Liquid detergent for clothing

Abstract

To provide a liquid detergent for clothing that contains an internal olefin sulfonic acid or a salt thereof and water, and that enables enhanced removal performance for mud stains adhering to fabrics.SOLUTION: A liquid detergent for clothing comprises the following Components (a), (b), (c), and water, wherein in Component (b), the content ratio of a compound in which R1b is a lauryl group is 80 mass% or more and 100 mass% or less: Component (a): an internal olefin sulfonic acid having 16 carbon atoms or a salt thereof, Component (b): a specific compound represented by general formula (b1): R1bO-[(PO)x / (EO)y]-SO3M, and Component (c): a specific quaternary ammonium salt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent for clothing, a method for cleaning clothing, and the use of an anionic surfactant and a quaternary ammonium salt to enhance the cleaning power of muddy soils on clothing. [Background technology]

[0002] Conventionally, anionic surfactants, such as alkylbenzene sulfonates and olefin sulfonates (e.g., internal olefin sulfonates obtained from internal olefins having double bonds internally rather than at the ends of the olefin chains), and nonionic surfactants, such as nonionic surfactants containing an oxyalkylene group having 2 to 3 carbon atoms, have been widely used as cleaning ingredients for household and industrial use. Furthermore, quaternary ammonium compounds having an aliphatic alkyl group have been used as antibacterial agents.

[0003] Patent Document 1 discloses a liquid detergent composition for clothing that contains an alkylbenzene sulfonate, an anionic surfactant with a specific structure, a quaternary ammonium salt, a nonionic surfactant, and water, and that has excellent cleaning properties for particle stains, stains, and body stains. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-141661 Summary of the Invention [Problem to be solved by the invention]

[0005] Internal olefin sulfonates are known as cleaning components in liquid detergents for clothing. While laundry detergents containing internal olefin sulfonates have excellent cleaning properties for stains adhering to clothing, there has been a demand for further improvement in the cleaning properties for muddy stains adhering to clothing.

[0006] The present invention provides a liquid detergent for clothing, which contains an internal olefin sulfonic acid or a salt thereof and water and has improved detergency for removing muddy stains from clothing. [Means for solving the problem]

[0007] The present invention has discovered that in a liquid detergent for clothing containing an internal olefin sulfonic acid or its salt and water, the cleaning ability of mud stains adhering to clothing is improved by using in combination a polyoxyalkylene alkyl ether sulfate containing a polyoxypropylene group and an alkyl group with a high content of lauryl groups, and a quaternary ammonium salt having two aliphatic hydrocarbon groups having 6 to 10 carbon atoms.

[0008] The present invention comprises the following components (a), (b), (c) and water, wherein in component (b), R 1b The present invention relates to a liquid detergent for clothing, in which the content of compounds in which the group is a lauryl group is 80% by mass or more and 100% by mass or less. Component (a): Internal olefin sulfonic acid having 16 carbon atoms or its salt Component (b): a compound represented by the following general formula (b1):

[0009] R 1b O-〔(PO) x / (EO) y -SO3M (b1) [In the formula, R 1b is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, PO is an oxypropylene group, EO is an oxyethylene group, x is the average number of moles of PO groups added and is a number of 0.5 to 5, y is the average number of moles of EO groups added and is a number of 1 to 5, M is a cation, and " / " indicates that the PO groups and EO groups may be bonded either in blocks or randomly. Component (c): a quaternary ammonium salt represented by the following general formula (c1):

[0010] [ka]

[0011] [In the formula, R 11c , R 12c are the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, and R 13c , R 14c are groups selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, and X - is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms.

[0012] The present invention also relates to a method for washing clothes, in which muddy clothes are washed with a cleaning solution prepared by diluting the liquid detergent for clothes with water at a concentration of 100 to 4,000 times.

[0013] The present invention also provides a composition comprising the above-mentioned components (a), (b), (c) and water, wherein in component (b), R 1b The present invention relates to the use of components (b) and (c) to enhance the cleaning power of mud stains adhering to clothing by applying a liquid detergent for clothing, the liquid detergent containing a compound whose compound is a lauryl group in an amount of 80% by mass or more and 100% by mass or less. [Effects of the Invention]

[0014] According to the present invention, the cleaning properties of a liquid detergent for clothing containing an internal olefin sulfonic acid or a salt thereof and water can be further improved for removing mud stains adhering to clothing. DETAILED DESCRIPTION OF THE INVENTION

[0015] The inventors have discovered that in a liquid detergent for clothing containing an internal olefin sulfonic acid or its salt having 16 carbon atoms and water, by further using a polyoxyalkylene alkyl ether sulfate, in which the alkyl group contains a high content of lauryl groups and a sulfate ester salt containing an oxypropylene group, in combination with a quaternary ammonium salt having two aliphatic hydrocarbon groups having 6 to 10 carbon atoms, it is possible to make it easier to disperse mud stains adhering to clothing in the cleaning solution.

