A method for enhancing the whitening effect of a liquid detergent composition for textile products.

Abstract

To provide a method for enhancing the whitening effect of a liquid detergent composition for textile products containing a nonionic surfactant and a fluorescent whitening agent having a sulfonic acid group. [Solution] A method for enhancing the whitening effect of a liquid detergent composition for textile products containing the following components (a), (c), (d) and water, wherein the method involves increasing the mass ratio of the content of component (d) to the content of component (c) in the liquid detergent composition for textile products ((d) / (c)). (a) component: a fluorescent whitening agent having a sulfonic acid group or a salt thereof; (c) component: a nonionic surfactant having an aliphatic hydrocarbon group having 10 to 18 carbon atoms and a polyoxyalkylene group; (d) component: an anionic surfactant having one or more groups selected from a sulfonic acid group and a sulfate ester group or a salt thereof.

Description

[Technical Field]

[0001] The present invention relates to a method for enhancing the whitening effect of a liquid detergent composition for textile products. [Background technology]

[0002] Traditionally, liquid laundry detergents containing nonionic surfactants, anionic surfactants, and water have been used. In recent years, it has become known that treating clothing after wear with a laundry detergent composition containing dialkyl (8-10 carbon atoms) quaternary ammonium salts can impart an antibacterial effect to the clothing.

[0003] For example, Patent Document 1 discloses a liquid laundry detergent composition containing a quaternary ammonium salt having hydrocarbon groups of a specific chain length, an inorganic sulfate, and water, which has excellent deodorizing properties. Patent Document 2 discloses a liquid detergent composition containing a nonionic surfactant, a long-chain amine, and a dilong-chain alkyl type cationic surfactant, which has cleaning power, softening effect, does not cause yellowing, and has excellent low-temperature stability.

[0004] It is also known that fluorescent whitening agents are sometimes incorporated into liquid detergent compositions for textile products such as clothing, and the inclusion of fluorescent whitening agents can enhance the whiteness of textile products after washing. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2017-8137 [Patent Document 2] Japanese Patent Publication No. 2003-206500 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] On the other hand, it has newly been found that when a fluorescent whitening agent having a sulfonic acid group is blended in a liquid detergent composition for textile products containing a nonionic surfactant as a main cleaning component, the effect of enhancing the whiteness of the textile products after washing (whitening effect) is insufficient. Therefore, it is desired that a preferable whitening effect is exhibited even in a liquid detergent composition for textile products containing a nonionic surfactant as a main cleaning component. The present invention relates to a method for enhancing the whitening effect of a liquid detergent composition for textile products containing a nonionic surfactant and a fluorescent whitening agent having a sulfonic acid group.

Means for Solving the Problems

[0007] The present invention relates to the following [1] to [5]. [1] A method for enhancing the whitening effect of a liquid detergent composition for textile products containing the following component (a), component (c), component (d) and water, wherein the mass ratio of the content of component (d) to the content of component (c) ((d) component / (c) component) in the liquid detergent composition for textile products is increased. Component (a): A fluorescent whitening agent having a sulfonic acid group or a salt thereof Component (c): A nonionic surfactant having an aliphatic hydrocarbon group having 10 to 18 carbon atoms and a polyoxyalkylene group Component (d): An anionic surfactant having at least one group selected from a sulfonic acid group and a sulfate group or a salt thereof [2] The enhancing method according to [1] above, wherein component (a) contains a fluorescent whitening agent having a sulfonic acid group or a salt thereof and a biphenyl group. [3] The enhancing method according to [1] or [2] above, wherein component (a) contains a 4,4'-bis(2-sulfostyryl)biphenyl dialkali metal salt. [4] The enhancing method according to any one of [1] to [3] above, wherein the liquid detergent composition for textile products further contains, as component (b), at least one compound selected from the group consisting of dichlorosan and a cationic surfactant having two aliphatic hydrocarbon groups having 8 carbon atoms. 〔5〕 A liquid detergent composition for textile products containing the following components (a), (c), (d) and water, wherein the mass ratio of the content of component (d) to the content of component (c) ((d) component / (c) component) in the liquid detergent composition for textile products is 0.01 or more. Component (a): A fluorescent whitening agent having a sulfonic acid group or a salt thereof Component (c): A nonionic surfactant having an aliphatic hydrocarbon group with 10 to 18 carbon atoms and a polyoxyalkylene group Component (d): An anionic surfactant having one or more groups selected from a sulfonic acid group and a sulfate ester group or a salt thereof

Effects of the Invention

[0008] According to the present invention, a method for enhancing the whitening effect of a liquid detergent composition for textile products containing a nonionic surfactant and a fluorescent whitening agent having a sulfonic acid group can be provided.

Modes for Carrying Out the Invention

[0009] The inventors of the present invention noticed that in a liquid detergent composition for textile products having a nonionic surfactant as a main cleaning component, when a fluorescent whitening agent having a sulfonic acid group is blended, the whitening effect that can be expected by the blending tends not to be achieved. Although it is speculation, it is considered that the adsorption of the fluorescent whitening agent to the textile product is inhibited because the fluorescent whitening agent having a sulfonic acid group is incorporated into the micelles of the nonionic surfactant.

[0010] As a result of further studies by the inventors of the present invention to solve such problems, it was found that by using an anionic surfactant having a specific structure in combination with a composition containing a specific nonionic surfactant and a fluorescent whitening agent, the whitening effect is enhanced. Such an effect is presumably due to the anionic surfactant inhibiting the incorporation of the fluorescent whitening agent into the micelles in the nonionic surfactant.

[0011] [Method for Enhancing Whitening Effect] The present invention relates to a method for enhancing the whitening effect of a liquid detergent composition for textile products containing the following components (a), (c), (d), and water, wherein the method for enhancing the whitening effect involves increasing the mass ratio of the content of component (d) to the content of component (c) in the liquid detergent composition for textile products ((d) / (c)).

[0012] <(a) Components> (a) Component is a fluorescent whitening agent having a sulfonic acid group or a salt thereof. Component (a) preferably contains one or more fluorescent whitening agents selected from the group consisting of fluorescent whitening agents having a sulfonic acid group or a salt thereof and a biphenyl group, and fluorescent whitening agents having a sulfonic acid group or a salt thereof and a stilbene group. The fluorescent whitening agent as component (a) may be blended into the liquid detergent composition for textile products as one type, or two or more types.

[0013] (a) In component (a), preferred examples of fluorescent whitening agents having a sulfonic acid group or a salt thereof and a biphenyl group include 4,4'-bis(2-sulfostyryl)biphenyl dialkali metal salt (preferably sodium) and 4,4'-bis(2-sulfo-4 chlorostyryl)biphenyl dialkali metal salt (preferably sodium), with 4,4'-bis(2-sulfostyryl)biphenyl disodium being particularly preferred in terms of whitening effect. (a) Examples of fluorescent whitening agents having a sulfonic acid group or a salt thereof and a stilbene group include compounds of general formula (A) (where M is sodium), and 4,4'-bis((4-amino-6-morpholino-1,3,5-triazinyl-2)amino)stilbene-2,2'-disulfonic acid metal salt (preferably sodium) is preferred.

[0014] [ka]

[0015] <(c) component> Component (c) is a nonionic surfactant having an aliphatic hydrocarbon group with 10 to 18 carbon atoms and a polyoxyalkylene group. Component (c) has the effect of adhering to textile products and washing away dirt.

