Clothing detergent

Abstract

The present invention relates to a clothing detergent which contains a water-soluble aluminium salt, an enzyme, a polymer having a carboxyl group or a salt thereof, and one or more surfactants selected from an anionic surfactant and a nonionic surfactant. The present invention makes it possible to provide a clothing detergent which has excellent cleaning properties and which suppresses the problem of dye migration that occurs when the aforementioned water-soluble aluminium salt is used in combination with an enzyme and a surfactant.

Description

Laundry detergent

[0001] The present invention relates to a laundry detergent and a method for cleaning laundry.

[0002] There has been a demand for improved cleaning performance of laundry detergents.

[0003] For example, Patent Document 1 discloses a powder detergent for textile products that contains an anionic surfactant, a water-soluble aluminum salt, an alkali metal sulfate and an alkali metal chloride, a specific alkali agent, and a specific carboxylate, and that has excellent solubility, feel on the hands, and detergency.

[0004] International Publication No. WO-A-2017002760

[0005] The present inventors have newly discovered that the use of a water-soluble aluminum salt, which has long been known to enhance the comfort of hand-washing, in combination with an enzyme and a surfactant improves cleaning effectiveness. On the other hand, they have also newly discovered that when a detergent having such a composition is used, discoloration of clothing may occur when partially colored clothing or when differently colored clothing is washed in the same bath. The present invention relates to providing a clothing detergent and a method for washing clothing that suppress the dye transfer problem that occurs when the water-soluble aluminum salt is used in combination with an enzyme and a surfactant and has excellent cleaning properties.

[0006] The present invention relates to the following [1] to

[16] . [1] A laundry detergent containing the following components (a), (b), (c), and (d), wherein the pH at 25°C when 2 g of the laundry detergent is dissolved in 1 L of ion-exchanged water is 9.0 or more and 12.0 or less: component (a): a water-soluble aluminum salt component (b): an enzyme component (c): a polymer having a carboxy group or a salt thereof (excluding those corresponding to component (a)) component (d): one or more surfactants selected from anionic surfactants and nonionic surfactants. [2] The laundry detergent according to the above [1], wherein the component (c) is one or more polymers selected from the following components (c1) and (c2). Component (c1): a polysaccharide polymer having a carboxy group or a salt thereof. Component (c2): a vinyl polymer having a carboxy group or a salt thereof. [3] The laundry detergent according to the above item [2], wherein the mass ratio of the content of the component (c2) to the content of the component (c1) (content of component (c2) / content of component (c1)) is 0 or more and 3.0 or less. [4] The laundry detergent according to any one of the above items [1] to [3], wherein the mass ratio of the content of the anionic surfactant in component (d) to the content of component (d) (content of anionic surfactant in component (d) / content of component (d)) is 0.5 or more and 1 or less. [5] The laundry detergent according to any one of the above items [1] to [4], wherein the component (a) is an inorganic water-soluble aluminum salt. [6] The laundry detergent according to any one of the above items [1] to [5], wherein the component (b) is one or more enzymes selected from proteases and amylases. [7] The laundry detergent according to any one of [1] to [6] above, wherein the component (a) is aluminum sulfate, the component (b) is a protease, the component (c) is one or more polymers selected from the following components (c1) and (c2), and the component (c1) is a polysaccharide polymer having a carboxy group or a salt thereof, and the component (c2) is a vinyl polymer having a carboxy group or a salt thereof, and the component (d) is one or more surfactants selected from the following components (d1-1) and (d1-3), and nonionic surfactants represented by the following general formula (d2-1):Component (d1-1): alkyl or alkenyl sulfate ester Component (d1-3): anionic surfactant having a sulfonate group R. ４ (CO) ｍ O-(AO) ｎ -R ５ (d2-1) [In the formula, R ４ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R ５is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is the number 0 or 1. AO is an alkyleneoxy group containing an ethyleneoxy group and having from 2 to 4 carbon atoms. n is the average number of moles added, and is a number of from 1 to 30.] [8] The laundry detergent according to any one of [1] to [7] above, which is one or more solid detergents selected from powder, granules, and granular forms. [9] A method for washing clothes, which comprises contacting clothes with a washing solution containing the following components (a), (b), (c), and (d), and water, and having a pH of from 9.0 to 12.0 at 25°C: Component (a): a water-soluble aluminum salt Component (b): an enzyme Component (c): a polymer having a carboxy group or a salt thereof (excluding those corresponding to component (a)) Component (d): one or more surfactants selected from anionic surfactants and nonionic surfactants

[10] The cleaning method according to [9] above, wherein the component (c) is one or more polymers selected from the following components (c1) and (c2): Component (c1): a polysaccharide polymer having a carboxy group or a salt thereof Component (c2): a vinyl polymer having a carboxy group or a salt thereof

[11] The cleaning method according to

[10] above, wherein the mass ratio of the content of the component (c2) to the content of the component (c1) in the cleaning solution (content of component (c2) / content of component (c1)) is 0 or more and 3.0 or less.

