably 2° dH or more, even more preferably 3° dH or more, and preferably 20° dH or less, more preferably 10° dH or less, even more preferably 8° dH or less, and even more preferably 6° dH or less. It is also preferable that the rinse solution has a hardness in this range. The German hardness is measured by the following method.

[0026] <Method of measuring water hardness in Germany> 〔reagent〕 0.01 mol / L EDTA·2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, manufactured by Sigma-Aldrich) ·Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories Co., Ltd.) Ammonia buffer solution for hardness measurement (67.5 g of ammonium chloride dissolved in 570 ml of 28 w / v% ammonia water, and then made up to 1000 ml with ion-exchanged water) [Method of measuring hardness] First, 20 mL of sample (raw water or rinse solution) is taken into a conical beaker with a whole pipette, and 2 mL of ammonia buffer solution for hardness measurement is added. Furthermore, 0.5 mL of Universal BT indicator is added, and it is confirmed that the solution after addition is reddish purple. While shaking the conical beaker well, add 0.01 mol / L EDTA·2Na solution from the burette and the end point of the titration is when the sample turns blue. The total hardness in the sample is calculated from the titration volume T (mL) of the EDTA·2Na solution using the following formula. Hardness (°DH)=(T×0.01×F×56.0774×100) / A T:0.01mol / L Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, sample volume) F: Factor of 0.01mol / L EDTA·2Na solution

[0027] In the present invention, the pH of the rinse solution when it comes into contact with the textile product is 6.5 or less, preferably 5.5 or less, more preferably 5.0 or less, and preferably 3.5 or more, more preferably 4.0 or more, from the viewpoint of fiber residue. The pH of the rinse solution when it comes into contact with the textile product may be 6.5 or less, from the viewpoint of fiber residue, and the pH may vary during rinsing. The pH is the pH at the temperature when rinsing is performed. The pH is measured by the following method.

[0028] [pH measurement method] A composite electrode for pH measurement (glass-ground sleeve type, manufactured by HORIBA) is connected to a pH meter (pH / ion meter F-23, manufactured by HORIBA) and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) is used as the internal solution of the pH electrode. Next, a 100 mL beaker is filled with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution), and the beaker is immersed in a thermostatic bath at 25°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and the calibration operation is performed in the order of pH 6.86 → pH 9.18 → pH 4.01. The sample to be measured (rinse solution) is adjusted to the temperature when rinsing is performed, and the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

[0029] The pH of the rinse liquid may be adjusted by adding a pH adjuster, which will be described later, to the water.

[0030] The present invention has found that by rinsing at pH 6.5 or less in the presence of components (a) and (b), the component (a) attached to the textile product is less likely to be washed away from the textile product, and the amount of component (a) remaining in the textile product can be increased. The components (a) and (b) may coexist with the textile product at least during rinsing, and a predetermined rinsing solution may be applied. In the present invention, from the viewpoint of fiber residue, it is preferable to wash the textile product with a cleaning solution containing components (a) and (b) (hereinafter also referred to as the cleaning solution of the present invention) and then supply water to the textile product containing components (a) and (b) to rinse the textile product so that the rinsing solution having a pH of 6.5 or less comes into contact with the textile product. Usually, the textile product after washing is dehydrated to separate the cleaning solution, but the textile product before rinsing after dehydration retains the cleaning solution containing components (a) and (b), and in the present invention, the textile product in such a state can be subjected to rinsing. Therefore, in the present invention, it is preferable to wash the textile product with a cleaning solution containing components (a) and (b).

[0031] The cleaning solution of the present invention will now be described. From the viewpoint of fiber residue, the concentration of component (a) in the cleaning solution of the present invention may be preferably 0.01 ppm or more, more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, even more preferably 0.25 ppm or more, and preferably 10 ppm or less, more preferably 2.5 ppm or less, and even more preferably 1 ppm or less. In the present invention, ppm is a unit representing a mass ratio (the same applies to ppm below).

[0032] In the washing method of the present invention, the amount (mg / kg) of component (a) in the washing liquid of the present invention is, from the viewpoint of fiber residue, preferably 0.2 or more, more preferably 2 or more, and preferably 200 or less, more preferably 50 or less, even more preferably 20 or less, and still more preferably 10 or less, based on the mass (kg) of the dry textile product.

[0033] From the viewpoint of fiber residue, the concentration of component (b) in the cleaning solution of the present invention may be preferably 10 ppm or more, more preferably 30 ppm or more, even more preferably 50 ppm or more, still more preferably 100 ppm or more, and preferably 3000 ppm or less, more preferably 1500 ppm or less, even more preferably 750 ppm or less, and still more preferably 300 ppm or less.

[0034] When the cleaning solution of the present invention contains the component (b1), the concentration of the component (b1) in the cleaning solution may be, from the viewpoint of fiber residue, preferably 5 ppm or more, more preferably 15 ppm or more, even more preferably 25 ppm or more, still more preferably 50 ppm or more, still more preferably 100 ppm or more, and preferably 2000 ppm or less, more preferably 1000 ppm or less, still more preferably 500 ppm or less, and still more preferably 300 ppm or less.

[0035] When the cleaning solution of the present invention contains the component (b2), the concentration of the component (b2) in the cleaning solution may be, from the viewpoint of fiber residue, preferably 5 ppm or more, more preferably 15 ppm or more, even more preferably 30 ppm or more, still more preferably 50 ppm or more, still more preferably 100 ppm or more, and preferably 2000 ppm or less, more preferably 1000 ppm or less, still more preferably 750 ppm or less, still more preferably 500 ppm or less, and still more preferably 300 ppm or less.

[0036] In the cleaning solution of the present invention, the mass ratio (b) / (a) of the content of component (b) to the content of component (a), from the viewpoint of fiber residue, is preferably at least 10, more preferably at least 30, even more preferably at least 50, still more preferably at least 100, and preferably at most 8000, more preferably at most 4000, even more preferably at most 2000, still more preferably at most 1000, and still more preferably at most 500. Here, the content of component (b) is the total content of component (b), i.e., the total content of components (b1) and (b2).