[0016] Component (c) is not particularly limited as long as it is a nonionic surfactant having such a structure and is used in the field of detergents for textile products. From the viewpoint of detergency against dirt on textile products, it is preferable to contain a nonionic surfactant having a structure represented by the following general formula (c1-1). R 8 (CO) m O-(AO) n -R 9 (c1-1) [In the formula, R 8 is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 9 is a hydrogen atom or a methyl group. CO is a carbonyl group, m is a number of 0 or 1. The AO group is an alkyleneoxy group having 2 to 4 carbon atoms. n is the average number of added moles and is a number of 1 or more and 30 or less.]

[0017] In the general formula (c1-1), the number of carbon atoms of R 8 is 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, from the viewpoint of further enhancing detergency.

[0018] R 8 is an aliphatic hydrocarbon group, and from the viewpoint of further enhancing detergency, it is preferably a group selected from an alkyl group and an alkenyl group, and from the viewpoint of further enhancing the enhancing effect of the present invention, it is more preferably an alkyl group. The aliphatic hydrocarbon group which is R 8 may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The linear aliphatic hydrocarbon group may be a linear primary aliphatic hydrocarbon group or a linear secondary aliphatic hydrocarbon group. R 8Preferred specific groups include one or more groups selected from primary or secondary octyl groups, decyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, tetradecenyl groups, hexadecenyl groups, and octadecenyl groups.

[0019] In the general formula (c1-1), m is a number of 0 or 1, and is preferably 0 from the viewpoint of further improving cleaning performance. In general formula (c1-1), R 9 This is either a hydrogen atom or a methyl group, and from the viewpoint of further improving cleaning performance, it is preferably a hydrogen atom.

[0020] In general formula (c1-1), the AO group is an alkylene oxy group having 2 to 4 carbon atoms, preferably an alkylene oxy group having 2 to 3 carbon atoms, and more preferably an alkylene oxy group selected from the group consisting of ethylene oxy groups and propylene oxy groups. When a nonionic surfactant having the structure represented by general formula (c1-1) contains multiple AO groups, the multiple AO groups may be ethylene oxy groups, or alkylene oxy groups containing an ethylene oxy group and another alkylene oxy group, such as an alkylene oxy group having 3 or 4 carbon atoms. For example, an alkylene oxy group containing an ethylene oxy group and a propylene oxy group is also possible. A propylene oxy group is preferred as the other alkylene oxy group. When the multiple AO groups contain an ethylene oxy group and an alkylene oxy group having 3 or 4 carbon atoms, the ethylene oxy group and the alkylene oxy group having 3 or 4 carbon atoms may be bonded in a block-type or random-type bond. The ethylene oxy group and the propylene oxy group may be bonded in a block-type or random-type bond. If the material contains both an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be linked in a block or random manner.

[0021] In general formula (c1-1), n ​​is the average number of moles of AO groups added, and is a number between 1 and 30. In general formula (c1-1), n ​​is preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and 30 or less, from the viewpoint of further improving washability, and preferably 25 or less, more preferably 20 or less, even more preferably 16 or less, even more preferably 14 or less, even more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of further improving stability after compounding. n is a raw material for the compound represented by general formula (c1-1), R 8 (CO) m The number of moles of alkylene oxide with 2 to 4 carbon atoms added to 1 mole of OH may be one mole, or it may be the average number of moles of alkylene oxide with 2 to 4 carbon atoms added after the addition reaction.

[0022] <(d) component> In the present invention, component (d) is an anionic surfactant having one or more groups selected from sulfonic acid groups and sulfate ester groups, or salts thereof. Component (d) is used from the viewpoint of improving the cleaning performance against stains on textile products.

[0023] (d) The component more preferably contains one or more anionic surfactants selected from the group consisting of the following components (d1), (d2), and (d3). (d1) Components: Alkyl or alkenyl sulfates or salts thereof (d2) Components: Polyoxyalkylene alkyl or alkenyl ether sulfate esters having an alkylene oxy group or salts thereof (d3) Components: Alkylbenzenesulfonic acid, olefin sulfonic acid, alkanesulfonic acid or salts thereof

[0024] More specifically, component (d1) may be one or more anionic surfactants selected from alkyl sulfate esters with 10 to 18 carbon atoms in the alkyl group, and alkenyl sulfate esters with 10 to 18 carbon atoms in the alkenyl group, or salts thereof. From the viewpoint of further improving cleaning performance, component (d1) is preferably one or more anionic surfactants selected from alkyl sulfate esters with 12 to 14 carbon atoms in the alkyl group, or salts thereof. Salts of component (d1) may be alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0025] (d2) As for the component, an anionic surfactant represented by the following general formula (2) is preferred. R 5 O-(AO)n-SO3Y (2) [In the formula, R 5 (AO) is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, the AO group is an alkylene oxy group having 2 to 4 carbon atoms, the (AO)n group is a polyoxyalkylene group containing a propylene oxy group, n is the average number of moles of AO groups added, which is between 0.5 and 10, and Y is a counter salt that dissociates in water to become a cation, Y + These include hydrogen ions, alkali metal ions, alkaline earth metal ions (half an atom), ammonium ions, or organic ammonium ions.

[0026] Regarding component (d2), R 5 The carbon group is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, and from the viewpoint of further enhancing the bactericidal effect of the composition, the carbon number is preferably 12 or more. On the other hand, from the same viewpoint, the carbon number is preferably 14 or less. Therefore, R 5Preferred aliphatic hydrocarbon groups include one or more aliphatic hydrocarbon groups selected from primary or secondary decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, and hexadecyl groups. Furthermore, from the viewpoint of further enhancing the bactericidal effect of the composition, R 5 When the mass of preferred aliphatic hydrocarbon groups is taken as 100% by mass, the proportion of carbon atoms in the aliphatic hydrocarbon group having 16 carbon atoms is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0027] In general formula (2), the AO group is an alkylene oxy group having 2 to 4 carbon atoms. The alkylene oxy group having 2 to 4 carbon atoms is selected from the group consisting of ethylene oxy group, propylene oxy group, and butylene oxy group. The (AO)n group is a polyoxyalkylene group containing a propylene oxy group. That is, the (AO)n always contains a propylene oxy group and may contain polyoxyalkylene groups of other structures. Polyoxyalkylene groups other than the propylene oxy group include ethylene oxy group and butylene oxy group. When the (AO)n group contains an ethylene oxy group and a propylene oxy group, the ethylene oxy group and the propylene oxy group may be bonded in a block type or a random type. In the present invention, the (AO)n group being a polyoxyalkylene group containing a propylene oxy group means that R in general formula (2) is 5 It may be understood that the compound is obtained by an addition reaction in which propylene oxide is always used when adding an alkylene oxide with 2 to 4 carbon atoms to an OH group.

[0028] In general formula (2), n is the average number of moles of AO groups added, and is a number between 0.5 and 10. In general formula (2), n is preferably 0.6 or more from the viewpoint of further enhancing cleaning ability and sterilization effect, more preferably 2 or more from the viewpoint of further enhancing cleaning power, and preferably 6 or less, more preferably 5 or less from the viewpoint of further enhancing sterilization effect. The ratio n1 / n2, which is the ratio of the average number of moles of ethyleneoxy groups added (n1) to the average number of moles of propyleneoxy groups added (n2), is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, even more preferably 0.8 or less, even more preferably 0.6 or less, even more preferably 0.4 or less, even more preferably 0.2 or less, and from the same viewpoint, 0 or more. n1 / n2 may also be 0. The average number of moles of AO groups added is R in general formula (2) above. 5 The number of moles of alkylene oxide with 2 to 4 carbon atoms per mole of OH may be the number of moles of OH that react with and add.