[0016] <Component (a)> Component (a) is an internal olefin sulfonic acid having 16 carbon atoms or a salt thereof. Component (a) has the effect of cleaning mud stains adhering to clothing. The internal olefin sulfonic acid having 16 carbon atoms and its salts can be used alone or in combination with two or more types having different double bond positions.

[0017] C16 internal olefin sulfonic acid or its salt can be obtained by sulfonating a C16 internal olefin. The internal olefin refers to an olefin in which the double bond is located inside the 2-position. Internal olefins can be obtained, for example, by isomerizing 1-olefins obtained by dehydrating 1-alcohols. Sulfonation of internal olefins quantitatively produces β-sultone, and a portion of the β-sultone converts to γ-sultone and olefin sulfonic acid. These are then converted to hydroxyalkanesulfonates and olefin sulfonates in the neutralization and hydrolysis steps (e.g., J. Am. Oil Chem. Soc. 69, 39 (1992)). The hydroxy group of the resulting hydroxyalkanesulfonates is located within the alkane chain, while the double bond of the olefin sulfonates is located within the olefin chain. The resulting product is primarily a mixture of these, and some of these may contain trace amounts of hydroxyalkanesulfonates with a hydroxy group at the end of the carbon chain or α-olefin sulfonates with a double bond at the end of the carbon chain. In this specification, these products and mixtures thereof are collectively referred to as internal olefin sulfonates (component (a)). Furthermore, hydroxyalkanesulfonates are referred to as hydroxy forms of internal olefin sulfonates (hereinafter also referred to as HAS), and olefin sulfonates are referred to as olefin forms of internal olefin sulfonates (hereinafter also referred to as IOS).

[0018] Examples of salts of component (a) include alkali metal salts, alkaline earth metal (half atom) salts, ammonium salts, and organic ammonium salts. Examples of alkali metal salts include sodium salts and potassium salts. Examples of organic ammonium salts include alkanolammonium salts having 1 to 6 carbon atoms, such as monoethanolammonium salts. In the present invention, when the mass of component (a) is used, the mass is converted into the mass of the sodium salt.

[0019] <(b) Component> Component (b) is a compound represented by the following general formula (b1), and in component (b), R 1b The content of the compound in which the group is a lauryl group is 80% by mass or more and 100% by mass or less. The component (b) can be used alone or in combination of two or more. The component (b) in the present invention can further enhance the cleaning ability of the component (a) for removing mud stains from clothing by using it together with the component (c) described below. R 1b O-〔(PO) x / (EO) y -SO3M (b1) [In the formula, R 1b is an aliphatic hydrocarbon group having 10 to 16 carbon atoms, PO is an oxypropylene group, EO is an oxyethylene group, x is the average number of moles of PO groups added and is a number of 0.5 to 5, y is the average number of moles of EO groups added and is a number of 1 to 5, M is a cation, and " / " indicates that the PO groups and EO groups may be bonded either in blocks or randomly.

[0020] In general formula (b1), R 1b R is an aliphatic hydrocarbon group having 10 or more carbon atoms, preferably 12 or more carbon atoms, from the viewpoint of further improving the cleaning properties of mud stains adhering to clothing, and from the same viewpoint, having 16 or less carbon atoms, preferably 14 or less carbon atoms. 1b The alkyl group may be an aliphatic alkyl group or an aliphatic alkenyl group, preferably an aliphatic alkyl group, and more preferably a linear aliphatic alkyl group.

[0021] (b) In the component, R 1bThe content of the compound in which R is a lauryl group is 80% by mass or more and 100% by mass or less means that, in the component (b), R 1b The total mass converted into aliphatic alcohol, i.e., R contained in component (b) 1b R 1b This means that the ratio of the mass of lauryl groups contained in the compound represented by general formula (b1) converted into aliphatic alcohol, i.e., the mass of lauryl groups contained in component (b) converted into lauryl alcohol, to the total mass converted into —OH is 80 mass% or more and 100 mass% or less. In addition, in component (b), R 1b The content ratio of the compound in which is a lauryl group may be the ratio of the mass of lauryl alcohol contained in the aliphatic alcohol used as a raw material when producing component (b) to the total mass of aliphatic alcohols having 10 to 16 carbon atoms contained in the aliphatic alcohol used as a raw material. In the present invention, in order to further enhance the detergency of a liquid laundry detergent containing component (a) and water for muddy soils by using component (c) in combination, R 1b The content of the compound in which is a lauryl group is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 95% by mass or more, and 100% by mass or less. In the component (b), R 1b is a lauryl group is 100%, that is, in general formula (b1), 1b is a lauryl group.