[0037] When the cleaning solution of the present invention contains the component (b1), the mass ratio (b1) / (a) of the content of the component (a) to the content of the component (b1) in the cleaning solution is, from the viewpoint of fiber residue, preferably not less than 10, more preferably not less than 30, even more preferably not less than 50, still more preferably not less than 100, and preferably not more than 4000, more preferably not more than 2000, even more preferably not more than 1000, still more preferably not more than 600, and still more preferably not more than 500. It is preferable that the (b) / (a) satisfies the above range, and that the (b1) / (a) also satisfies the above range.

[0038] When the cleaning solution of the present invention contains the component (b2), the mass ratio (b2) / (a) of the content of the component (a) to the content of the component (b2) in the cleaning solution is, from the viewpoint of fiber residue, preferably not less than 10, more preferably not less than 30, even more preferably not less than 60, still more preferably not less than 100, and preferably not more than 4000, more preferably not more than 2000, even more preferably not more than 1500, still more preferably not more than 1000, and still more preferably not more than 500. It is preferable that the (b) / (a) satisfies the above range, and that the (b2) / (a) also satisfies the above range.

[0039] When the cleaning solution of the present invention contains the component (b1) and the component (b2), the mass ratio of the content of the component (b1) to the content of the component (b2) in the cleaning solution, (b1) / (b2), is, from the viewpoint of fiber residue, preferably 0.01 or more, more preferably 0.1 or more, even more preferably 0.2 or more, still more preferably 0.35 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.

[0040] The cleaning solution of the present invention contains water. That is, the remainder other than the components (a) and (b) and any optional components may be water. Examples of water include ion-exchanged water, tap water, groundwater, and river water.

[0041] The cleaning solution of the present invention may contain a surfactant other than the component (b) (hereinafter referred to as component (b')). The component (b') may be one or more surfactants selected from the following components (b'1) and (b'2). Component (b'1): Anionic surfactant other than component (b1) Component (b'2): a nonionic surfactant other than component (b2)

[0042] From the viewpoint of fiber retention, examples of the component (b'1) include one or more selected from alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates other than component (b1-1), polyoxyalkylene alkenyl ether sulfates other than component (b1-1), alkylbenzenesulfonic acids, alkenylbenzenesulfonic acids, alkanesulfonic acids, α-olefinsulfonic acids, internal olefinsulfonic acids other than component (b1-2), alkyl or dialkyl sulfosuccinic acids, alkenyl or dialkenyl sulfosuccinic acids, polyoxyalkylene alkyl or polyoxyalkylene dialkyl sulfosuccinic acids, polyoxyalkylene alkyl or polyoxyalkylene dialkyl sulfosuccinic acids, alkylsuccinic acids, alkenylsuccinic acids, fatty acids, and salts thereof.

[0043] Among these, from the viewpoint of fiber retention, one or more anionic surfactants selected from the compound represented by the following general formula (b'1-1) [hereinafter referred to as component (b'1-1)], the compound represented by general formula (b'1-2) [hereinafter referred to as component (b'1-2)], and the compound represented by general formula (b'1-3) [hereinafter referred to as component (b'1-3)] may be mentioned.

[0044] R 1-1 -B-SO3M (b'1-1) [In general formula (b'1-1), R 1-1 is a hydrocarbon group having 8 to 22 carbon atoms, B is a benzene ring, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. 1-1a The sulfonic acid group is bonded at the para position.

[0045] In general formula (b'1-1), R 1-1 From the viewpoint of fiber retention, is a hydrocarbon group having 8 or more carbon atoms, preferably 9 or more, more preferably 10 or more, and 22 or less, preferably 18 or less, more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the general formula (b'1-1), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and further preferably sodium. The content of the component (b'1-1) in the present invention is based on the amount of the compound converted into a sodium salt.

[0046] R 1-2 -O-(EO) p -SO3M (b'1-2) [In general formula (b'1-2), R 1-2 is a hydrocarbon group having 8 to 22 carbon atoms, EO is an ethyleneoxy group, p is the average number of moles of EO added and is a number of 0.1 to 10, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium.

[0047] In general formula (b'1-2), R 1-2 From the viewpoint of fiber retention, is a hydrocarbon group having 8 or more carbon atoms, preferably 9 or more, more preferably 10 or more, and 22 or less, preferably 18 or less, more preferably 16 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In general formula (b'1-2), EO is an ethyleneoxy group. In the general formula (b'1-2), p is a number of 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and 10 or less, preferably 5 or less, more preferably 3 or less, from the viewpoint of fiber retention. In the general formula (b'1-2), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and further preferably sodium. The content of the component (b'1-2) in the present invention is based on the amount of the compound converted into a sodium salt.

[0048] R 1-3 -COOM (b'1-3) [In general formula (b'1-3), R 1-3 is a hydrocarbon group having 8 to 22 carbon atoms, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium.

[0049] In general formula (b'1-3), R 1-3 From the viewpoint of fiber retention, is a hydrocarbon group having 8 or more carbon atoms, preferably 9 or more, more preferably 10 or more, and 22 or less, preferably 18 or less, more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In the general formula (b'1-3), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (1 / 2 atom) such as magnesium or calcium, or an organic ammonium. M is more preferably an alkali metal such as sodium or potassium, or an alkanol ammonium such as monoethanol ammonium or diethanol ammonium, and further preferably sodium. The content of the component (b'1-3) in the present invention is based on the amount of the compound converted into a sodium salt.

[0050] From the viewpoint of fiber retention, examples of the (b'2) component include one or more selected from alkyl monoglyceryl ethers, polyoxyalkylene monoalkyl or alkenyl ethers other than the (b2-2) component, polyoxyalkylene fatty acid esters other than the (b2-1) component, sorbitan-based nonionic surfactants, aliphatic alkanolamides, fatty acid monoglycerides, and sucrose fatty acid esters.