[0029] In general formula (2), Y is the counter salt that dissociates in water to become a cation, and Y + Examples of alkali metal ions include alkali metal ions, alkaline earth metal (half-atom) ions, ammonium ions, or organic ammonium ions. Examples of alkali metal ions include sodium ions and potassium ions. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0030] (d3) More specifically, the component may include one or more anionic surfactants selected from alkylbenzene sulfonates with 10 to 18 carbon atoms in the alkyl group, alkenylbenzene sulfonates with 10 to 18 carbon atoms in the alkenyl group, alkane sulfonates with 10 to 18 carbon atoms in the alkyl group, α-olefin sulfonates with 10 to 18 carbon atoms in the α-olefin portion, α-sulfo fatty acid salts with 10 to 18 carbon atoms in the fatty acid portion, α-sulfo fatty acid lower alkyl ester salts with 10 to 18 carbon atoms in the fatty acid portion and 1 to 5 carbon atoms in the ester portion, and internal olefin sulfonates with 14 to 18 carbon atoms.

[0031] Internal olefin sulfonates, which have 16 to 18 carbon atoms, can be obtained by sulfonating internal olefins, which have 16 to 18 carbon atoms. The internal olefin refers to an olefin in which the double bond is located internally from the 2nd position. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively generates β-sartone, and a portion of the β-sartone is converted to γ-sartone and olefin sulfonic acid. These are further converted to hydroxyalkane sulfonates and olefin sulfonates in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)).

[0032] Here, the hydroxyl group of the resulting hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. Furthermore, the resulting product is mainly a mixture of these, and may also contain trace amounts of hydroxyalkanesulfonates having a hydroxyl group at the end of the carbon chain, or α-olefin sulfonates having a double bond at the end of the carbon chain. In this specification, these individual products and mixtures thereof are collectively referred to as internal olefin sulfonates. Hydroxyalkanesulfonates are also referred to as the hydroxy derivative of internal olefin sulfonates (hereinafter also referred to as HAS), and olefin sulfonates are also referred to as the olefin derivative of internal olefin sulfonates (hereinafter also referred to as IOS).

[0033] From the viewpoint of further improving cleaning performance, internal olefin sulfonates with 16 or 18 carbon atoms are preferred. From the viewpoint of further enhancing cleaning performance, the (d3) component is preferably one or more anionic surfactants selected from α-olefin sulfonates with 10 to 18 carbon atoms in the α-olefin portion, and internal olefin sulfonates with 14 to 18 carbon atoms.

[0034] (d3) Examples of salts of component (d3) include alkali metal salts, alkaline earth metal (1 / 2 atom) salts, ammonium salts, or organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts containing alkanolamines with 2 to 6 carbon atoms.

[0035] 〔water〕 The liquid detergent composition for textile products contains water. The water can be deionized water (sometimes called ion-exchanged water) or water to which sodium hypochlorite has been added at a rate of 1 mg / kg to 5 mg / kg. Tap water can also be used.

[0036] <Composition, etc.> The content of component (a) in the liquid detergent composition for textile products according to the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of imparting a whitening effect to textile products. On the other hand, from the viewpoint of formulation stability, it is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.2% by mass or less.

[0037] The content of component (c) in the liquid detergent composition for textile products according to the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of further improving cleaning performance. On the other hand, from the viewpoint of the likelihood of problems arising in the present invention, it is preferably 30% by mass or less, more preferably 28% by mass or less, and even more preferably 25% by mass or less.

[0038] The content of component (d) in the liquid detergent composition for textile products according to the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of further improving stability after compounding. On the other hand, from the viewpoint of the likelihood of problems arising in the present invention, it is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0039] Furthermore, the total amount of component (c) and component (d) in the liquid detergent composition for textile products according to the present invention is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more, from the viewpoint of cleaning performance. On the other hand, from the viewpoint of the likelihood of problems arising in the present invention, it is 30% by mass or less, preferably 28% by mass or less, and more preferably 25% by mass or less.

[0040] In the method for enhancing the whitening effect of the present invention, it is preferable to increase the mass ratio of the content of component (d) to the content of component (c) in the detergent composition. More specifically, in the liquid detergent composition for textile products according to the present invention, the mass ratio of the content of component (d) to the content of component (c) [(d) / (c)] is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of further enhancing the whitening effect of the liquid detergent composition for textile products. From a similar viewpoint, it is preferably 5 or less, more preferably 4 or less, even more preferably 3 or less, even more preferably 2 or less, even more preferably 1 or less, and even more preferably 0.5 or less.

[0041] The composition of the present invention contains water. The amount of water may be the remainder after excluding essential components such as component (a) and other optional components.

[0042] <Optional ingredients> The liquid detergent composition for textile products according to the present invention may contain the following components as optional components.

[0043] <(b) Component> The composition according to the present invention preferably further contains, as component (b), one or more compounds selected from the group consisting of dicrosan (4,4'-dichloro-2-hydroxydiphenyl ether) and cationic surfactants having two aliphatic hydrocarbon groups with 8 carbon atoms. The inclusion of component (b) imparts a bactericidal effect to the detergent composition.

[0044] Cationic surfactants having two aliphatic hydrocarbon groups with eight carbon atoms include, for example, quaternary ammonium salts of compounds represented by the following general formula (1).

[0045] [ka]

[0046] [In the formula, R 1 and R 2 Each of these is an alkyl group having 8 carbon atoms, and R 3 and R 4Each of these is a group independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, X - It is a monovalent anion.

[0047] In general formula (1), R 1 and R 2 Each of these is an alkyl group having 8 carbon atoms. Examples of alkyl groups include linear or branched alkyl groups, preferably linear alkyl groups, and more preferably saturated linear hydrocarbon groups having 8 carbon atoms, i.e., octyl groups. 1 and R 2 R may be an alkyl group having 8 carbon atoms other than an octyl group, but from the viewpoint of cleaning power, 1 and R 2 It is even more preferable that both are octyl groups.

[0048] In general formula (1), R 3 and R 4 Each of these groups is independently selected from the group consisting of alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms. Specific examples of alkyl groups having 1 to 3 carbon atoms include the methyl group, ethyl group, and propyl group. Specific examples of hydroxyalkyl groups having 1 to 3 carbon atoms include the hydroxymethyl group, hydroxyethyl group, and hydroxypropyl group. 3 and R 4 From the viewpoint of further enhancing the bactericidal effect, the alkyl group is preferably one or more carbon atoms with 3 or fewer carbon atoms, and more preferably a group selected from methyl and ethyl groups.

[0049] In general formula (1), X -It is a monovalent anion. As the monovalent anion, a monovalent anion selected from the group consisting of halide ions and alkyl sulfate ions having 1 to 3 carbon atoms is preferred. Specific examples of halide ions are chloride ions and bromide ions, and chloride ions are preferred from the viewpoint of further enhancing the bactericidal effect. Specific examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions, and methyl sulfate ions and ethyl sulfate ions are preferred from the viewpoint of further enhancing the bactericidal effect.