[0022] In general formula (b1), PO is an oxypropylene group, and x is the average number of moles of oxypropylene groups added, and is a number of 0.5 to 5. From the viewpoint of further improving the cleanability of mud stains adhering to clothing when used in combination with component (c) in the present invention, x is 0.5 or more, preferably 0.7 or more, more preferably 1 or more, even more preferably 1.1 or more, still more preferably 1.2 or more, and from the same viewpoint, x is 5 or less, preferably 4 or less, more preferably 3.5 or less, even more preferably 3 or less, and still more preferably 2.5 or less.

[0023] In general formula (b1), EO is an oxyethylene group, and y is the average number of moles of oxyethylene groups added, and is a number of 1 to 5. From the viewpoint of further improving the cleanability of mud stains adhering to clothing when used in combination with component (c) in the present invention, y is 1 or more, preferably 1.1 or more, more preferably 1.3 or more, even more preferably 1.5 or more, still more preferably 2 or more, and from the same viewpoint, y is 5 or less, preferably 4 or less, more preferably 3.5 or less, even more preferably 3 or less, and still more preferably 2.5 or less.

[0024] The oxypropylene group and the ethyleneoxy group are preferably bonded in a block from the viewpoint of further enhancing the cleaning properties of mud stains adhering to clothing when used in combination with component (c) in the present invention, and R 1b O-group, -(PO) x -(EO) y It is preferable that they are bonded in block in the order of -. That is, the compound of general formula (b1) is R 1b O-(PO) x -(EO) y The compound represented by -SO3M is preferred.

[0025] In general formula (b1), M may be an alkali metal ion, an alkaline earth metal (half atom) ion, an ammonium ion, or an organic ammonium ion. Examples of alkali metal ions include sodium ions and potassium ions. Examples of organic ammonium ions include alkanolammonium ions having 1 to 6 carbon atoms, such as monoethanolammonium ions. In the present invention, when the mass of component (b) is used, the mass is converted into that of the sodium salt.

[0026] The component (b) in the present invention can be produced by a known method. For example, it can be obtained by the production method shown below. However, the component (b) in the present invention is not limited to compounds produced by this production method. Step (I): A step of adding propylene oxide and ethylene oxide to an aliphatic alcohol having 10 to 18 carbon atoms and containing 80 to 100% by mass of lauryl alcohol.

[0027] In step (I), propylene oxide and ethylene oxide are added to an aliphatic alcohol having from 10 to 18 carbon atoms and containing from 80 to 100% by mass of lauryl alcohol. The addition rate of propylene oxide per mole of the alcohol is the rate represented by x in general formula (b1), and the addition rate of ethylene oxide per mole of the alcohol is the rate represented by y in general formula (b1). The addition of propylene oxide and ethylene oxide may be simultaneous, or propylene oxide may be added first and then ethylene oxide, or vice versa.

[0028] A conventionally known method can be used to carry out step (I). That is, the alcohol and 0.5 to 1 mol % of KOH relative to the alcohol are charged into an autoclave as a catalyst, the mixture is heated and dehydrated, and then predetermined amounts of propylene oxide and ethylene oxide are added and reacted at a temperature of about 120 to 160°C. The autoclave used is preferably equipped with a stirrer, a temperature controller, and an automatic feeder.

[0029] In step (II), the alkoxylate obtained in step (I) is sulfated and then neutralized. Examples of sulfation methods include those using sulfur trioxide (liquid or gaseous), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid, etc. However, from the viewpoint of preventing the generation of waste sulfuric acid, waste hydrochloric acid, etc., a method in which sulfur trioxide is continuously supplied in gaseous or liquid form simultaneously with the alkoxylate is preferred.

[0030] The neutralization method of sulfates includes a batch method in which sulfates are added to a predetermined amount of neutralizing agent and neutralized while stirring, and a loop method in which sulfates and neutralizing agent are continuously supplied into a pipe and neutralized using a stirrer mixer, but the present invention is not limited to this neutralization method. Neutralizing agents that can be used here include aqueous alkali metal hydroxide solutions, ammonia water, triethanolamine, etc.