[12] The cleaning method according to any one of [9] to

[11] above, wherein the mass ratio of the content of the anionic surfactant in the component (d) to the content of the component (d) in the cleaning solution (content of anionic surfactant in the component (d) / content of the component (d)) is 0.5 or more and 1 or less.

[13] The cleaning method according to any one of [9] to

[12] above, wherein the component (a) is an inorganic water-soluble aluminum salt.

[14] The cleaning method according to any one of [9] to

[13] above, wherein the component (b) is one or more enzymes selected from proteases and amylases.

[15] The cleaning method according to any one of [9] to

[14] above, wherein the component (a) is aluminum sulfate, the component (b) is a protease, the component (c) is one or more polymers selected from the following components (c1) and (c2), and the component (c1) is a polysaccharide polymer having a carboxy group or a salt thereof, the component (c2) is a vinyl polymer having a carboxy group or a salt thereof, and the component (d) is one or more surfactants selected from the following components (d1-1) and (d1-3), and nonionic surfactants represented by the following general formula (d2-1): component (d1-1): alkyl or alkenyl sulfate ester, and component (d1-3): anionic surfactant having a sulfonate group R. ４ (CO) ｍ O-(AO) ｎ -R ５ (d2-1) [In the formula, R ４ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R ５ is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is a number of 0 or 1. AO is an alkyleneoxy group containing an ethyleneoxy group and having 2 to 4 carbon atoms. n is the average number of moles added and is a number of 1 to 30.]

[16] The cleaning method according to any one of [9] to

[15] above, wherein the clothing is dye-migratory clothing.

[0007] According to the present invention, it is possible to provide a clothing detergent and a clothing cleaning method that suppress the dye transfer problem that occurs when the above-mentioned water-soluble aluminum salt is used in combination with an enzyme and a surfactant, and that have excellent detergency. In the present invention, discoloration of clothing caused by washing clothing that is partially colored with different colors or other clothing of different colors in the same bath is referred to as dye transfer. Clothing that may discolor is also referred to as clothing with dye transfer properties. Furthermore, suppressing dye transfer is referred to as dye transfer suppression. Furthermore, the effect of suppressing dye transfer is referred to as dye transfer suppression effect.

[0008] The inventors have investigated the above-mentioned problems and newly discovered that the use of a polymer having a carboxy group or its salt results in excellent detergency while suppressing the dye migration problem. While the mechanism is unclear, it is believed that under alkaline pH conditions, aluminum present in the wash solution acts on the enzyme, enhancing the enzyme's detergency. On the other hand, under alkaline pH conditions, aluminum salts in the wash solution aggregate, making them less susceptible to the enzyme's action. Therefore, it is presumed that the polymer having a carboxy group or its salt redisperses the aluminum aggregates, thereby making it easier for the aluminum ions in the wash solution to act on the enzyme. It has also been newly discovered that the dye migration problem is more prevalent when the wash solution has an alkaline pH. While the mechanism is unclear, it is believed that under alkaline pH conditions, aluminum salts in the wash solution capture and aggregate dyes eluted from clothing, causing them to redeposit on the clothing, worsening dye migration. It is presumed that the polymer having a carboxy group or its salt redisperses the aluminum and dye aggregates, thereby inhibiting the dye from redepositing on the clothing. Therefore, the dye transfer suppression effect of the present invention is particularly preferably exhibited in an embodiment in which the pH of the washing liquid is alkaline.

[0009] [Clothing Detergent] The detergent of the present invention contains the following components (a), (b), (c), and (d). The detergent of the present invention is a detergent for clothing that cleans stains attached to clothing. The detergent of the present invention can be used for both hand washing and washing in a washing machine, but is preferably used for washing in a washing machine. The detergent of the present invention is a solid detergent or a liquid detergent, and a solid detergent is preferred from the viewpoints of making the pH of the washing liquid alkaline and of enzyme stability.

[0010] <Component (a)> The detergent of the present invention contains a water-soluble aluminum salt as component (a). As described above, component (a) can further enhance the cleaning effect. In the present invention, "water-soluble aluminum salt" refers to a compound that can dissolve in water and release aluminum ions into the water. More specifically, it refers to a compound that dissolves at least 1 g in 100 g of water at 20°C. The anion that serves as a counter ion to the aluminum ion in component (a) can be appropriately selected by those skilled in the art, as long as component (a) has the above-mentioned water-solubility properties. Note that aluminum ions are also contained in zeolites, typified by crystalline aluminosilicates commonly used in laundry detergents, but are excluded from the water-soluble aluminum salt of the present invention.