[0050] The content of component (b) in the liquid detergent composition for textile products according to the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.6% by mass or more, from the viewpoint of imparting an antibacterial effect to textile products. On the other hand, from the viewpoint of further improving stability after compounding, it is preferably 7% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0051] <Optional ingredients> The liquid detergent composition for textile products according to the present invention may contain the following components as optional components. [(e) component] From the viewpoint of further enhancing stability after formulation, the composition according to the present invention preferably contains an alkanolamine having 2 to 6 carbon atoms or a salt thereof as component (e). Examples of alkanolamines having 2 to 6 carbon atoms include one or more compounds selected from monoethanolamine, diethanolamine, methyldiethanolamine, and triethanolamine or a salt thereof, and from the viewpoint of further enhancing stability after formulation, monoethanolamine or a salt thereof is preferred. Component (e) also includes compounds contained in the composition as counterions of component (d) above.

[0052] When the composition according to the present invention contains component (e), from the viewpoint of further improving stability after formulation, the composition may contain component (e) in an amount of preferably 0.4% by mass or more, more preferably 0.6% by mass or more, even more preferably 0.8% by mass or more, even more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 7% by mass or less, and even more preferably 5% by mass or less. In the present invention, the content of component (e) in the composition represents the content as an amine.

[0053] [(f) component] The composition according to the present invention may contain an inorganic salt.

[0054] The inorganic salt may contain one or more inorganic salts selected from alkali metal halides, alkali metal sulfates, alkaline earth metal halides, and alkaline earth metal sulfates. Examples of alkali metal halides include sodium chloride and potassium chloride. Examples of alkali metal sulfates include sodium sulfate and potassium sulfate. Examples of alkaline earth metal halides include calcium chloride and magnesium chloride. Examples of alkaline earth metal sulfates include magnesium sulfate.

[0055] The content of component (f) in the composition is preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.5% by mass or less. On the other hand, the lower limit is preferably an amount greater than 0% by mass, and more preferably 0.01% by mass or more. The content of component (f) in the composition can be calculated as the amount of component (f) blended.

[0056] [(g) Component] Component (g) is a fatty acid or a salt thereof having 12 to 24 carbon atoms. Component (g) can further enhance cleaning performance. Fatty acids or salts thereof having 12 to 24 carbon atoms are compounds having an aliphatic hydrocarbon group with 11 to 23 carbon atoms as a hydrophobic group and a carboxylic acid or a salt thereof as a hydrophilic group. More specifically, components (g) include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, or salts thereof. Component (g) may be contained in the composition as an acid or as a salt. From the viewpoint of further enhancing cleaning performance, the content of component (g) in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.4% by mass or more, and even more preferably 0.6% by mass or more. From the viewpoint of further enhancing stability after compounding, it is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less. (g) The content of component (g) shall be expressed as the content converted to its acid form.

[0057] [(h) component] In the present invention, component (h) is one or more compounds selected from monovalent to tetravalent carboxylic acids or hydroxycarboxylic acids (excluding those containing a nitrogen atom) having a hydrocarbon group with 1 to 6 carbon atoms, or salts thereof.

[0058] Specifically, preferred (h) components include glycolic acid, lactic acid, malonic acid, succinic acid, maleic acid, malic acid, tartaric acid, citric acid (mp153℃), benzoic acid, or salts thereof. From the viewpoint of odor, preferably one or more selected from glycolic acid, citric acid, lactic acid, benzoic acid, or salts thereof is preferred, and more preferably citric acid or a salt thereof. From the viewpoint of further enhancing the stability after formulation, the content of component (h) in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and from the same viewpoint, 5% by mass or less, more preferably 3% by mass or less. The content of component (h) shall be calculated as the acid type.

[0059] [(j) component] The composition according to the present invention may contain an organic solvent having a hydroxyl group as component (j). Component (j) is preferably an organic solvent having a hydroxyl group with a CLogP of -2.0 or more and 2.0 or less. In this invention, CLogP is calculated using ChemProperty from Perkin Elmer's ChemBio Draw Ultra ver.14.0. A higher ClogP value indicates higher hydrophobicity.

[0060] (j) Component is an organic solvent having hydroxyl groups, preferably with a CLogP of -2.0 or higher, more preferably -1.8 or higher, even more preferably -1.5 or higher, even more preferably -1.2 or higher, even more preferably -1.0 or higher, even more preferably 0 or higher, even more preferably 0.5 or higher, and preferably 2.0 or lower, more preferably 1.8 or lower, and even more preferably 1.5 or lower, from the viewpoint of storage stability.

[0061] (j) The component may be one or more organic solvents selected from the following components (j1) to (j4). (j1) Components: Monohydric alcohol with 2 to 6 carbon atoms. (j2) Components: Alcohols with 2 to 12 carbon atoms and a valency of 2 to 12. (j3) Components: Organic solvents having hydrocarbon groups, ether groups, and hydroxyl groups with 1 to 8 carbon atoms (however, hydrocarbon groups exclude aromatic groups). (j4) Components: Organic solvent having aromatic groups, ether groups, and hydroxyl groups, which may be partially substituted.

[0062] Specific examples of components (j1) to (j4) are shown below. The numbers in parentheses are the calculated values ​​(CLogP) of each component obtained using the above ChemProperty.

[0063] (j1) Examples of monohydric alcohols with 2 to 6 carbon atoms that are component (j1) include ethanol (-0.24), 1-propanol (0.29), 2-propanol (0.07), and phenol (1.48).

[0064] (j2) Examples of alcohols having 2 to 12 carbon atoms and a valency of 2 to 12 include ethylene glycol (-1.4), propylene glycol (-1.1), butylene glycol (-0.73), hexylene glycol (-0.02), diethylene glycol (-1.3), triethylene glycol (-1.5), tetraethylene glycol (-1.66), dipropylene glycol (-0.69), tripropylene glycol (-0.55), and glycerin (-1.5).

[0065] (j3) The component is an organic solvent having hydrocarbon groups, ether groups, and hydroxyl groups with 1 to 8 carbon atoms (however, hydrocarbon groups exclude aromatic groups), for example, diethylene glycol monomethyl ether (-0.78), triethylene glycol monomethyl ether (-0.96), diethylene glycol monoethyl ether (-0.39), diethylene glycol diethyl ether (0.52), diethylene glycol monobutyl ether (0.67), dipropylene glycol monomethyl ether (-0.16), dipropylene glycol monoethyl ether (0.23), tripropylene glycol monomethyl ether ( Examples include (-0.03), 1-methoxy-2-propanol (-0.30), 1-ethoxy-2-propanol (0.09), 1-methylglycerin ether (-1.43), 2-methylglycerin ether (-0.73), 1,3-dimethylglycerin ether (-0.67), 1-ethylglycerin ether (-1.04), 1,3-diethylglycerin ether (0.11), triethylglycerin ether (0.83), 1-pentylglyceryl ether (0.54), 2-pentylglyceryl ether (1.25), 1-octylglyceryl ether (2.1), and 2-ethylhexylglyceryl ether (2.0).

[0066] (j4) Examples of organic solvents having aromatic groups, ether groups, and hydroxyl groups, which may be partially substituted, include 2-phenoxyethanol (1.2), diethylene glycol monophenyl ether (1.25), triethylene glycol monophenyl ether (1.08), polyethylene glycol monophenyl ether with an average molecular weight of approximately 480 (cannot be calculated), 2-benzyloxyethanol (1.1), and diethylene glycol monobenzyl ether (0.96).