[0031] <(c) component> Component (c) is a quaternary ammonium salt represented by the following general formula (c1): Component (c) can be used singly or in combination of two or more. When used in combination with component (b), component (c) can further enhance the cleaning ability of a liquid laundry detergent containing component (a) and water to remove muddy stains from clothing.

[0032] [ka]

[0033] [In the formula, R 11c , R 12care the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, and R 13c , R 14c are groups selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, and X - is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms.

[0034] In general formula (c1), R 11c , R 12c are the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, and from the viewpoint of further improving the cleaning properties of mud stains adhering to clothing when used in combination with the above-mentioned component (b), are preferably aliphatic hydrocarbon groups having 8 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 8 carbon atoms. 11c , R 12c R is preferably the same aliphatic hydrocarbon group, from the viewpoint of further enhancing the cleaning properties of mud stains adhering to clothing when used in combination with the above-mentioned component (b). 11c , R 12c The aliphatic hydrocarbon group R may be a linear or branched alkyl group, and from the viewpoint of further enhancing the cleaning properties, a linear alkyl group is preferred. 11c , R 12c Specific examples of the aliphatic hydrocarbon group include a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0035] In general formula (c1), R 13c , R 14c are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Specific examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0036] In general formula (c1), X -is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms. Specific examples of the halide ion include chloride ion and bromide ion, with chloride ion being preferred from the viewpoint of further improving cleaning performance. Specific examples of the alkyl sulfate ion having 1 to 3 carbon atoms include methyl sulfate ion, ethyl sulfate ion, and propyl sulfate ion, with methyl sulfate ion and ethyl sulfate ion being preferred from the viewpoint of further improving cleaning performance.

[0037] More preferred specific examples of component (c) include one or more compounds selected from N,N-dihexyl-N,N-dimethylammonium salt, N,N-diheptyl-N,N-dimethylammonium salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dihexyl-N-methyl-N-ethylammonium salt, N,N-diheptyl-N-methyl-N-ethylammonium salt, N,N-dioctyl-N-methyl-N-ethylammonium salt, N,N-dihexyl-N-methyl-N-hydroxyethylammonium salt, N,N-diheptyl-N-methyl-N-hydroxyethylammonium salt, N,N-dioctyl-N-methyl-N-hydroxyethylammonium salt, N-hexyl-N-octyl-N,N-dimethylammonium salt, and N-octyl-N-decyl-N,N-dimethylammonium salt. From the viewpoint of further enhancing the cleaning properties of mud stains adhering to clothing when used in combination with the aforementioned component (b), component (c) preferably contains a quaternary ammonium salt having two aliphatic hydrocarbon groups each having 8 carbon atoms, and more preferably one or more compounds selected from N,N-dioctyl-N,N-dimethylammonium salt and N,N-dioctyl-N-methyl-N-ethylammonium salt. The salts are preferably chlorides, methyl sulfates, or ethyl sulfates. In the present invention, the mass of component (c) is expressed as the mass converted into the chloride.

[0038] <Water> The liquid detergent for clothing of the present invention contains water. The water can be ion-exchanged water or water to which sodium hypochlorite has been added in an amount of 1 mg / kg to 5 mg / kg. Tap water can also be used.

[0039] <Composition of liquid laundry detergent> The content of component (a) in the liquid laundry detergent of the present invention is preferably 4% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of further improving the cleaning ability of mud stains adhering to clothing, and from the same viewpoint is preferably 65% ​​by mass or less, more preferably 55% by mass or less, even more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0040] The content of component (b) in the liquid laundry detergent of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of further improving the cleaning ability of mud stains adhering to clothing, and from the same viewpoint is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

[0041] The total content of components (a) and (b) in the liquid laundry detergent of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of further improving the cleaning ability of mud stains adhering to clothing, and from the same viewpoint is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0042] In the liquid detergent for clothing of the present invention, the mass ratio of the content of component (b) to the content of component (a), i.e., component (b) / component (a) (mass ratio), is preferably 0.3 or more, more preferably 0.5 or more, even more preferably 0.7 or more, still more preferably 1.0 or more, still more preferably 1.2 or more, from the viewpoint of further improving the cleaning ability of mud stains adhered to clothing, and from the same viewpoint, is preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less.