[0011] The water-soluble aluminum salt is preferably an inorganic water-soluble aluminum salt, and examples of the inorganic water-soluble aluminum salt include one or more selected from potassium alum (potassium aluminum sulfate), ammonium alum (ammonium aluminum sulfate), sodium alum (sodium aluminum sulfate), aluminum sulfate, aluminum acetate, aluminum chloride, and aluminum nitrate.

[0012] The water-soluble aluminum salt may be a hydrate, and examples of the hydrate of the water-soluble aluminum salt include one or more selected from potassium aluminum sulfate dodecahydrate, sodium aluminum sulfate dodecahydrate, ammonium aluminum sulfate dodecahydrate, aluminum chloride hexahydrate, and aluminum sulfate 14-18 hydrate.

[0013] From the viewpoint of further enhancing the cleaning effect, component (a) is preferably one or more water-soluble aluminum salts selected from aluminum sulfate, aluminum chloride, aluminum nitrate, and hydrates thereof, and more preferably one or more water-soluble aluminum salts selected from aluminum sulfate, aluminum chloride, and hydrates thereof. In the present invention, the mass of component (a) is used as a value converted into the mass of metallic aluminum. That is, the mass of component (a) is calculated as the mass of metallic aluminum equimolar to the aluminum ions contained in component (a).

[0014] <Component (b)> The cleansing agent of the present invention contains an enzyme as component (b). From the viewpoint of further enhancing the cleansing effect, component (b) is preferably one or more enzymes selected from proteases, lipases, and amylases, and more preferably one or more enzymes selected from proteases and amylases.

[0015] From the viewpoint of further enhancing the cleaning effect, the optimum 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. Suitable proteases for use in the present invention include serine proteases (EC 3.4.21) and metalloproteases (EC 3.4.17 or EC 3.4.24). Suitable examples of proteases include neutral or alkaline serine proteases such as subtilisin (EC 3.4.21.62).

[0016] The origin of the protease is not limited, but may be animal, plant, or microbial, with microbial sources such as bacteria and fungi being preferred. Further suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be an alkaline microbial protease and / or a serine protease, such as a trypsin-type protease.

[0017] Suitable commercially available proteases include from Novozymes A / S: Alcalase, Duralase, Durazyme, Relase, Relase 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 Enzymes sold as Key, Progress Excel, Blaze, Blaze Evity, Blaze Exceed and Esperase, from Danisco / DuPont: Preferenz P, Effectenz P, Excellenz P, Maxatase, Maxacal, Maxapem, Purafect, Purafect Prime, Purafect MA, Purafect Ox, Purafect Examples of suitable proteases include, but are not limited to, enzymes sold under the names OxP, Puramax, Properase, Purafast, FN2, FN3, FN4, Excellase, Opticlean, and Optimase, enzymes sold under the name Axapem by Gist-Brocases N.V., enzymes sold under the name BLAP (the sequence shown in Figure 29 of U.S. Pat. No. 5,352,604) and variants thereof (Henkel AG) by Henkel AG, and enzymes sold under the name Lavergy Pro by BASF. Also suitable are alkaline proteases and variants thereof described in Japanese Patent No. 3,479,509.

[0018] From the viewpoint of further enhancing the cleaning effect of component (a), the optimum pH of the lipase at 35°C is preferably 4 or higher, more preferably 7 or higher, even more preferably 8 or higher, still more preferably 9 or higher, still more preferably 9.5 or higher, and preferably 12 or lower, more preferably 11 or lower.

[0019] Suitable lipases for use in the present invention include, for example, triacylglycerol lipase (EC 3.1.1.3), phospholipase A2 (EC 3.1.1.4), lysophospholipase (EC 3.1.1.5), monoglyceride lipase (EC 3.1.1.23), galactolipase (EC 3.1.1.26), phospholipase A1 (EC 3.1.1.32), lipoprotein lipase (EC 3.1.1.34), etc. Examples of lipases include lipases and cutinases from the genera Bacillus, Thermomyces, Pseudomonas, Humicola, and Streptomyces, and may also be chemically or genetically modified mutants of these enzymes. Suitable commercially available lipases include, but are not limited to, enzymes sold by Novozymes A / S as: Lipolase, Lipex, Lipex Evity, Lipolex, Lipoclean, and by Danisco / DuPont as: Preferenz L, Lumafast, Lipomax.

[0020] From the viewpoint of further enhancing the cleaning effect of component (a), the optimum pH of amylase 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.

[0021] Suitable amylases for use in the present invention include α-amylase (EC 3.2.1.1), β-amylase (EC 3.2.1.2) and / or glucoamylase (EC 3.2.1.3), etc. Suitable examples of amylases include neutral or alkaline α-amylases, preferably those of microbial origin such as bacteria or fungi. Neutral or alkaline amylases include, for example, those derived from Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermo, Bacillus subtilis, or other Bacillus species, including chemically or genetically modified mutants thereof. Suitable commercially available amylases include, but are not limited to, enzymes sold by Novozymes A / S as: Duramyl, Termamyl, Termamyl Ultra, Fungamyl, Stainzyme, Stainzyme Plus, Amplify, Amplify Prime, Natalase, Supramyl, Liquozyme X and BAN, and enzymes sold by Danisco / DuPont as: Preferenz S, Effectenz S, Rapidase, Purastar, Powerase.