[0067] (j) Component is preferably one or more selected from phenoxyethanol, diethylene glycol monobutyl ether, ethanol, propylene glycol, and ethylene glycol, more preferably one or more selected from phenoxyethanol, diethylene glycol monobutyl ether, propylene glycol, and ethanol, even more preferably one or more selected from phenoxyethanol, diethylene glycol monobutyl ether, and ethanol, and even more preferably one or more selected from phenoxyethanol and diethylene glycol monobutyl ether.

[0068] The liquid detergent composition for textile products according to the present invention contains component (j) in an amount preferably of 0.5% by mass or more, more preferably of 1.0% by mass or more, even more preferably of 1.5% by mass or more, even more preferably of 3% by mass or more, even more preferably of 4% by mass or more, and preferably 10% by mass or less, more preferably of 9.5% by mass or less, even more preferably of 9.0% by mass or less, even more preferably of 7.0% by mass or less, and even more preferably of 6% by mass or less, from the viewpoint of storage stability, foam dissipation, and suppression of musty odor.

[0069] [(k) component] Component (k) is a soil-release agent. The term "soil-release agent" is sometimes used to refer to a dirt-releasing agent. Soil-release agents are known as compounds that, when applied to textile products before use, such as wearing them, improve the removal of dirt from textile products during post-use washing, even if dirt adheres to the textile product during use. In the present invention, by using a soil-release agent as one of the components contained in the textile product cleaning agent composition, it is possible to clean the textile product and apply the soil-release agent to the textile product simultaneously, which is efficient.

[0070] (k) component may include, for example, one or more polysaccharide derivatives having one or more groups selected from a cationic group and a hydrocarbon group having 1 to 18 carbon atoms as component (k1), one or more polymers having one or more units selected from alkylene terephthalate units and alkylene isophthalate units, and an oxyalkylene unit as component (k2), and one or more polyalkylene imine polymers having a polyoxyalkylene group as component (k3), and a polymer selected from two or more monomers having one or more hydrophilic groups selected from monomers having a cationic group, a polyoxyalkylene group, a carboxyl group or its salt, a sulfonic acid group or its salt, a sulfate ester group or its salt, and a polymer selected from two or more monomers having one or more hydrophobic groups selected from aliphatic hydrocarbon groups having 3 to 18 carbon atoms, an aromatic hydrocarbon group, and a cycloalkyl group.

[0071] The (k1) component is one or more polysaccharide derivatives having one or more groups selected from hydrocarbon groups and cationic groups having 1 to 18 carbon atoms. The (k1) component in the present invention is characterized by being a polysaccharide derivative in which one or more groups selected from a cationic group and a hydrocarbon group having 1 to 18 carbon atoms are bonded directly or via a linking group to a group obtained by removing a hydrogen atom from the hydroxyl group of a polysaccharide or a derivative thereof, which is a precursor compound of the (k1) component. It should be noted that the phrase "one or more groups selected from a cationic group and a hydrocarbon group having 1 to 18 carbon atoms are bonded directly or via a linking group to a group obtained by removing a hydrogen atom from the hydroxyl group of a polysaccharide or a derivative thereof" does not include bonding modes in which a cationic atom of a cationic group, such as a nitrogen cation, is directly covalently bonded to the oxygen atom of the hydroxyl group of the polysaccharide or a derivative thereof.

[0072] Examples of polysaccharides include one or more polysaccharides selected from cellulose, guar gum, or starch. Component (k1) is a polysaccharide derivative, but a polysaccharide derivative can be used as a precursor compound to obtain it. That is, component (k1) may be a derivative of a polysaccharide derivative. Examples of polysaccharide derivatives that are precursor compounds of component (k1) include polysaccharide derivatives in which some or all of the hydrogen atoms of the hydroxyl group of the polysaccharide are substituted with a hydroxyalkyl group having 1 to 4 carbon atoms (hereinafter also referred to as a hydroxyalkyl substituted product). The hydroxyalkyl group having 1 to 4 carbon atoms is preferably a hydroxyalkyl group having 2 to 4 carbon atoms. Examples of hydroxyalkyl groups having 2 to 4 carbon atoms include one or more groups selected from hydroxyethyl, hydroxypropyl, and hydroxybutyl groups, with one or more groups selected from hydroxyethyl and hydroxypropyl groups being preferred. The (k1) component may be a compound obtained by introducing one or more groups selected from hydrocarbon groups and cationic groups having 1 to 18 carbon atoms into a polysaccharide or polysaccharide derivative selected from one or more polysaccharides selected from cellulose, guar gum, or starch, or from hydroxyalkyl substituted products thereof.

[0073] The (k2) component is a polymer having one or two units selected from alkylene terephthalate units and alkylene isophthalate units, as well as oxyalkylene units. Examples of alkylene terephthalate units include one or more selected from ethylene terephthalate units, propylene terephthalate units, and butylene terephthalate units, with ethylene terephthalate units being preferred among these. Examples of alkylene isophthalate units include one or more selected from ethylene isophthalate units, propylene isophthalate units, and butylene isophthalate units, with ethylene isophthalate units being preferred among these. Examples of polyoxyalkylene units include one or more selected from polyoxyethylene units, polyoxypropylene units, and polyoxyethylene-polyoxypropylene units.

[0074] The molar ratio of oxyalkylene units to one or more units selected from alkylene terephthalate units and alkylene isophthalate units, which is (number of moles of oxyalkylene units) / (number of moles of one or more units selected from alkylene terephthalate units and alkylene isophthalate units), is preferably 0.6 or less, more preferably 0.5 or less, even more preferably 0.4 or less, and preferably 0 or more, and more preferably 0.1 or more, from the viewpoint of further improving cleaning performance.

[0075] The weight-average molecular weight of component (k2) is preferably 300 or more, more preferably 500 or more, even more preferably 1000 or more, and preferably 20000 or less, and more preferably 15000 or less, from the viewpoint of improving adsorption to textile products and thereby improving the cleanability of dirt attached to textile products after use. Note that the weight-average molecular weight of component (k2) is the value obtained by measuring the value by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as the solvent and converting it based on the calibration curve for PEG (polyethylene glycol).

[0076] Component (k3) is a polyalkyleneimine polymer having a polyoxyalkylene group. The oxyalkylene group of the polyoxyalkylene group can be an oxyalkylene group having 2 to 3 carbon atoms, specifically one or more groups selected from oxyethylene groups and oxypropylene groups. The alkylene group of the polyalkyleneimine can be an alkylene group having 2 to 6 carbon atoms. More specifically, one or more groups selected from ethylene groups and butylene groups having various bonding modes can be selected. The number of polyoxyalkylene groups bonded to the polyalkyleneimine is preferably such that an average of 3 to 100 polyoxyalkylene groups are bonded to each active hydrogen atom of the polyalkyleneimine. The weight-average molecular weight of the polyalkyleneimine polymer is preferably 300 or more, more preferably 500 or more, even more preferably 1000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less, from the viewpoint of further improving the cleanability of dirt attached to textile products.

[0077] Examples of compounds of (k4) include the compounds described in Japanese Patent Publication No. 2007-247126. More specifically, the present invention provides a fiber stain-removing agent comprising a polymer having the following constituent units (k4A) and (k4B), wherein the content of constituent unit (k4A) in the polymer is 1 to 99% by weight, the content of constituent unit (k4B) is 1 to 50% by weight, and which also has an arbitrary constituent unit (k4C), and having a weight-average molecular weight of 2,000 to 300,000, as well as a method for treating fibers, which involves treating fibers in an aqueous solution containing this stain-removing agent and adjusted to a pH of 2 to 9. (k4A) Constituent unit derived from an unsaturated bond-containing monomer having at least one amino group selected from primary to tertiary amino groups. (k4B) A constituent unit derived from an unsaturated bond-containing monomer having at least one hydrophobic group selected from linear, branched, or cyclic alkyl or alkenyl groups, or arylalkyl or aryl groups, having 4 to 22 carbon atoms, and not having a primary to tertiary amino group.