[0043] The mass of component (c) relative to 100 parts by mass of the total content of components (a) and (b) in the liquid laundry detergent of the present invention is, from the viewpoint of further improving the cleaning ability of mud stains adhering to clothing, preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 6 parts by mass or more, even more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, and from the same viewpoint, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less. The liquid detergent for clothing of the present invention preferably contains component (c) in the range of parts by mass when the total content of components (a) and (b) in the detergent is converted to 100 parts by mass.

[0044] From the viewpoint of further enhancing the cleaning ability of mud stains adhering to clothing, the content of component (c) in the liquid detergent for clothing of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 2% by mass or more, still more preferably 2.5% by mass or more, still more preferably 3% by mass or more, still more preferably 4% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less, and still more preferably 5% by mass or less.

[0045] <Clothing> In the present invention, the term "clothing" is not particularly limited, but examples thereof include undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, and the like, which are made from fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics using hydrophobic fibers such as acrylic fibers, polyester fibers, and nylon fibers, and hydrophilic fibers such as cotton and silk.

[0046] <Optional ingredients> The liquid laundry detergent of the present invention may optionally contain, as component (d), an anionic surfactant or a nonionic surfactant other than the aforementioned component (a) or (b), as long as the effects of the present invention are not impaired. From the viewpoint of further improving the cleaning ability of muddy stains, the ratio of the mass of the component (d) contained in the liquid laundry detergent to the total mass of the components (a) and (b), i.e., component (d) / [component (a) + component (b)] (mass ratio), is preferably 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.03 or less, and may even be 0. The liquid laundry detergent of the present invention may optionally contain, as component (e), a cationic surfactant other than the component (c), as long as the effects of the present invention are not impaired. From the viewpoint of further improving the cleaning ability of muddy stains, the ratio of the amount of component (e) to the amount of component (c) contained in the liquid laundry detergent, i.e., component (e) / component (c) (mass ratio), is preferably 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.03 or less, and may even be 0. Other optional components that may be included in the liquid laundry detergent of the present invention include organic solvents having a hydroxyl group, such as ethylene glycol, propylene glycol, glycerin, phenoxyethanol, and diethylene glycol butyl ether; hydrotropes such as cumene sulfonic acid, paratoluene sulfonic acid, meta-xylene sulfonic acid, or salts thereof; one or more enzymes selected from cellulase, amylase, pectinase, protease, and lipase; and phenolic antibacterial agents. Examples of phenolic antibacterial agents include antibacterial agents having an aromatic hydrocarbon group in which one or more hydrogen atoms of the aromatic hydrocarbon are substituted with a hydroxyl group within the molecule. Examples of phenolic antibacterial agents include chlorophenolic antibacterial agents. Examples of chlorophenolic antibacterial agents include 4,4'-dichloro-2-hydroxydiphenyl ether (diclosan).

[0047] <How to wash clothes> The present invention provides a method for washing clothes, which comprises washing muddy clothes with a cleaning solution prepared by diluting the liquid detergent for clothes with water at a concentration of 100 to 4,000 times. The method for washing clothes of the present invention may involve washing muddy clothes with a cleaning solution prepared by diluting the liquid laundry detergent with water at a dilution ratio of 100 to 4,000. The dilution ratio is the volume (milliliters) of water used in the cleaning solution divided by the mass (g) of the liquid laundry detergent. The dilution ratio may be calculated, for example, from the recommended usage amount indicated on a label attached to a container containing the liquid laundry detergent. Furthermore, if the recommended usage amount indicated on the label indicates the mass of the liquid laundry detergent relative to the mass of the clothes, the dilution ratio may be calculated by multiplying the mass (kg) of the clothes by 20,000 and using this value as the volume (milliliters) of water.

[0048] Although not limited thereto, it is presumed that, in the liquid detergent for clothing of the present invention, the aggregate formed by the components (a), (b), and (c) adsorbs to muddy stains adhering to clothing while maintaining the aggregate even when diluted in the washing solution, making the muddy stains more easily dispersible in the washing solution, thereby improving the cleaning performance of the muddy stains. Therefore, the degree to which the liquid detergent for clothing of the present invention is diluted is considered to be one of the factors for further improving the cleaning performance of muddy stains adhering to clothing. In the method for washing clothes of the present invention, from the viewpoint of further improving the cleaning performance of muddy stains adhering to clothing, it is preferable to wash muddy-stained clothing with a cleaning solution in which the liquid detergent for clothing is diluted with water by 100 times or more, preferably 200 times or more, more preferably 500 times or more, even more preferably 750 times or more, and from the same viewpoint, by 4,000 times or less, preferably 3,500 times or less. That is, in the method for washing clothes of the present invention, the dilution ratio is 100 times or more, preferably 200 times or more, more preferably 500 times or more, and even more preferably 750 times or more, from the viewpoint of further improving the cleaning ability of mud stains adhering to clothes, and from the same viewpoint, it is 4,000 times or less, preferably 3,500 times or less.