[0051] Among these, from the viewpoint of fiber retention, one or more nonionic surfactants selected from the compound represented by the following general formula (b'2-1) [hereinafter referred to as component (b'2-1)] and the compound represented by the general formula (b'2-2) [hereinafter referred to as component (b'2-2)] may be mentioned.

[0052] R 2-1 -O-(EO) n -R 2-2 (b'2-1) [In general formula (b'2-1), R 2-1 is a hydrocarbon group having 9 to 18 carbon atoms, EO is an ethyleneoxy group, n is the average number of moles of EO added and is a number of 3 to 50, R 2-2 is a hydrogen atom or a methyl group.

[0053] In general formula (b'2-1), R 2-1 From the viewpoint of fiber retention, is a hydrocarbon group having 9 or more carbon atoms, preferably 10 or more, more preferably 11 or more, and 18 or less, preferably 15 or less, more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In general formula (b'2-1), EO is an ethyleneoxy group. In general formula (b'2-1), n ​​is a number of 3 or more, preferably 5 or more, more preferably 10 or more, and 50 or less, preferably 30 or less, more preferably 20 or less, from the viewpoint of fiber retention. In general formula (b'2-1), R 2-2 is preferably a hydrogen atom.

[0054] R 2-3 -O-(EO)x -(PO) y -(EO) z -R 2-4 (b'2-2) [In general formula (b'2-2), R 2-3 is a hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, EO and PO are block-bonded in this order, y is the average number of moles of PO added and is a number of 1 to 6, x and z are the average number of moles of EO added, x+z is a number of 3 to 50, R 2-4 is a hydrogen atom or a methyl group.

[0055] In general formula (b'2-2), R 2-3 From the viewpoint of fiber retention, is a hydrocarbon group having 10 or more carbon atoms, preferably 11 or more, more preferably 12 or more, and 24 or less, preferably 18 or less, more preferably 14 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group. In general formula (b'2-2), y is a number of 1 or more, preferably 1.5 or more, more preferably 2 or more, and 6 or less, preferably 5 or less, more preferably 4 or less, from the viewpoint of fiber retention. In general formula (b'2-2), x+z is a number of 3 or more, preferably 5 or more, more preferably 10 or more, and 50 or less, preferably 30 or less, more preferably 25 or less, from the viewpoint of fiber retention. In general formula (b'2-2), R 2-4 is preferably a hydrogen atom.

[0056] The cleaning liquid of the present invention may further contain, as optional components, components known to be used in detergents, fabric softeners, etc., such as the following components (1) to (16), within a range that does not affect the effects of the present invention.

[0057] (1) Other surfactants From the viewpoint of fiber retention, the other surfactants are not particularly limited, but include one or more surfactants selected from (c) cationic surfactants and (d) amphoteric surfactants.

[0058] From the viewpoint of fiber retention, examples of the (c) cationic surfactant include compounds represented by the following general formula (c1).

[0059] [ka]

[0060] [In the formula, R 1c is a chain hydrocarbon group having 8 to 24 carbon atoms, R 2c is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 3c and R 4c are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; - is an alkyl sulfate ion having 1 to 3 carbon atoms, or a halide ion.

[0061] In general formula (c1), R 1c From the viewpoint of fiber retention, the carbon number of the chain hydrocarbon group is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less.

[0062] R 2c is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, R 2c From the viewpoint of fiber retention, the carbon number of the chain hydrocarbon group is preferably 9 or more, more preferably 10 or more, and is preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. R 2c From the viewpoint of fiber retention, the chain hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

[0063] R 3c , R 4care each independently an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0064] R 1c , R 2c Specific examples of the chain hydrocarbon group are octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl groups, and from the viewpoint of fiber retention, nonyl and decyl groups are preferred, with decyl group being more preferred.

[0065] Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group. - is CH3SO4 - , CH3CH2SO4 - , or a halide ion.

[0066] More specific examples of the compound represented by the general formula (c1) from the viewpoint of fiber retention include one or more compounds selected from N-ethyl-N,N-dimethyltetradecyl ammonium salt, trimethylhexadecyl ammonium salt, N,N-dioctyl-N,N-dimethyl ammonium salt, N,N-dinonyl-N,N-dimethyl ammonium salt, N,N-didecyl-N,N-dimethyl ammonium salt, N,N-dioctyl-N-ethyl-N-methyl ammonium salt, N,N-dinonyl-N-ethyl-N-methyl ammonium salt, and N,N-didecyl-N-ethyl-N-methyl ammonium salt. Mono-long chain ammonium salts and di-long chain ammonium salts can also be used in combination. The counter ion of these salts is CH3SO4 - , CH3CH2SO4 - , or a halide ion such as chloride ion.

[0067] As the cationic surfactant, from the viewpoint of fiber retention, a bispyridinium compound can also be mentioned. Examples of the bispyridinium compound include those described in British Patent No. 1533952, Japanese Patent Publication No. 52-105228, and International Publication No. 2014 / 100807. Specifically, from the viewpoint of fiber retention, the bispyridinium compound is preferably a compound represented by the following general formula (c3) or a compound represented by the following general formula (c4).

[0068] [ka]

[0069] [wherein Y is an alkylene or alkenylene group having 4 to 18 carbon atoms; R 5c each represents an alkyl group having 6 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group with or without halogen substitution, and A is an anion. q is 1 or 2, r is 1 or 2, and q×r=2.

[0070] A is a monovalent or divalent anion, for example, chloride, bromide, phosphate, orthosilicate, an organic acid, for example, a compound of the formula R 6c It can be an anion from a compound such as an organic acid having -COO- or an alkyl (having 1 to 40 carbon atoms) sulfonic acid. Here, R 6c is hydrogen, hydroxyl, or an alkyl group having from 1 to 40 carbon atoms. A may be an anion from an acid agent which is a pH adjuster as described below.

[0071] From the viewpoint of fiber retention, examples of organic acids corresponding to the anion of A include acetic acid, propionic acid, phosphoric acid, glycolic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, glycyrrhizic acid, salicylic acid, stearic acid, phosphonic acid, trifluoroacetic acid, cyanoacetic acid, 4-cyanobenzoic acid, 2-chlorobenzoic acid, 2-nitrobenzoic acid, phenoxyacetic acid, and benzenesulfonic acid.