[0022] <Component (c)> The component (c) of the present invention is a polymer having a carboxy group or a salt thereof (excluding those corresponding to component (a)). The component (c) not only improves the cleaning properties but also can suppress the problem of dye transfer that occurs when the above-mentioned water-soluble aluminum salt is used in combination with an enzyme and a surfactant. In the present invention, the preferred component (c) is one or more polymers selected from the following components (c1) and (c2). Component (c1): a polysaccharide polymer having a carboxy group or a salt thereof Component (c2): a vinyl polymer having a carboxy group or a salt thereof

[0023] [Component (c1)] The component (c1) of the present invention is a polysaccharide polymer having a carboxy group or a salt thereof. In the present invention, the polysaccharide polymer means a polymer having a plurality of sugar skeletons.

[0024] Examples of polysaccharide polymers having a carboxy group or a salt thereof include one or more polysaccharide polymers selected from starch, cellulose, alginic acid, carrageenan, gellan gum, heparin, chondroitin sulfate, xanthan gum, gum arabic, guar gum, and agarose, to which an anionic group, such as carboxymethylated, carboxyethylated, or maleated group, has been chemically introduced. Examples of carboxy groups or salts thereof include alkali metal salts and ammonium salts. These polysaccharide polymers having a carboxy group or a salt thereof may be used alone or in combination. From the viewpoint of achieving a higher dye transfer inhibition effect, one or more polysaccharide polymers selected from carboxymethylated cellulose and carboxymethylated starch, and salts thereof, are preferred. Examples of salts are one or more salts selected from alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, and ammonium salts. These compounds can generally be obtained by immersing cellulose or starch in a concentrated sodium hydroxide solution and reacting it with monochloroacetic acid.

[0025] From the viewpoint of further enhancing the cleaning effect or further enhancing the dye transfer inhibiting effect, the degree of substitution (DS) of the carboxy group or a salt thereof in the polysaccharide polymer is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and preferably 1 or less, more preferably 0.8 or less, even more preferably 0.7 or less, even more preferably 0.6 or less, and even more preferably 0.5 or less. The degree of substitution (DS) of the carboxy group or a salt thereof in the polysaccharide polymer can be determined by the following method.

[0026] [Degree of substitution (DS) of carboxyl groups or their salts in polysaccharide polymer] 2 g of component (c1) is weighed out and placed in a 300 mL Erlenmeyer flask with a stopper. 100 mL of nitric acid solution (a solution obtained by adding 100 mL of concentrated nitric acid to 1000 mL of methanol) is added and stirred for 3 hours to convert the polysaccharide polymer having carboxyl groups or their salts into an acid form (hereinafter referred to as acid-form polysaccharide polymer). 1.5 to 2.0 g of the acid-form polysaccharide polymer is weighed out and placed in a 300 mL Erlenmeyer flask with a stopper. The acid-form polysaccharide polymer is moistened with 15 mL of 80% methanol, 100 mL of 0.1 N NaOH is added, and the mixture is stirred at room temperature for 3 hours. Using phenolphthalein as an indicator, the 0.1 N NaOH is added. ２ SO ４ The excess NaOH is back-titrated with 0.1N NaOH. The DS of a polysaccharide polymer having a carboxy group or a salt thereof is calculated by the following formula: A = [(100 x F - B x F') x 0.1] / (bone-dry mass (g) of acid-type polysaccharide polymer) DS = (molecular weight of monosaccharide forming polysaccharide / 1000) x A / (1 - 0.058 x A) A: amount (mL) of 0.1N NaOH required to neutralize 1 g of acid-type polysaccharide polymer B: amount (mL) of 0.1N NaOH ２ SO ４ Titration value (mL) F: 0.1N-H ２ SO ４ F': Factor of 0.1N-NaOH

[0027] From the viewpoint of further enhancing the cleaning effect or further enhancing the dye transfer inhibiting effect, the weight-average molecular weight of the polysaccharide polymer having a carboxy group or a salt thereof is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 200,000 or more, and is preferably 7,000,000 or less, more preferably 5,000,000 or less, even more preferably 3,000,000 or less, still more preferably 2,000,000 or less, still more preferably 1,000,000 or less, and still more preferably 700,000 or less. The weight-average molecular weight of the polysaccharide polymer having a carboxy group or a salt thereof can be determined by the following method.