[0078] The polymer in this invention can preferably be obtained by copolymerizing monomer (k4A) and monomer (k4B). In addition to monomer (k4A) and monomer (k4B), an unsaturated bond-containing monomer (hereinafter referred to as monomer (k4C)) that can copolymerize with monomer (k4A) and monomer (k4B) may also be copolymerized to the extent that the effects of this invention are not impaired.

[0079] Examples of monomers (k4A) include (meth)acrylic acid esters, (meth)acrylamides, styrenes, and diallyl compounds, all of which have an amino group. Here, "(meth)acrylic" means acrylic or methacrylic. Examples of monomers (k4B) include at least one selected from (meth)acrylic acid esters, (meth)acrylamides, vinyl esters and vinyl ethers, and styrenes, which have a linear, branched, or cyclic alkyl or alkenyl group or arylalkyl group having 4 to 22 carbon atoms, preferably 8 to 22 carbon atoms, and more preferably 12 to 22 carbon atoms. Examples of monomers (k4C) include (meth)acrylic acid esters or (meth)acrylamides having a hydroxyalkyl group with 1 to 22 carbon atoms, (meth)acrylic acid esters having a polyalkylene (alkylene group with 1 to 8 carbon atoms; linear or branched) oxide chain, (meth)acrylic acid esters of polyhydric alcohols; acrylamides, vinyl compounds having a carboxyl group, vinyl compounds having a sulfonic acid group, and the like.

[0080] The polymer in this invention contains 50% by weight or more of the constituent unit (i4A) relative to the total weight of the constituent units of the polymer. From the viewpoint of adsorption, 60% by weight or more is preferred, and 70% by weight or more is more preferred. The upper limit is 99% by weight or less, 95% by weight or less is preferred, and 90% by weight or less is more preferred. Furthermore, it contains 1% by weight or more of the constituent unit (k4B), preferably 3% by weight or more, more preferably 5% by weight or more, and even more preferably 10% by weight or more. The upper limit is 50% by weight or less, and preferably 45% by weight or less. The copolymerization amount of these monomers (k4C) is preferably 0 to 49% by weight, more preferably 0 to 40% by weight, and even more preferably 0 to 30% by weight, relative to the total amount of monomers. In the present invention, the weight-average molecular weight of the polymer is 2,000 to 30,000, and preferably 2,000 to 20,000, from the viewpoint of ease of controlling adsorption / desorption to fibers.

[0081] Furthermore, the weight-average molecular weight (Mw) of the polymer in this invention shall be the value obtained by gel permeation chromatography (GPC). The eluent shall be one of the following: water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile, or a combination of these solvents, and the molecular weight shall be expressed in terms of polyethylene oxide or polystyrene. The polymer structure can be random, grafted, or blocked, but random or grafted is preferred, with random being more preferred.

[0082] [(m) component] The liquid detergent composition for textile products according to the present invention may contain an enzyme. As component (m), from the viewpoint of further enhancing the cleaning effect, one or more enzymes selected from protease, lipase, and amylase are preferred, and one or more enzymes selected from protease and amylase are more preferred.

[0083] The optimal pH of the protease at 35°C is preferably 4 or higher, more preferably 7 or higher, even more preferably 8 or higher, even more preferably 9 or higher, even more preferably 9.5 or higher, and preferably 12 or lower, more preferably 11 or lower, from the viewpoint of further enhancing the washing effect. Suitable proteases used in the present invention include serine proteases (EC 3.4.21) and metalloproteases (EC 3.4.17 or EC 3.4.24). Examples of suitable proteases include neutral or alkaline serine proteases such as subtilisin (EC 3.4.21.62).

[0084] The origin of the protease is not limited, but may be of animal, plant, or microbial origin, with those of microbial origin such as bacteria or fungi being preferred. More suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one embodiment, the suitable protease may be an alkaline microbial protease and / or a serine protease such as a trypsin-type protease.

[0085] Suitable commercially available proteases include those sold as Alcalase, Duralase, Durazyme, Relax, Relax Ultra, Savinase, Savinase Ultra, Savinase Evity, Primase, Polarzyme, Kannase, Liquanase, Liquanase Ultra, Liquanase Evity, Ovozyme, Coronase, Coronase Ultra, Coronase Evity, Neutrase, Everlase, Progress Uno, Progress Key, Progress Excel, Blaze, Blaze Evity, Blaze Exceed, and Esperase from Novozymes A / S, and from Danisco / DuPont: Preferenz P, Effectenz P, Excellentz P, Maxatase, Maxacal, Maxapem, Purafect, Purafect Prime, Purafect MA, Purafect Ox, and Purafect Examples of suitable enzymes include, but are not limited to, enzymes marketed as OxP, Puramax, Properase, Purafast, FN2, FN3, FN4, Excellase, Opticlean, and Optimase; enzymes marketed as Axapem by Gist-Brocases NV; BLAP (the sequence shown in Figure 29 of U.S. Patent No. 5,352,604) and its variants (Henkel AG) by Henkel AG; and enzymes marketed as Lavergy Pro by BASF. Alkaline proteases described in Japanese Patent No. 3479509 and their variants are also preferred.

[0086] The optimal pH of lipase at 35°C is preferably 4 or higher, more preferably 7 or higher, even more preferably 8 or higher, even more preferably 9 or higher, even more preferably 9.5 or higher, and preferably 12 or lower, more preferably 11 or lower, from the viewpoint of further enhancing the washing effect.

[0087] Suitable lipases used in the present invention include, for example, triacylglycerol lipase (EC3.1.1.3), phospholipase A2 (EC3.1.1.4), lysophospholipase (EC3.1.1.5), monoglyceride lipase (EC3.1.1.23), galactolipase (EC3.1.1.26), phospholipase A1 (EC3.1.1.32), and lipoprotein lipase (EC3.1.1.34). Examples include lipases and cutinases from the genera Bacillus, Thermomyces, Pseudomonas, Humicola, and Streptomyces, and furthermore, chemically or genetically modified mutants of these enzymes may also be used. Suitable commercially available lipases include, but are not limited to, those sold by Novozymes A / S as Lipolase, Lipex, Lipex Evity, Lipolex, and Lipoclean, and those sold by Danisco / DuPont as Preferenz L, Lumafast, and Lipomax.

[0088] The optimal pH of amylase at 35°C, from the viewpoint of further enhancing the washing effect, is preferably 4 or higher, more preferably 7 or higher, even more preferably 8 or higher, even more preferably 9 or higher, even more preferably 9.5 or higher, and preferably 12 or lower, more preferably 11 or lower.