[0072] From the viewpoint of fiber retention, preferred bispyridinium compounds are compounds of general formula (c4), and further octenidine dihydrochloride (in general formula (c4), R 5c is an n-octyl group, Y is an n-decenyl group, A is Cl, q is 1, and r is 2, CAS number 70775-75-6). In the detergent composition for fabric products of the present invention, the cationic surfactant may be used alone or in combination of two or more kinds.

[0073] From the viewpoint of fiber retention, the amphoteric surfactant (d) may be one or more surfactants selected from betaine surfactants and amine oxide surfactants. Specifically, from the viewpoint of fiber retention, the amphoteric surfactant (d) may be one or more amphoteric surfactants selected from sulfobetaine, carbobetaine, and amine oxide.

[0074] From the viewpoint of fiber residual properties, examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkyl group preferably has 10 or more and 18 or less carbon atoms; N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkyl group has 10 or more and 18 or less carbon atoms; N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, in which the alkanoyl group has 10 or more and 18 or less carbon atoms; and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, in which the alkanoyl group has 10 or more and 18 carbon atoms.

[0075] From the viewpoint of fiber retention, examples of carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaines having an alkyl group with 10 to 18 carbon atoms and compounds represented by the following general formula.

[0076] [ka]

[0077] [In the formula, R 1d represents an alkyl or alkenyl group having 7 to 21 carbon atoms; R 2d represents a propylene group, and R 1d and R 4d each independently represents an alkyl group having 1 to 3 carbon atoms.

[0078] As the amine oxide, from the viewpoint of fiber retention, a compound of the following general formula is preferable.

[0079] [ka]

[0080] [In the formula, R 5d represents a hydrocarbon group having 7 to 22 carbon atoms, which is preferably an alkyl or alkenyl group from the viewpoint of fiber retention, more preferably an alkyl group; R 6d and R 7d are the same or different and each represents an alkyl group having 1 to 3 carbon atoms. D represents an -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. m and p represent m=0 and p=0 or m=1 and p=1.

[0081] (2) pH adjuster From the viewpoint of fiber retention, an acidic or alkaline agent may be contained as a pH adjuster. The acid agent may be one or more selected from organic acids and inorganic acids. From the viewpoint of fiber retention, the organic acid may be one or more selected from citric acid, malic acid, acetic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, propionic acid, oxalic acid, glutaric acid, adipic acid, gallic acid, mellitic acid, cinnamic acid, salicylic acid, phthalic acid, benzoic acid, pyruvic acid, oxaloacetic acid, and aconitic acid. From the viewpoint of fiber residue, the inorganic acid may be one or more selected from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and carbonic acid. From the viewpoint of fiber retention, examples of the alkaline agent include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which one or more and three or less groups bonded to nitrogen atoms are alkanol groups having 2 to 4 carbon atoms, and the remaining are alkyl groups or hydrogen atoms having 1 to 4 carbon atoms. From the viewpoint of fiber retention, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. From the viewpoint of fiber retention, a hydrogen atom or a methyl group is preferable other than the alkanol group, and a hydrogen atom is particularly preferable. From the viewpoint of fiber retention, examples of the alkanolamine include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine.

[0082] (3) Chelating agents From the viewpoint of fiber retention, specific examples of the chelating agent include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, and the like, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, malic acid, and the like, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof.

[0083] (4) Anti-redeposition agents and / or polymeric dispersants From the viewpoint of fiber retention, examples of anti-redeposition agents and / or polymer-based dispersants include polyacrylic acid, polymaleic acid, carboxymethyl cellulose, and the like.

[0084] (5) Bleach From the viewpoint of fiber residual properties, examples of bleaching agents include hydrogen peroxide, sodium percarbonate, and sodium perborate.

[0085] (6) Bleach activator From the viewpoint of fiber residue, examples of bleach activators include tetraacetylethylenediamine and bleach activators represented by general formulas (I-2) to (I-7) of JP-A-6-316700.

[0086] (7) Enzymes From the viewpoint of fiber retention, the enzyme may be one or more enzymes selected from amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase, cellulase, protease and lipase.

[0087] (8) Fluorescent dyes From the viewpoint of fiber retention, examples of the fluorescent dye include fluorescent dyes commercially available as Tinopal CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0088] (9) Antioxidants From the viewpoint of fiber retention, examples of the antioxidant include known antioxidant compounds such as butylated hydroxytoluene (common name: BHT), butylated hydroxyanisole (common name: BHA), distyrenated cresol, ascorbic acid (common name: vitamin C), tocopherol (common name: vitamin E), coffee bean extract (chlorogenic acid), and green tea extract (catechin), as well as known inorganic salts such as sodium sulfite and sodium hydrogen sulfite.

[0089] (10) From the viewpoint of fiber residue, colorants, fragrances, antibacterial preservatives other than component (a), ultraviolet protection agents, antifoaming agents such as silicones, etc.

[0090] (11) Organic solvents having a hydroxyl group From the viewpoint of fiber residue, one or more compounds selected from the following components (11-1) to (11-6) are used as the organic solvent having a hydroxyl group. (11-1) Component: A monohydric alcohol having an aliphatic hydrocarbon group having 2 to 6 carbon atoms From the viewpoint of fiber retention, examples of the component (11-1) include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0091] (11-2) Component: dihydric to hexahydric alcohol having 2 to 6 carbon atoms From the viewpoint of fiber retention, examples of the component (11-2) include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-Methyl-2,4-pentanediol is also called hexylene glycol.

[0092] Component (11-3): polyalkylene glycol containing an alkylene glycol unit having 2 to 4 carbon atoms From the viewpoint of fiber retention, examples of the component (11-3) include polyalkylene glycols selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols having a weight-average molecular weight of 400 or more and 4,000 or less, and polypropylene glycols having a weight-average molecular weight of 400 or more and 4,000 or less.