[0028] [Weight-average molecular weight of polysaccharide polymer having a carboxy group or a salt thereof] The weight-average molecular weight of a powdery raw material of a polysaccharide polymer having a carboxy group or a salt thereof is determined by dissolving the powdery raw material in water and measuring the aqueous solution by size exclusion chromatography (SEC) under the following conditions. <SEC measurement conditions> Measurement apparatus: "SEC-8320" manufactured by Tosoh Corporation Eluent: 0.2 mol / L phosphate buffer / acetonitrile = 9 / 1 (V / V%) Guard column: "PWXL (6 mm x 4 cm)" manufactured by Tosoh Corporation Analytical column: "G4000PWxL + G2500PWxL (7.8 mm x 30 cm)" manufactured by Tosoh Corporation Flow rate: 1 mL / min Column temperature: 40°C Injection volume: 100 μL Sample size: 1 mg / mL Molecular weight conversion standard: PEO manufactured by Tosoh Corporation (SE-150 (977,000), SE-70 (580,000), SE-30 (394,000), SE-15 (143,000), SE-8 (101,000), SE-2 (21,000)) Detector: RI

[0029] [Component (c2)] The component (c2) of the present invention is a vinyl polymer having a carboxy group or a salt thereof. Component (c2) not only enhances detergency but also suppresses the dye migration problem that occurs when the water-soluble aluminum salt is used in combination with an enzyme and a surfactant.

[0030] As the component (c2) of the present invention, from the viewpoint of further enhancing the cleaning effect or further enhancing the dye transfer inhibiting effect, a polymer having, as a constituent unit, a monomer unit derived from one or more monomers selected from acrylic acid, methacrylic acid, and salts thereof is preferred.

[0031] From the viewpoint of further enhancing the cleaning effect or the dye transfer inhibiting effect, the content of the above-mentioned structural units in component (c2) of the present invention is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, and preferably 100 mol% or less. Examples of monomers other than acrylic acid and methacrylic acid or salts thereof that serve as monomer units constituting component (c2) include maleic acid and salts thereof, fumaric acid and salts thereof, hydroxyacrylic acid and salts thereof, and succinic acid and salts thereof.

[0032] The monomer units constituting component (c2) may include, to the extent that the effects of the present invention are not impaired, structural units derived from (meth)acrylic acid esters having an unsubstituted or substituted, saturated or unsaturated alkyl group having 1 to 4 carbon atoms, or structural units derived from (meth)acrylic acid esters having an aralkyl group. Examples of such (meth)acrylic acid esters include, for example, one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, and polyethylene glycol mono(meth)acrylate. Other examples of the monomer units constituting component (c2) include vinyl monomer units having a phosphate group and / or a salt thereof.

[0033] Examples of salts of component (c2) include alkali metal salts such as sodium salts, and alkanolamine salts having 2 to 6 carbon atoms such as monoethanolamine.

[0034] The method for synthesizing the polymer of component (c2) is not particularly limited, and any known method can be selected. Examples of methods for obtaining the polymer of component (c2) include bulk polymerization, precipitation polymerization, aqueous solution polymerization, and reverse phase suspension polymerization. Among these, aqueous solution polymerization is particularly preferred from the viewpoint of performance and ease of polymerization control. In this case, the types and amounts of polymerization initiators, polymerization inhibitors, and other additives are not particularly limited.

[0035] On the other hand, when two or more of the above-mentioned monomers are copolymerized as component (c2), it is preferable to use acrylic acid and / or its salts and maleic acid and / or its salts as monomers from the viewpoint of further enhancing the cleaning effect or the dye migration inhibition effect. This copolymer may be either a block type or a random type. Furthermore, from the viewpoint of further enhancing the cleaning effect or the dye migration inhibition effect, the weight-average molecular weight of component (c2) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 2,500 or more, and from the same viewpoint, it is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less.

[0036] The weight-average molecular weight of the (c2) component is measured by GPC (gel permeation chromatography) under the following conditions: 1. Conversion standard: Value obtained using a polyacrylic acid (AMERICAN STANDARDS CORP) standard sample as a calibration curve. 2. Eluent: 0.2 mol / L phosphate buffer / CH ３ CN = 9 / 1 (volume ratio), pH = 7 3. Column: PWXL + G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation) 4. Detector: RI 5. Sample concentration: 5 mg / mL 6. Injection volume: 0.1 mL 7. Measurement concentration: 40°C 8. Flow rate: 1.0 mL / min

[0037] <Component (d)> The component (d) of the present invention is one or more surfactants selected from anionic surfactants (component (d1)) and nonionic surfactants (component (d2)). Component (d) can further enhance the cleaning properties of stains adhering to clothing.

[0038] [Component (d1)] The component (d1) of the present invention is an anionic surfactant. Specific examples of the component (d1) include one or more anionic surfactants selected from the following components (d1-1), (d1-2), (d1-3), and (d1-4).