[0089] Suitable amylases for use in the present invention include α-amylase (EC3.2.1.1), β-amylase (EC3.2.1.2), and / or glucoamylase (EC3.2.1.3). Examples of suitable amylases include neutral or alkaline α-amylases, preferably of microorganismal origin such as bacteria or fungi. Examples of neutral or alkaline amylases include those derived from Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermo, Bacillus subutilis, or other species of the genus Bacillus, as well as chemically or genetically modified mutants thereof. Suitable commercially available amylases include, but are not limited to, those sold by Novozymes A / S as Duramyl, Termamyl, Termamyl Ultra, Fungamyl, Stainzyme, Stainzyme Plus, Amplify, Amplify Prime, Natalase, Supramyl, Liquozyme X, and BAN, and those sold by Danisco / DuPont as Preferenz S, Effectenz S, Rapidase, Purastar, and Powerase.

[0090] From the viewpoint of further enhancing the cleaning effect, the enzyme content in the composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less, in terms of protein content.

[0091] [(n) component] Examples of enzyme stabilizers, which are component (n), include boron compounds, calcium ion sources (calcium ion supply compounds), and bihydroxy compounds. Suitable examples of boron compounds include borax, boric acid, and sodium borate; suitable calcium ion sources include calcium chloride and calcium acetate; and suitable bihydroxy compounds include glycerin, 1,2-hexanediol, 1,2-dodecanediol, glucose, sorbitol, and maltose. Among these, calcium chloride is particularly advantageous in terms of economy. The liquid detergent composition according to the present invention contains 0.01 to 3% by weight of component (n), which is an enzyme stabilizer, preferably 0.01 to 2% by weight, and more preferably 0.01 to 0.5% by weight.

[0092] The composition according to the present invention may contain other components known in the field of detergents for textile products, such as bleaching agents (perborate, bleach activators, etc.), anti-redeposition agents, reducing agents (sulfites, etc.), anti-foaming agents (silicone, etc.), fragrances, colorants, antibacterial agents, etc. (except those that fall under component (b)).

[0093] [Liquid detergent composition for textile products] Another aspect of the present invention is a liquid detergent composition for textile products containing the above-mentioned components (a), (c), (d), and water, wherein the mass ratio of the content of component (d) to the content of component (c) in the liquid detergent composition for textile products ((d) / (c)) is 0.01 or more.

[0094] In the liquid detergent composition for textile products of the present invention, specific and preferred examples of components (a), (c), (d), and water, as well as specific and preferred examples of optional components such as component (b), can be appropriately selected from those described in the method for enhancing the whitening effect of the present invention.

[0095] In addition, regarding the composition and preferred composition of the component (a), component (c), component (d), water, and optional components including component (b) in the liquid detergent composition for textile products of the present invention, they are the same as those described in the liquid detergent composition for textile products according to the method for enhancing the whitening effect of the present invention.

[0096] Furthermore, regarding the preferred upper limit and lower limit of the mass ratio of the content of component (d) to the content of component (c) ((d) component / (c) component) in the liquid detergent composition for textile products of the present invention, they can also be appropriately selected from those described in the method for enhancing the whitening effect of the present invention.

[0097] The liquid detergent composition for textile products of the present invention is a liquid detergent composition for textile products that washes dirt adhering to textile products such as clothing. The liquid detergent composition for textile products of the present invention can be used for both hand washing and machine washing, but it is preferably used for machine washing.

[0098] 〔pH of the liquid detergent composition for textile products〕 The pH (25 °C, stock solution) of the liquid detergent composition for textile products of the present invention is preferably 5 or more, more preferably 6 or more, still more preferably 6.5 or more, even more preferably 7 or more, and from the same perspective, preferably 10 or less, more preferably 9.5 or less, still more preferably 9 or less, even more preferably 8.5 or less, from the viewpoint of further enhancing the stability after formulation. The pH of the composition can be measured according to the <pH measurement method> below.

[0099] <pH measurement method> Connect the pH measuring composite electrode (HORIBA glass ground-joint sleeve type) to the pH meter (HORIBA pH / ion meter F-23) and turn on the power. Use saturated potassium chloride aqueous solution (3.33 mol / L) as the internal solution for the pH electrode. Next, fill 100 mL beakers with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), and immerse them in a 25°C constant temperature bath for 30 minutes. Immerse the pH measuring electrode in the standard solutions adjusted to constant temperature for 3 minutes and perform calibration in the order of pH 9.18 → pH 4.01 → pH 6.86. Adjust the sample to be measured to 25°C, immerse the electrode of the pH meter in the sample, and measure the pH after 1 minute.

[0100] Examples of clothing to be washed in this invention include denim pants and jackets, batik, undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, etc., and the invention is particularly useful in embodiments where clothing that is prone to color transfer is to be washed. Examples of fibers that make up the clothing include hydrophobic fibers such as acrylic, polyester, and nylon, and hydrophilic fibers such as cotton.

[0101] [Textile products] The textile products in this invention include clothing and non-clothing products, specifically, denim pants and jackets, batik, undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, and other textile products, and the invention is particularly useful in embodiments where textile products with color transfer properties are to be processed. The fibers constituting the textile products include hydrophobic fibers such as acrylic, polyester, and nylon, and hydrophilic fibers such as cotton. [Examples]

[0102] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and do not imply any limitation.

[0103] <Composition ingredients> The following ingredients were used in the examples and comparative examples. Note that the amounts of each ingredient in the table represent the amount of the active ingredient, not the amount of the product. [(a) component] (a-1): 4,4'-Bis(2-sulfostyryl)biphenyldisodium salt (Chinopar CBS-X, manufactured by BASF)

[0104] [(b) component] (b-1): Dioctyldimethylammonium chloride (85% by mass ethanol solution, containing 2 parts by mass of dioctyldimethylamine per 100 parts by mass of quaternary ammonium salt)

[0105] [(c) component] (c-1): In the above general formula (c1-1), R 8 is a mixed alkyl group (lauryl group / myristyl group = 7 / 3 (mass ratio)), m is 0, (AO) n However, to an alcohol with a mixed alkyl group as the hydrocarbon group, 4 moles of propyleneoxy were added, followed by 17 moles of ethyleneoxy groups (n=21), R 9 It is a compound of H. (c-2): In the above general formula (c1-1), R 8 (A) is a lauryl group, m is 0, (AO) is an ethylene oxy group, n is 10, R 9 It is a compound of H. (c-3): In the above general formula (c1-1), R 8 (AO) is a mixed alkyl group (a secondary alkyl group with 10 to 10 carbon atoms), m is 0, (AO) is an ethylene oxy group, n is 3, R 9 It is a compound of H.

[0106] [(d) component] (d-1): In the above general formula (2), R 5 (A) is a dodecyl group, and (AO)n is a compound obtained by adding a propylene oxide group to dodecyl alcohol at a ratio of 0.6 moles per mole, then esterifying with sulfuric acid, and neutralizing with sodium hydroxide (n=0.6). + A compound in which sodium ions are present. (d-2): Potassium C16 internal olefin sulfonate obtained by the following manufacturing method (corresponding to component (d3) above).

[0107] • Production of C16 internal olefin a1 Internal olefin a1 with 16 carbon atoms, which will be the raw material for (d-2), was produced according to the method described below. The internal olefin with 16 carbon atoms was produced in accordance with production example C of Japanese Patent Application Publication No. 2014-76988. The double bond distribution of the internal olefin is as follows. In internal olefin a1, the mass percentage of internal olefins with double bonds at the following positions was 1st / 2nd / 3rd / 4th / 5th / 6th / 7th / 8th = 2.3% / 23.6% / 18.9% / 17.5% / 13.7% / 11.2% / 6.4% / 6.4% (total 100 mass%).