[0093] Component (11-4): a monoalkyl ether of (mono- or poly)alkylene glycol having an alkylene glycol unit having from 2 to 4 carbon atoms and an alkyl group having from 1 to 4 carbon atoms. From the viewpoint of fiber residue, examples of the component (11-4) include compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0094] (11-5) Component: Alkyl glyceryl ether having an alkyl group with 1 to 8 carbon atoms Examples of the (11-5) component, from the viewpoint of fiber retention, include alkyl glyceryl ethers selected from 1-methyl glyceryl ether, 2-methyl glyceryl ether, 1,3-dimethyl glyceryl ether, 1-ethyl glyceryl ether, 1,3-diethyl glyceryl ether, triethyl glyceryl ether, 1-pentyl glyceryl ether, 2-pentyl glyceryl ether, 1-octyl glyceryl ether, and 2-ethylhexyl glyceryl ether.

[0095] (11-6) Component: Aromatic alkyl ether of (mono- or poly-)alkylene glycol having an alkylene glycol unit having 2 or 3 carbon atoms From the viewpoint of fiber retention, examples of the (11-6) component include compounds selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether having an average molecular weight of about 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

[0096] In the above components (11-4) and (11-6), the term "(mono- or poly)alkylene glycol" means a monoalkylene glycol or a polyalkylene glycol. Also, the term "polyalkylene glycol" means a glycol containing 2 to 9 alkylene glycol units.

[0097] (12) Hydrotropes From the viewpoint of fiber retention, the hydrotrope is an organic compound having an anionic group, and further includes alkylbenzene carboxylic acid or alkylbenzene sulfonic acid having one or two alkyl groups selected from methyl, ethyl, or propyl groups and one sulfonic acid or carboxylic acid group, or a salt thereof, and benzoic acid or a salt thereof. More specifically, from the viewpoint of fiber retention, the hydrotrope is paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, or benzoic acid, and the salt is preferably an alkali metal salt.

[0098] (13)Fragrance From the viewpoint of fiber retention, the perfume has a masking effect and, in some cases, may itself be a substrate having deodorizing properties. As the fragrance, from the viewpoint of fiber retention, for example, the fragrances described in "Basic Knowledge of Fragrances and Fragrances, edited by Nakajima Mototaka, published by Sangyo Tosho Co., Ltd., 4th printing, April 20, 2005" and the fragrances described in JP-T-10-507793 can be used. In addition, the fragrance technology described in JP-A-2014-213072 can be used, and silicate ester fragrances and microcapsule fragrances can also be used.

[0099] (14) Deodorizing base material From the viewpoint of fiber residual property, examples of deodorizing base materials include polyhydroxyamine compounds described in JP 2018-29836 A. Examples of polyhydroxyamine compounds include tris(hydroxymethyl)aminomethane, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1,3-propanediol, and combinations of these with inorganic acids such as hydrochloric acid.

[0100] (15) Fabric softener From the viewpoint of fiber retention, the softener base is preferably a quaternary ammonium salt compound of the following general formula:

[0101] [ka]

[0102] [In the formula, R 1e , R 2e , R 3e are each independently a residue (acyl group) obtained by removing OH from a fatty acid having 16 to 22 carbon atoms, or a hydrogen atom. 1e , R 2e , R 3e At least one of R is an acyl group. 4e is an alkyl group having 1 to 3 carbon atoms; Z - is an anion.

[0103] The softening base may be a mixture of quaternary ammonium salt compounds of the general formula above. Such a mixture may be, for example, a mixture of quaternary ammonium salt compounds of the general formula above, 4e is an alkyl group having 1 to 3 carbon atoms; Z - A mixture of quaternary ammonium salts, where R is an organic or inorganic anion. 1e is a fatty acid residue (x) obtained by removing OH from a fatty acid having 16 to 22 carbon atoms, and R 2e and R 3e Compound (e1) in which R is a hydrogen atom; 1e and R 2e is the fatty acid residue (x), and R 3e Compound (e2) in which R is a hydrogen atom; 1e , R 2e and R 3e is the fatty acid residue (x).

[0104] R 1e , R 2e , R 3eFurthermore, from the viewpoint of fiber retention, the fatty acid residue (x) is preferably a residue obtained by removing OH (hydroxyl group) from a fatty acid having 16 or more and 22 or less carbon atoms, preferably 16 or more and 18 or less carbon atoms. Specific examples of fatty acids from the viewpoint of fiber retention include one or more selected from stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, safflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, olive oil fatty acid, hydrogenated palm oil fatty acid, beef tallow fatty acid, and hydrogenated beef tallow fatty acid. From the viewpoint of fiber retention, in the general formula, R 4e is preferably a methyl group or an ethyl group. From the viewpoint of fiber retention, in the general formula, Z - is an organic or inorganic anion, and is preferably an anion selected from a halogen ion such as a chlorine ion, an alkyl sulfate ion having 1 to 3 carbon atoms, a fatty acid ion having 12 to 18 carbon atoms, and a benzenesulfonate ion which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms. From the viewpoint of fiber retention, in the present invention, an alkyl sulfate ion having 1 to 3 carbon atoms is more preferred, and a methyl sulfate ion or an ethyl sulfate ion is even more preferred. The quaternary ammonium salt compound of the general formula can be obtained by subjecting an esterification reaction product obtained by a method of subjecting a fatty acid to a dehydration esterification reaction with triethanolamine, or a method of subjecting a fatty acid lower alkyl ester (wherein the lower alkyl is a methyl group, an ethyl group, or a propyl group) to a transesterification reaction with triethanolamine, and then subjecting the resulting esterification reaction product to a quaternization reaction with an alkylating agent.

[0105] (16) Fabric softener From the standpoint of fiber retention, examples of softening aids include polyhydric alcohol fatty acid esters such as glycerin, sorbitol, and pentaerythritol.