[0039] Component (d1-1): alkyl or alkenyl sulfate ester salt; Component (d1-2): polyoxyalkylene alkyl or alkenyl ether sulfate ester salt having an alkyleneoxy group; Component (d1-3): an anionic surfactant having a sulfonate group; Component (d1-4): a fatty acid having from 12 to 24 carbon atoms or a salt thereof (excluding component (e) described below).

[0040] More specifically, the component (d1-1) can be one or more anionic surfactants selected from alkyl sulfates having an alkyl group with 10 to 18 carbon atoms, and alkenyl sulfates having an alkenyl group with 10 to 18 carbon atoms. From the viewpoint of further enhancing the dye transfer inhibitory effect, the component (d1-1) is preferably one or more anionic surfactants selected from alkyl sulfates having an alkyl group with 12 to 14 carbon atoms.

[0041] More specifically, component (d1-2) may include one or more anionic surfactants selected from polyoxyalkylene alkyl ether sulfate salts having an alkyl group with 10 to 18 carbon atoms and an average number of added moles of alkyleneoxy groups of 1 to 3, and polyoxyalkylene alkenyl ether sulfate salts having an alkenyl group with 10 to 18 carbon atoms and an average number of added moles of alkyleneoxy groups of 1 to 3. Examples of the oxyalkylene group include oxyalkylene groups having 2 to 3 carbon atoms. Examples of the oxyalkylene group having 2 to 3 carbon atoms include one or more groups selected from oxypropylene groups and oxyethylene groups. The average number of added moles of alkyleneoxy groups refers to the average number of moles of alkyleneoxy groups contained in the polyoxyalkylene alkyl ether sulfate salt or polyoxyalkylene alkenyl ether sulfate salt. The average is a molar average that also includes cases where there is 0 mole of alkyleneoxy groups (i.e., alkyl ether sulfate salts). From the viewpoint of further enhancing the dye transfer inhibitory effect, the component (d1-2) is preferably a polyoxyethylene alkyl ether sulfate in which the average number of moles of ethyleneoxy groups added is 1 or more and 2.2 or less, and more preferably a polyoxyethylene alkyl ether sulfate in which the alkyl group has 12 or more and 14 or less carbon atoms and the average number of moles of ethyleneoxy groups added is 1 or more and 2.2 or less.

[0042] The anionic surfactant having a sulfonate group, which is the component (d1-3), refers to an anionic surfactant having a sulfonate salt as the hydrophilic group. More specific examples of the component (d1-3) include one or more anionic surfactants selected from alkylbenzenesulfonates having from 10 to 18 carbon atoms in the alkyl group, alkenylbenzenesulfonates having from 10 to 18 carbon atoms in the alkenyl group, alkanesulfonates having from 10 to 18 carbon atoms in the alkyl group, α-olefinsulfonates having from 10 to 18 carbon atoms in the α-olefin moiety, α-sulfofatty acid salts having from 10 to 18 carbon atoms in the fatty acid moiety, and α-sulfofatty acid lower alkyl ester salts having from 10 to 18 carbon atoms in the fatty acid moiety and from 1 to 5 carbon atoms in the ester moiety. From the viewpoint of further enhancing the dye transfer inhibition effect, the component (d1-3) is preferably an alkylbenzenesulfonate having from 11 to 14 carbon atoms in the alkyl group.

[0043] The component (d1-4) is a fatty acid having from 12 to 24 carbon atoms or a salt thereof (excluding the component (e) described below). The fatty acid having from 12 to 24 carbon atoms or a salt thereof is an anionic surfactant having an aliphatic hydrocarbon group having from 11 to 23 carbon atoms as the hydrophobic group and a carboxylic acid or a salt thereof as the hydrophilic group. More specific examples of the component (d1-4) include lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, and / or salts thereof.

[0044] When the anionic surfactant (d1) is a salt, the salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and even more preferably a sodium salt. When the component (d1) of the present invention is a salt, the mass of the salt is the mass converted into the sodium salt. Here, the mass of the salt converted into the sodium salt means the mass calculated by replacing the salt with an equimolar amount of sodium salt.

[0045] The powder detergent for clothing of the present invention preferably contains, as component (d1), one or more anionic surfactants selected from components (d1-1) and (d1-3).

[0046] In the laundry detergent of the present invention, the mass ratio ([(d1-1)+(d1-3)] / (d1)) of the total content of the components (d1-1) and (d1-3) ((d1-1)+(d1-3)) to the content of the component (d1) is, from the viewpoint of further enhancing the dye transfer inhibiting effect, preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.6 or more, still more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 1 or less, more preferably 0.95 or less. Here, in the mass ratio [(d1-1)+(d1-3)] / (d1), [(d1-1)+(d1-3)] refers not only to an embodiment in which the laundry detergent of the present invention contains both the component (d1-1) and the component (d1-3), but also to an embodiment in which the laundry detergent of the present invention contains only one of the component (d1-1) or the component (d1-3).