[0049] <The use of ingredients (b) and (c) to enhance the cleaning power of mud stains on clothing> The present invention also provides a composition comprising the following components (a), (b), (c) and water, wherein in component (b), R 1b The present invention provides a method for applying a liquid detergent for clothing, the content of which is 80% by mass or more and 100% by mass or less of a compound in which the compound is a lauryl group, to the washing of clothing, and a method for enhancing the cleaning power of mud stains adhering to clothing, the present invention provides a method for using the components (b) and (c) to enhance the cleaning power of mud stains adhering to clothing. Component (a): Internal olefin sulfonic acid having 16 carbon atoms or its salt Component (b): a compound represented by the following general formula (b1): R 1b O-〔(PO) x / (EO) y -SO3M (b1) [In the formula, R 1bis an aliphatic hydrocarbon group having 10 to 16 carbon atoms, PO is an oxypropylene group, EO is an oxyethylene group, x is the average number of moles of PO groups added and is a number of 0.5 to 5, y is the average number of moles of EO groups added and is a number of 1 to 5, M is a cation, and " / " indicates that the PO groups and EO groups may be bonded either in blocks or randomly. Component (c): a quaternary ammonium salt represented by the following general formula (c1):

[0050] [ka]

[0051] [In the formula, R 11c , R 12c are the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, and R 13c , R 14c are groups selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, and X - is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms.

[0052] It has been discovered that in a liquid laundry detergent containing the above-mentioned component (a) and water, the components (b) and (c) can be used to enhance the cleaning power of mud stains adhering to clothing.

[0053] In the method of use of the present invention, the specific contents of the components (a), (b), (c), water and laundry detergent are the same as those described above for the liquid laundry detergent. [Example]

[0054] <Composition ingredients> In the examples and comparative examples, the following components were used: [Component (a)] (a-1): An internal olefin sulfonate having 16 carbon atoms obtained by the following production method: ·Production of internal olefin a1 with 16 carbon atoms According to the method below, an internal olefin a1 having 16 carbon atoms, which is used as a raw material for component (a-1), was produced. The internal olefin having 16 carbon atoms was produced in accordance with Production Example C of JP 2014-76988 A. The double bond distribution of the internal olefin is as follows: In the internal olefin a1, the mass proportions of the internal olefins having double bonds at the following positions were 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% by mass).

[0055] 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 each component was then separated by GC. The resulting percentage of the double bond distribution of the internal olefin was calculated from each peak area, and this percentage was used as the mass percentage. For olefins with 16 carbon atoms, internal olefins with a double bond at the 7th position and internal olefins with a double bond at the 8th position cannot be distinguished structurally, but they can be distinguished after sulfonation. Therefore, for convenience, the amount of internal olefins with a double bond at the 7th position divided by 2 is 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" (30 m x 250 μm x 0.15 μm, manufactured by Frontier Labs), detector (hydrogen flame ionization detector (FID)), injection temperature 300 °C, detector temperature 350 °C, He flow rate 4.6 mL / min

[0056] [Production of (a-1)] The sulfonation reaction of the internal olefin a1 was carried out in a thin-film sulfonation reactor equipped 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 / internal olefin during the sulfonation reaction was set to 1.09. The resulting sulfonated product was added to an alkaline aqueous solution prepared with 1.5 molar equivalents of potassium hydroxide relative to the theoretical acid value, and neutralized at 30°C for 1 hour with stirring. The neutralized product was hydrolyzed by heating at 160°C for 1 hour in an autoclave to obtain a crude product of potassium internal olefin sulfonate with 16 carbon atoms. 300 g of the crude product was transferred to a separatory funnel, and 300 mL of ethanol was added. Oil-soluble impurities were extracted and removed by adding 300 mL of petroleum ether per addition. During this process, inorganic compounds (mainly potassium sulfate) precipitated at the oil-water interface upon the addition of ethanol were also separated and removed from the aqueous phase by oil-water separation. This extraction and removal procedure was repeated three times. The aqueous phase was evaporated to dryness to obtain potassium internal olefin sulfonate.