[0106] Examples of textile products include fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using the hydrophobic and hydrophilic fibers, and products obtained using the fabrics, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitted clothing, socks, underwear, tights, and masks. The fibers constituting the textile product may be either hydrophobic or hydrophilic. The fibers may be either natural fibers, chemical fibers, or a mixture thereof. From the viewpoint of fiber retention, it is preferable that the textile product contains chemical fibers. Examples of hydrophobic fibers include protein fibers (milk protein casein fibers, Promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fibers, carbon fibers, alumina fibers, silicone carbide fibers, rock fibers (rock fibers), slag fibers (slag fibers), and metal fibers (gold thread, silver thread, steel fiber). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.).

[0107] In the washing method of the present invention, the amount (mg / L) of the component (a) relative to the total amount of water used for rinsing may be, from the viewpoint of fiber residue, preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, still more preferably 0.025 or more, and preferably 5 or less, more preferably 1 or less, and even more preferably 0.2 or less.

[0108] From the viewpoint of fiber residual property, the temperature of the rinse liquid is preferably 0°C or higher, more preferably 3°C or higher, even more preferably 5°C or higher, and preferably 70°C or lower, more preferably 60°C or lower, even more preferably 50°C or lower, and still more preferably 40°C or lower.

[0109] From the viewpoint of fiber retention, the rinsing time is preferably 10 seconds or more, more preferably 30 seconds or more, and preferably 30 minutes or less, more preferably 10 minutes or less, even more preferably 8 minutes or less, and even more preferably 5 minutes or less.

[0110] Rinsing can be performed by rinsing with a pool of water, rinsing with running water, or a combination of these. The contact of the rinsing liquid with the textile product can be carried out, for example, by supplying a previously prepared rinsing liquid containing components (a) and (b) and having a pH of 6.5 or less to the textile product. In addition, the rinsing of the present invention may be performed by supplying water having a pH of 6.5 or less to a textile product containing components (a) and (b) so that the rinsing liquid containing components (a) and (b) and having a pH of 6.5 or less comes into contact with the textile product. Alternatively, the rinsing method of the present invention may be carried out by blending the (a) component, the (b) component and the pH adjuster in a cleaning agent, treating the textile product so that the (a) component, the (b) component and the pH adjuster remain in the textile product after washing, supplying water (whose pH may be 6.5 or less or may be greater than 6.5) to the textile product after washing to adjust its pH to 6.5 or less, and contacting the textile product with the rinse liquid having a pH of 6.5 or less in the presence of the (a) component and the (b) component. In general, when domestic water such as tap water is used for rinsing, the pH is close to neutral, so that if the textile product contains an acidic agent as a pH adjuster, the acidic agent functions as a pH lowering agent, and a rinse liquid having a pH of 6.5 or less can be easily obtained. That is, if the cleaning liquid is acidic and water having a pH of more than 6.5 is supplied to a textile product containing the (a) component to adjust its pH to 6.5 or less, the rinsing method of the present invention may be carried out without the step of preparing rinse water having a pH of 6.5 or less in advance.

[0111] The washing method of the present invention can be carried out, for example, in a washing machine for home or commercial use. In washing in a washing machine, a textile product is washed with a detergent, and then dehydrated as necessary, and then rinsed. In this case, the washing method of the present invention can be carried out by rinsing the textile product with a rinse solution having a pH of 6.5 or less in the presence of components (a) and (b). Components (a) and (b) can be made to coexist with the textile product during rinsing by, for example, blending components (a) and (b) in a detergent or washing solution, supplying components (a) and (b) to the textile product before rinsing, blending components (a) and (b) in a rinse solution, or a combination of these methods.

[0112] In the washing method of the present invention, the concentration of the component (a) in the rinse liquid may be, from the viewpoint of fiber residue, preferably 0.001 ppm or more, more preferably 0.005 ppm or more, even more preferably 0.01 ppm or more, still more preferably 0.025 ppm or more, and preferably 1 ppm or less, more preferably 0.25 ppm or less, and even more preferably 0.1 ppm or less.

[0113] In the washing method of the present invention, the amount (mg / kg) of component (a) in the rinse liquid may be, from the viewpoint of fiber residue, preferably 0.02 or more, more preferably 0.2 or more, and preferably 20 or less, more preferably 5 or less, even more preferably 2 or less, and still more preferably 1 or less, based on the mass (kg) of the dry textile product.

[0114] In the washing method of the present invention, the concentration of the (b) component in the rinse liquid may be, from the viewpoint of fiber residue, preferably 1 ppm or more, more preferably 3 ppm or more, even more preferably 5 ppm or more, still more preferably 10 ppm or more, and preferably 300 ppm or less, more preferably 150 ppm or less, even more preferably 75 ppm or less, and still more preferably 30 ppm or less.

[0115] In the washing method of the present invention, when the rinse liquid contains the component (b1), the concentration of the component (b1) in the rinse liquid may be, from the viewpoint of fiber residue, preferably 0.5 ppm or more, more preferably 1.5 ppm or more, even more preferably 2.5 ppm or more, still more preferably 5 ppm or more, still more preferably 10 ppm or more, and preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 50 ppm or less, and still more preferably 30 ppm or less.

[0116] In the washing method of the present invention, when the rinsing liquid contains the component (b2), the concentration of the component (b2) in the rinsing liquid may be, from the viewpoint of fiber residue, preferably 0.5 ppm or more, more preferably 1.5 ppm or more, even more preferably 3 ppm or more, still more preferably 5 ppm or more, still more preferably 10 ppm or more, and preferably 200 ppm or less, more preferably 100 ppm or less, still more preferably 75 ppm or less, still more preferably 50 ppm or less, and still more preferably 30 ppm or less.

[0117] In the present invention, the mass ratios of (b) / (a), (b1) / (a), (b2) / (a), and (b1) / (b2) in the rinsing liquid may each be within the ranges described above for the cleaning liquid of the present invention. In the present invention, the rinsing liquid may also contain the optional components described for the cleaning liquid of the present invention.

[0118] In the washing method of the present invention, from the viewpoint of fiber residue, a rotary washing machine can also be used for rinsing. From the viewpoint of fiber residue, specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and an agitator washing machine. These rotary washing machines can be commercially available for home use. In the present invention, it is preferable to use a drum washing machine, since the amount of water used for one wash can be further reduced.