[0047] The component (d2) is preferably a nonionic surfactant represented by the following general formula (d2-1): ４ (CO) ｍ O-(AO) ｎ -R ５ (d2-1) [In the formula, R ４ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R ５ is a hydrogen atom or a methyl group; CO is a carbonyl group, and m is the number 0 or 1; AO is an alkyleneoxy group containing an ethyleneoxy group and having 2 to 4 carbon atoms; and n is the average number of moles added, which is a number of 1 to 30.

[0048] In general formula (d2-1), R ４ From the viewpoint of further improving the cleaning property, the number of carbon atoms in R 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. ４ is an aliphatic hydrocarbon group, preferably a group selected from alkyl groups and alkenyl groups.

[0049] In general formula (d2-1), AO is an alkyleneoxy group containing an ethyleneoxy group and having from 2 to 4 carbon atoms, preferably an alkyleneoxy group containing an ethyleneoxy group and having from 2 to 3 carbon atoms, and more preferably an ethyleneoxy group. AO may also be an alkyleneoxy group containing an ethyleneoxy group and another alkyleneoxy group, for example, a propyleneoxy group. The other alkyleneoxy group is preferably a propyleneoxy group. When AO contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be bonded in a block or random manner.

[0050] In general formula (d2-1), n ​​represents the average number of moles of AO added and is a number of 1 to 30. In general formula (d2-1), n ​​is 3 or more, preferably 6 or more, and more preferably 10 or more, and is 30 or less, preferably 25 or less, and more preferably 20 or less, from the viewpoint of further improving detergency.

[0051] In the laundry detergent of the present invention, the mass ratio of the content of the anionic surfactant in the component (d) to the content of the component (d) (content of the anionic surfactant in the component (d) / content of the component (d)) is preferably 0.5 or more, more preferably 0.55 or more, even more preferably 0.6 or more, still more preferably 0.65 or more, and preferably 1 or less, from the viewpoint of further enhancing the dye transfer inhibitory effect.

[0052] A preferred embodiment of the laundry detergent of the present invention is as follows: The component (a) is aluminum sulfate, the component (b) is the protease, the component (c) is one or more polymers selected from the components (c1) and (c2), and the component (d) is one or more surfactants selected from the group consisting of one or more anionic surfactants selected from the components (d1-1) and (d1-3) and the nonionic surfactants represented by the general formula (d2-1).

[0053] <Composition, etc.> The content of component (a) in the detergent of the present invention is, in terms of the amount of metallic aluminum, preferably 0.07% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.12% by mass or more, from the viewpoint of further enhancing the cleaning effect, and is, in terms of the amount of metallic aluminum, preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.3% by mass or less, from the viewpoint of further enhancing the dye transfer inhibitory effect. Here, "amount of metallic aluminum" means, as described above, that the mass of component (a) is used as a value converted into the mass of metallic aluminum.

[0054] From the viewpoint of further enhancing the cleaning effect, the content of component (b) in the detergent of the present invention 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, in terms of the protein amount, and preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1% by mass or less.

[0055] From the viewpoint of further enhancing the cleaning effect, the content of component (a) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.25 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 0.7 parts by mass or less, per part by mass of component (b).

[0056] From the viewpoint of further enhancing the cleaning effect and the dye transfer inhibiting effect, the content of component (c) in the detergent of the present invention 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 7% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less.

[0057] When the detergent of the present invention uses the component (c1) as the component (c), from the viewpoint of further enhancing the dye transfer inhibiting effect, the content of the component (c1) in the laundry detergent is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, even more preferably 0.7% by mass or more, still more preferably 1% by mass or more, still more preferably 1.5% by mass or more, still more preferably 1.7% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 6% by mass or less, still more preferably 5% by mass or less, and still more preferably 3% by mass or less.

[0058] In the cleaning agent of the present invention, the mass ratio of the content of component (c2) to the content of component (c1) (component (c2) / component (c1)) is preferably 0 or more, more preferably 0.05 or more, even more preferably 0.1 or more, even more preferably 0.2 or more, still more preferably 0.3 or more, and is preferably 3.0 or less, more preferably 1.5 or less, even more preferably 1.3 or less, still more preferably 1.0 or less, still more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.7 or less, and still more preferably 0.6 or less.

[0059] From the viewpoint of further enhancing the cleaning effect, the content of component (d) in the cleaning agent of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less.

[0060] [Optional Components] [Component (e): Alkaline Agent] The component (e) of the present invention is one or more alkaline agents selected from the following components (e1), (e2), (e3), and (e4). An alkaline agent refers to an agent that has the effect of raising the pH of water. Component (e1): one or more compounds selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal silicates. Component (e2): an aluminosilicate containing an alkali metal as a constituent element. Component (e3): a tripolyphosphate. Component (e4): an alkanolamine having from 2 to 6 carbon atoms. For example, one or more compounds selected from monoethanolamine, monomethylethanolamine, dimethylmonoethanolamine, and triethanolamine.