[0057] [(b) component] (b-1): Polyoxypropylene polyoxyethylene lauryl ether sulfate sodium (a compound obtained by reacting a compound obtained by adding 2 moles of propylene oxide to 1 mole of lauryl alcohol, and then adding 2 moles of ethylene oxide to the compound, with SO3 gas, and then neutralizing the compound with an aqueous sodium hydroxide solution; in the general formula (b1), R 1b The group is a lauryl group, x is the number 2, y is the number 2, and the polyoxypropylene group and the polyoxyethylene group are in this order. 1b Attached to the O group, X - is a sodium ion.

[0058] [(b') component] (b'-1): Polyoxypropylene polyoxyethylene alkyl ether sodium sulfate (a compound obtained by adding 2 moles of propylene oxide to 1 mole of a mixed alcohol containing lauryl alcohol and myristyl alcohol in a ratio of lauryl alcohol / myristyl alcohol = 70 / 30 (mass ratio), and then adding 2 moles of ethylene oxide to the resulting compound, and then reacting the compound with SO3 gas and neutralizing it with an aqueous sodium hydroxide solution; in the general formula (b1), x is 2, y is 2, and the polyoxypropylene group and polyoxyethylene group are in this order, R 1b Attached to the O group, X - is a sodium ion. (b'-2): sodium lauryl sulfate ester (in the general formula (1b), R 1b The group is a lauryl group, x and y are both 0, and X - is a sodium ion. (b'-3): Polyoxyethylene lauryl ether sulfate sodium (a compound obtained by reacting a compound obtained by adding 2 moles of ethylene oxide to 1 mole of lauryl alcohol with SO3 gas and then neutralizing the compound with an aqueous sodium hydroxide solution, and in the general formula (b1), R 1b The group is a lauryl group, x is the number 0, y is the number 2, and X - is a sodium ion.

[0059] [(c) component] (c-1): N,N-dioctyl-N,N-dimethylammonium chloride (c-2): N,N-didecyl-N,N-dimethylammonium bromide (c-3): N,N-didecyl-N-ethyl-N-methylammonium ethyl sulfate (c-4): N-hexyl-N-octyl N,N-dimethylammonium bromide

[0060] 〔water〕 Ion-exchanged water

[0061] <Preparation of liquid laundry detergent> The method for preparing the liquid laundry detergent shown in Table 1 is as follows. A 5 cm long Teflon stirrer was placed in a 200 mL glass beaker and the mass was measured. Next, 90% by mass of water (30°C) was added to bring the total weight to 100 g, and while stirring with a magnetic stirrer at 100 r / min, component (a), component (b) or component (b'), and component (c) were added. After stirring for 30 minutes, ion-exchanged water was added to bring the total weight to 100 g. After stirring for 15 minutes at 100 r / min, a liquid laundry detergent was prepared.

[0062] [Mud cleaning performance evaluation] (1-1) Preparation of artificial mud-stained fabric Kanuma horticultural Akadama soil was dried at 120°C ± 5°C for 4 hours, then crushed and passed through a 150 mesh (100 μm) filter. The crushed soil was then dried at 120°C ± 5°C for 2 hours, after which 150 g was dispersed in 1000 L of Perclene to obtain a dispersion. A cloth (Tanitago Shoten Cotton 2003, cut into 10 cm x 10 cm pieces) was brought into contact with the resulting dispersion and brushed to remove the dispersion. Excess mud adhering to the cloth surface was then removed to obtain a soiled cloth for evaluating mud stains.

[0063] (1-2) Detergency test for muddy soiled cloth Five of the artificially mud-stained cloths (artificially contaminated cloths) prepared above and a cloth for adjusting the liquor ratio (Cotton 2003 manufactured by Tanigashira Shoten, cut to 6 cm x 6 cm) were placed in 600 mL of a cleaning solution prepared by diluting a liquid detergent for clothing 3,000 times, and washed under the following washing conditions using a stirring-type detergency tester (Tergotometer MS-8212 manufactured by Ueshima Seisakusho Co., Ltd.) A three-blade stirring rod for the tergotometer (bottom diameter 6.8 cm, maximum length of the blades in the radial direction from the stirring rod 4.0 cm) was used for stirring in the tergotometer. [Cleaning conditions] Spin speed: 85 rpm, Wash time: 10 minutes, Water hardness: 4°DH, Water temperature: 20°C, Rinse: 3 minutes with tap water, Spin: 3 minutes using the spinning layer of a two-layer washing machine (Hitachi, Ltd., two-layer washing machine PS-H45L)