[0119] As an embodiment of the present invention, for example, there is provided a washing method for washing a textile product and rinsing the washed textile product, comprising the steps of: A textile product is washed using a cleaning solution containing the components (a) and (b), The washed textile product containing the components (a) and (b) is rinsed by contacting the textile product with a rinse solution having a pH of 6.5 or less. The washing method may be appropriately applied to the washing method of the present invention. EXAMPLES

[0120] <Component (a)> a-1: Dichrosan

[0121] <(b) Component> ·b-1: (b1-1) component, in general formula (b1-1), R 1 is an alkyl group having 12 to 14 carbon atoms, and PO and EO are R 1 A compound in which a block bond is formed by bonding -O- to PO and EO in that order, q is 2, r is 2, and M is monoethanolammonium. b-2: (b1-2) component, potassium salt of internal olefin sulfonate having 16 carbon atoms (hereinafter also referred to as C16IOS)

[0122] C16IOS was obtained by using an internal olefin having a carbon number of 16, with reference to the method described in the manufacturing example of JP 2014-76988 A. The mass ratio of the olefin body (potassium olefin sulfonate) / hydroxy body (potassium hydroxyalkanesulfonate) in the obtained internal olefin sulfonate potassium salt of C16IOS was 17 / 83. The mass ratio of the position distribution of the sulfonic acid group of the hydroxy body in C16IOS was 1st / 2nd / 3rd / 4th / 5th / 6th / 7th / 8th / 9th positions=2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% / 0% (total 100% by mass). In addition, (IO-1S) / (IO-2S)≒1.6 (mass ratio). Here, (IO-1S) is the content of internal olefin sulfonate salts in which the sulfonic acid group is present at the 2nd or more and the 4th or less position, and (IO-2S) is the content of internal olefin sulfonate salts in which the sulfonic acid group is present at the 5th position or more.

[0123] The mass ratio of the position distribution of sulfonic acid groups in the internal olefin sulfonate salt was measured by high performance liquid chromatography / mass spectrometry (HPLC-MS). Specifically, hydroxy bodies to which sulfonic acid groups are bonded were separated by high performance liquid chromatography (HPLC) and each was identified by subjecting each to a mass spectrometer (MS). As a result, each ratio was calculated from the HPLC-MS peak area. In this specification, each ratio calculated from the peak area was calculated as a mass ratio. The apparatus and conditions used for the measurement were as follows: HPLC device "LC-20ASXR" (Shimadzu Corporation), column "ODS Hypersil (registered trademark)" (4.6 x 250 mm, particle size: 3 μm, Thermo Fisher Scientific), sample preparation (1000 times dilution with methanol), eluent A (10 mM ammonium acetate added water), eluent B (10 mM ammonium acetate added methacrylonitrile / water = 95 / 5 (v / v) solution), gradient (0 min (A / B = 60 / 40) → 15.1 to 20 min (30 / 70) → 20.1 to 30 min (60 / 40), MS device "LCMS-2020" (Shimadzu Corporation), ESI detection (anion detection m / z: 321.10 (component with carbon number 16), column temperature (40 ° C), flow rate (0.5 mL / min), injection volume (5 μL)

[0124] The mass ratio of the hydroxyl / olefin of the internal olefin sulfonate was measured by HPLC-MS. Specifically, the hydroxyl and olefin were separated by HPLC and each was identified by MS. As a result, the ratio of each was calculated from the HPLC-MS peak area. The apparatus and conditions used for the measurement were as follows: HPLC apparatus (trade name: Agilent Technology 1100, manufactured by Agilent Technologies), column (trade name: L-column ODS 4.6 x 150 mm, manufactured by Chemicals Evaluation and Research Institute, Japan), sample preparation (1000-fold dilution with methanol), eluent A (water with 10 mM ammonium acetate added), eluent B (methanol with 10 mM ammonium acetate added), gradient (0 min (A / B = 30 / 70%) → 10 min (30 / 70%) → 55 min (0 / 100%) → 65 min (0 / 100%) → 66 min (30 / 70%) → 75 min (30 / 70%)), MS apparatus (trade name: Agilent Technology 1100MS SL (G1946D)), MS detection (anion detection m / z 60-1600, UV 240 nm). In addition, a specified amount of α-olefin sulfonate having an aliphatic hydrocarbon group of the carbon number was added to C16IOS as an external standard, and the mass of C16IOS was calculated by comparing the peak area of ​​α-olefin sulfonate with that of C16IOS. The number of moles of C16IOS was calculated from the molecular weight of C16IOS. The molecular weight of C16IOS was calculated in the acid form. The molecular weight of the olefin form of the internal olefin sulfonate is 304.5, and the molecular weight of the HAS form is 322.6.

[0125] ·b-3: (b2-1) component, in general formula (b2-1), R 2 is an alkyl group having 16 to 18 carbon atoms, AO is an ethyleneoxy group, m is 15, R 3 Compounds in which is a methyl group ·b-4: (b2-2) component, in general formula (b2-2), R 4 is an alkyl group having 12 to 14 carbon atoms, s is 3.7, t is 16.5, and R 5 Compounds where is a hydrogen atom

[0126] <(b') component> ·b'-1: (b'1-1) component, in general formula (b'1-1), R 1-1 Compounds in which is an alkyl group having 10 to 14 carbon atoms and M is sodium ·b'-2: (b'1-2) component, in general formula (b'1-2), R 1-2 is an alkyl group having 10 to 16 carbon atoms, p is 2, and M is sodium ·b'-3: (b'2-1) component, in general formula (b'2-1), R 2-1 is an alkyl group having 12 to 14 carbon atoms, n is 10, R 2-2 Compounds where is a hydrogen atom

[0127] (1) Preparation of rinsing solutions with different pH levels Wakayama City tap water (pH 7.5) was mixed with 0.1 M hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to adjust the pH to 6.5, 6.0, 5.5, and 5.0 at 25°C to use as a rinse solution. For pH measurements, a pH meter (HORIBA pH / ion meter D-71) was used that had been calibrated in advance with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution).