[0108] The double bond distribution of the internal olefin a1 was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, the internal olefin was reacted with dimethyl disulfide to form a dithiolated derivative, and then each component was separated by GC. As a result, the proportion of the double bond distribution of the internal olefin was determined from the peak area of ​​each component, and this proportion was taken as the mass proportion. Note that in olefins with 16 carbon atoms, internal olefins with a double bond at position 7 and internal olefins with a double bond at position 8 are structurally indistinguishable, but they become distinguishable when sulfonated. For convenience, the amount of internal olefin with a double bond at position 7 was divided by 2 and shown in each column. The apparatus and analytical conditions used for the measurement are as follows. GC system "HP6890" (manufactured by Hewlett Packard), column "Ultra-Alloy-1HT capillary column" (30m x 250μm x 0.15μm, manufactured by Frontier Labs Co., Ltd.), detector (flame ion detector (FID)), injection temperature 300℃, detector temperature 350℃, He flow rate 4.6mL / min

[0109] Manufacturing of (d-2) The aforementioned internal olefin a1 was subjected to a sulfonation reaction using a thin-film sulfonation reactor with an external jacket, by passing sulfur trioxide gas and cooling water at 20°C through the reactor's external jacket. The molar ratio of SO3 to internal olefin during the sulfonation reaction was set to 1.09. The obtained sulfonate was added to an alkaline aqueous solution prepared with 1.5 molar times the theoretical acid value of potassium hydroxide, and neutralized at 30°C for 1 hour with stirring. The neutralized product was hydrolyzed by heating in an autoclave at 160°C for 1 hour to obtain a crude potassium sulfonate product of the C16 internal olefin. 300 g of the crude product was transferred to a separatory funnel, 300 mL of ethanol was added, and then 300 mL of petroleum ether was added in each step to extract and remove oil-soluble impurities. At this time, inorganic compounds (mainly potassium sulfate) precipitated at the oil-water interface due to the addition of ethanol were also separated and removed from the aqueous phase by oil-water separation. This extraction and removal operation was performed three times. Potassium olefin sulfonate was obtained by evaporating the aqueous phase to dryness.

[0110] [Optional ingredients] • Protease ·amylase • Calcium chloride (used as a 10% by mass aqueous solution) • Coconut oil fatty acids Butylcarbitol • Soil release agent (component (b-1) described in the examples of Japanese Patent Publication No. 2019-099820) • Dyes (The following mixed dyes: Green No. 202 / Yellow No. 203 / Red No. 106 / Blue No. 1 = 5 / 1 / 3 / 1 by mass) • Fragrance composition (Fragrance composition described in paragraph 0061 of Japanese Patent Publication No. 2016-204508) • Citric acid (used as a 50% by mass aqueous solution) • Monoethanolamine Ion-exchanged water

[0111] Examples 1-8 and Comparative Example 1 <Preparation of liquid detergent compositions for textile products> Using the above-mentioned ingredients, the textile cleaning agents shown in Table 1 were prepared by the following method. 90% of the amount of water needed to produce a final mass of 400g was placed in a 500ml glass beaker and heated to 40°C in a water bath. A 6cm diameter Teflon® rod-shaped stirrer bead was placed inside and rotated at 60 r / m with a magnetic stirrer. The specified amounts of the optional components were added and stirred for 5 minutes, then components (c) and (d) were added and stirred for 15 minutes. Next, a mixture containing the optional (b) component, heated to 40°C in the proportions shown in the table, was added and stirred for another 5 minutes, then component (a) was added and stirred for another 10 minutes. The pH was adjusted to 7.5 (40°C) with a 10% by mass sodium hydroxide solution or a 1% by mass hydrochloric acid aqueous solution. The remaining amount of water needed to produce a final mass of 100% by mass was added and stirred for 5 minutes, then the temperature was adjusted to 25°C while stirring in a 10°C water bath. The pH of the composition was measured again and adjusted to 7.5 (25°C) with a 10% by mass sodium hydroxide solution or a 1% by mass hydrochloric acid aqueous solution.

[0112] [Method for evaluating the whitening effect] The whitening effect was evaluated as follows: A 6x6cm piece of non-fluorescent cotton knit fabric (30g) and 600mL of cleaning solution were placed in a turgotometer (manufactured by Ueshima Seisakusho) and washed at 85rpm, 20°C, and for 10 minutes. The cleaning solution was prepared by diluting various cleaning agent compositions with Wakayama City tap water to a concentration of 1g / L. Afterwards, the fabric was spun dry for 1 minute in the spin-drying tub of a twin-tub washing machine PS-H35L (Hitachi). The spun-dry test fabric was placed in 600mL of tap water and rinsed in a turgotometer at 85rpm, 20°C, and for 3 minutes. It was then spun dry again for 1 minute in the spin-drying tub of the twin-tub washing machine and air-dried. The fluorescence intensity (IF value) of the treated fabric was measured using a SPECTRO COLOR METER MODEL PF-10 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). The ΔIF value was calculated by subtracting the IF value of the untreated fabric from the IF value of the fabric treated with the cleaning agent composition. In this evaluation, a higher ΔIF value indicates a superior fluorescence whitening effect. The results are shown in Table 1. In Table 1, the whitening effect (ΔIF value) of each example is shown as a relative value, with the whitening effect (ΔIF value) of Comparative Example 1 set to 1, and is listed in the "Enhancement of Whitening Effect" column.

[0113] [Table 1]

[0114] From Table 1, the following was found: From a comparison of the whitening effect of Comparative Example 1 and each example, it was found that the whitening effect was enhanced by incorporating an anionic surfactant having a specific structure of component (d). Furthermore, comparisons of Examples 1-4 and Examples 5-8 revealed that the whitening effect was enhanced as the value of component (d) / component (c) increased.

Claims

1. A method for enhancing the whitening effect of a liquid detergent composition for textile products containing the following components (a), (c), (d), and water, the method comprising increasing the mass ratio of the content of component (d) to the content of component (c) in the liquid detergent composition for textile products (component (d) / component (c)). (a) Components: Fluorescent whitening agent having a sulfonic acid group or a salt thereof (c) Component: Nonionic surfactant having an aliphatic hydrocarbon group with 10 to 18 carbon atoms and a polyoxyalkylene group. (d) Components: Anionic surfactant having one or more groups selected from sulfonic acid groups and sulfate ester groups, or salts thereof.

2. (a) The enhancement method according to claim 1, wherein the component comprises a fluorescent whitening agent having a sulfonic acid group or a salt thereof and a biphenyl group.

3. (a) The enhancement method according to claim 1 or 2, wherein the component comprises a 4,4'-bis(2-sulfostyryl)biphenyldialkali metal salt.

4. A liquid detergent composition for textile products further contains, as component (b), one or more compounds selected from the group consisting of dicrosan and cationic surfactants having two aliphatic hydrocarbon groups with eight carbon atoms. The enhancement method according to claim 1 or 2.

5. A liquid detergent composition for textile products containing the following components (a), (c), (d), and water, wherein the mass ratio of the content of component (d) to the content of component (c) in the liquid detergent composition for textile products (component (d) / component (c)) is 0.01 or more. (a) Components: Fluorescent whitening agent having a sulfonic acid group or a salt thereof (c) Component: Nonionic surfactant having an aliphatic hydrocarbon group with 10 to 18 carbon atoms and a polyoxyalkylene group. (d) Components: Anionic surfactant having one or more groups selected from sulfonic acid groups and sulfate ester groups, or salts thereof.

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