[0064] (1-3) Calculation method of cleaning rate and relative cleaning rate The detergency of the liquid laundry detergents of the examples was evaluated based on the cleaning rate calculated for each soiled cloth. Specifically, the detergency was evaluated by measuring the reflectance of the unsoiled cloth and the soiled cloth before and after washing using a spectrocolorimeter (Spectro Color Meter SE2000, manufactured by Nippon Denshoku Industries Co., Ltd.), and calculating the cleaning rate (%) (average of measurements of five soiled cloths) using the following formula. The higher the cleaning rate, the better the cleaning ability of the product for removing mud stains from clothing. Cleaning rate (%) = [(reflectance after cleaning - reflectance before cleaning) / (reflectance of original fabric - reflectance before cleaning)] x 100

[0065] Furthermore, the cleaning rate of each Example or Comparative Example was calculated using the following formula to give the relative cleaning rate, where the cleaning rate of Comparative Example 1 was set to 100. The relative cleaning rate was calculated using the following formula. The higher the relative cleaning rate, the better the cleaning ability of mud stains adhering to clothing. Relative cleaning rate (%) = [cleaning rate of each Example or Comparative Example listed in Table 1 / cleaning rate of Comparative Example 1] × 100

[0066] [Table 1]

Claims

1. The composition contains the following components (a), (b), and (c) and water, and in component (b), R １ｂ A liquid detergent for clothing, wherein the content of compounds in which is a lauryl group is 80% by mass or more and 100% by mass or less. Component (a): Internal olefin sulfonic acid having 16 carbon atoms or its salt Component (b): a compound represented by the following general formula (b1): R １ｂ O-〔(2O) ｘ / (EO) ｙ 〕-SO ３ M (b1) [In the formula, R １ｂ represents an aliphatic hydrocarbon group having from 10 to 16 carbon atoms, PO represents an oxypropylene group, EO represents an oxyethylene group, x represents the average number of moles of PO groups added and is a number from 0.5 to 5, y represents the average number of moles of EO groups added and is a number from 1 to 5, M represents a cation, and " / " indicates that the PO groups and EO groups may be bonded either in blocks or randomly. Component (c): a quaternary ammonium salt represented by the following general formula (c1): 【Chemical 1】 [In the formula, R １１ｃ , R １２ｃ are the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, R １３ｃ , R １４ｃ are groups selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, and X － is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms.

2. 2. The liquid detergent for clothing according to claim 1, wherein component (c) comprises a quaternary ammonium salt having two aliphatic hydrocarbon groups each having 8 carbon atoms.

3. 3. The liquid laundry detergent according to claim 1, wherein the total content of the components (a) and (b) in the liquid laundry detergent is 10% by mass or more and 70% by mass or less.

4. A method for washing clothes, comprising washing muddy soiled clothes with a cleaning solution prepared by diluting the liquid detergent for clothes according to claim 1 or 2 with water at a ratio of 100 to 4,000.

5. The composition contains the following components (a), (b), and (c) and water, and in component (b), R １ｂ The use of components (b) and (c) for enhancing the cleaning power of mud stains adhering to clothing by applying a liquid detergent for clothing, the liquid detergent containing a compound in which the compound is a lauryl group in an amount of 80% by mass or more and 100% by mass or less, to the washing of clothing. Component (a): Internal olefin sulfonic acid having 16 carbon atoms or its salt Component (b): a compound represented by the following general formula (b1): R １ｂ O-〔(2O) ｘ / (EO) ｙ 〕-SO ３ M (b1) [In the formula, R １ｂ represents an aliphatic hydrocarbon group having from 10 to 16 carbon atoms, PO represents an oxypropylene group, EO represents an oxyethylene group, x represents the average number of moles of PO groups added and is a number from 0.5 to 5, y represents the average number of moles of EO groups added and is a number from 1 to 5, M represents a cation, and " / " indicates that the PO groups and EO groups may be bonded either in blocks or randomly. Component (c): a quaternary ammonium salt represented by the following general formula (c1): 【Chemistry 2】 [In the formula, R １１ｃ , R １２ｃ are the same or different and are aliphatic hydrocarbon groups having 6 to 10 carbon atoms, R １３ｃ , R １４ｃ are groups selected from alkyl groups having 1 to 3 carbon atoms and hydroxyalkyl groups having 1 to 3 carbon atoms, and X － is an anion selected from a halide ion and an alkyl sulfate ion having 1 to 3 carbon atoms.

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