[0128] (2) Preparation of test cloth 1.7 kg of cotton cloth (Cotton 2003 (Tanigashou Shoten)) was washed twice in a fully automatic washing machine (National NA-F702P) on the standard cycle (4.7 g of Emulgen 108 (Kao Corporation) during washing, 47 L of water, 9 minutes of washing, 2 rinses, 3 minutes of spin-drying), then washed three times in water only (47 L of water, 9 minutes of washing, 2 rinses, 3 minutes of spin-drying), and dried at 25°C for 24 hours. It was then cut into a size of 6 cm x 6 cm to prepare the test cloth.

[0129] (3) Dichrosan Residue Test Five test cloths (2 g) and 40 g of the cleaning solution shown in Table 1 were placed in a screw tube No. 8 (Maruemu Co., Ltd.), and a cleaning process was performed for 10 minutes at 300 rpm using a reciprocating shaker (TAITEC, STORONGSHAKER SA-2DW). After the cleaning process was completed, the test cloths were dehydrated using a 50 mL syringe (Terumo Co., Ltd.), and the dehydrated test cloths and 40 g of the rinsing solution were placed in a screw tube No. 8 (Maruemu Co., Ltd.), and a rinsing process was performed for 5 minutes at 300 rpm at 25°C using a reciprocating shaker (TAITEC, STORONGSHAKER SA-2DW). After the rinsing process was completed, the test cloths were dehydrated using a 50 mL syringe (Terumo Co., Ltd.) and dried for 24 hours. Two randomly selected dried test cloths were sealed in screw tube No. 8 and the mass of the cloth was measured. 50 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto and ultrasonically treated for 30 minutes in an ultrasonic cleaner. The supernatant was then filtered through a PTFE filter (manufactured by Pall, pore size: 0.45 μm) to obtain a measurement solution. Next, Tinosan HP100 was diluted with methanol to prepare calibration curve solutions with diclosan concentrations of 0.015 μg / mL, 0.03 μg / mL, 0.15 μg / mL, 0.3 μg / mL, and 1.5 μg / mL. The amount of diclosan in the measurement solution was quantified using a liquid chromatography mass spectrometer (hereinafter abbreviated as LCMS device), and the amount of diclosan remaining on the test cloth from the calibration curve solution was determined. The results are shown in Table 1. LCMS equipment: Shimadzu Corporation LCMS2020 Eluent A: 10mmol / L ammonium acetate in distilled water Eluent B: 10mmol / L ammonium acetate in methanol Gradient conditions: Eluent A / B = 1:1 (0 min) → Eluent B (2-5 min) → Eluent A / Eluent B = 1 / 1 (5.1 min-8 min), flow rate: 0.6 mL / min, sample injection volume 5 μL, column temperature 40°C

[0130] [Table 1]

[0131] From the results in Table 1, it can be seen that in the presence of components (a) and (b), the amount of component (a) remaining is improved by rinsing the textile product with a rinse solution having a pH of 6.5 or less, as in the examples. From the results in Table 1, it can be seen that even when components (a) and (b) are blended into a detergent and then rinsed, rinsing is performed in a state in which components (a) and (b) coexist, so that even in a washing method in which components (a) and (b) are blended into a detergent, the effects of the present invention can be obtained by rinsing the textile product with a rinse solution having a pH of 6.5 or less. It is believed that an improvement in the amount of component (a) remaining in a textile product leads to an improvement in the antibacterial effect.

Claims

1. A washing method for washing a textile product and rinsing the washed textile product, wherein the rinsing is carried out by contacting the textile product with a rinse solution containing water and having a pH of 6.5 or less in the presence of the following components (a) and (b): (a) Phenolic antibacterial compounds Component (b): one or more surfactants selected from the following components (b1) and (b2): Component (b1): one or more anionic surfactants selected from the following components (b1-1) and (b1-2): Component (b1-1): Anionic surfactant represented by general formula (b1-1) R １ -O-[(POO) ｑ (EO) ｒ ]-SO ３ M (b1-1) [In general formula (b1-1), R １ is a hydrocarbon group having from 8 to 22 carbon atoms, PO is a propyleneoxy group, EO is an ethyleneoxy group, PO and EO are bonded in a block bond or a random bond, q is the average number of moles of PO added and is a number of from 1 to 5, r is the average number of moles of EO added and is a number of from 0.1 to 10, and M is a hydrogen atom, an alkali metal, an alkaline earth metal (1 / 2 atom), ammonium, or an organic ammonium. Component (b1-2): Internal olefin sulfonate having 14 to 20 carbon atoms Component (b2): one or more nonionic surfactants selected from the following components (b2-1) and (b2-2): Component (b2-1): a nonionic surfactant represented by general formula (b2-1) R ２ COO-(AO) ｍ -R ３ (b2-1) [In general formula (b2-1), R ２ is a hydrocarbon group having 9 to 24 carbon atoms, AO is an alkyleneoxy group, m is the average number of moles of AO added and is a number of 3 to 50, R ３ is a hydrogen atom or a methyl group. Component (b2-2): a nonionic surfactant represented by general formula (b2-2) 2 ４ ---(O) ｓ -(59) ｔ -2 ５ (b2-2) [In general formula (b2-4), R ４ is an aliphatic hydrocarbon group having 10 to 24 carbon atoms, EO is an ethyleneoxy group, PO is a propyleneoxy group, PO and EO are block bonded in this order, s is the average number of moles of PO added and is a number of 0.1 to 20, t is the average number of moles of EO added and is a number of 4 to 25, R ５ is a hydrogen atom or a methyl group.

2. 2. The washing method according to claim 1, wherein the pH of the rinse solution is 5.5 or less.

3. The washing method according to claim 1 or 2, wherein the component (a) is dichrosan.

4. The washing method according to claim 1 or 2, wherein the textile product contains chemical fibers.

5. 3. The washing method according to claim 1, wherein the textile product is washed with a cleaning solution containing the components (a) and (b), and then the textile product containing the components (a) and (b) is rinsed.