[0061] Component (e1) is one or more compounds selected from alkali metal carbonates, alkali metal bicarbonates, and alkali metal silicates. Component (e1) can be one or more compounds selected from sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, and sodium silicate. From the viewpoint of pH adjustment, component (e1) is preferably one or more compounds selected from sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, more preferably one or more compounds selected from sodium carbonate and sodium bicarbonate, and even more preferably sodium carbonate.

[0062] The component (e2) is one or more compounds selected from aluminosilicates containing alkali metals as constituent elements and smectite clays containing alkali metals as constituent elements. The aluminosilicates are compounds represented by the general formula (M Ｉ , M II １／２ ) ｍ (Al ｍ Si ｎ O ２（ｍ＋ｎ） ) xH ２ O, and M Ｉ is sodium, potassium and / or lithium, M IIis calcium, magnesium and / or barium, n is a number of 10 or more and 136 or less, m is a number of 10 or more and 90 or less, n≧m, and x is a number of 10 or more and 300 or less. Ｉ is preferably sodium and / or potassium, more preferably sodium. II is preferably magnesium and / or calcium, more preferably magnesium. n is preferably a number of 10 or more and 20 or less, and m is preferably a number of 10 or more and 19 or less. Examples of zeolite include zeolite A, zeolite P, ferrierite, and mordenite, and from the viewpoint of adjusting the pH and improving detergency, zeolite A is preferred.

[0063] Component (e3) is a tripolyphosphate. The salt is preferably an alkali metal salt, more preferably a sodium salt.

[0064] The component (e4) is an alkanolamine having from 2 to 6 carbon atoms. From the viewpoint of further improving cleaning properties, it is preferably one or more compounds selected from monoethanolamine, monomethylethanolamine, dimethylmonoethanolamine, and triethanolamine, and more preferably monoethanolamine.

[0065] When the cleaning agent of the present invention contains component (e), from the viewpoint of further enhancing the cleaning effect, the cleaning agent may contain component (e) in an amount of preferably 1 mass % or more, more preferably 10 mass % or more, even more preferably 20 mass % or more, still more preferably 30 mass % or more, and preferably 70 mass % or less, more preferably 60 mass % or less, and even more preferably 55 mass % or less.

[0066] [Component (f)] From the viewpoint of further enhancing the cleaning effect or the dye transfer inhibiting effect, the detergent of the present invention may contain, as component (f), one or more compounds selected from alkali metal sulfates and alkali metal chlorides. From the viewpoint of further enhancing the cleaning effect or the dye transfer inhibiting effect, one or more compounds selected from sodium sulfate and sodium chloride are preferred.

[0067] When the detergent of the present invention contains component (f), from the viewpoint of further enhancing the cleaning effect or further enhancing the dye transfer inhibiting effect, the detergent may contain component (f) in an amount of preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 92% by mass or less, more preferably 78% by mass or less, more preferably 50% by mass or less, even more preferably 26% by mass or less, still more preferably 20% by mass or less, still more preferably 15% by mass or less, and still more preferably 10% by mass or less.

[0068] [Component (g)] The detergent of the present invention may contain a polymer other than component (c) as component (g) to the extent that the effects of the present invention are not impaired. When component (g) is contained, the content of component (g) in the total polymers contained in the detergent of the present invention is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. When component (g) contains a quaternary ammonium group, the mass of the counterion is calculated as the mass converted into a chloride ion. When component (g) contains an anionic group other than a carboxy group that can dissociate in water to form an anion, the mass of the counterion is calculated as the mass converted into a Na ion. Here, the mass of the counterion converted into a chloride ion means the mass calculated by replacing the counterion with an equimolar amount of chloride ions, and the mass of the counterion converted into a Na ion means the mass calculated by replacing the counterion with an equimolar amount of Na ions.

[0069] [Component (h)] The cleaning agent of the present invention may contain a surfactant other than component (d) as component (h) to the extent that the effects of the present invention are not impaired. Examples of component (d) include one or more surfactants selected from cationic surfactants and amphoteric surfactants. When component (h) is contained, the content of component (h) in the total amount of components (a) and (h) contained in the cleaning agent of the present invention is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less. When component (h) is a cationic surfactant, the mass of component (h) is the mass of the counter ion of the cation of component (h) converted into chloride ion. The mass of the counter ion converted into chloride ion is as defined above.

[0070] The cationic surfactant may be one or more cationic surfactants selected from the following components (h1) and (h2). Component (h1): A quaternary ammonium compound having one aliphatic hydrocarbon group having from 12 to 16 carbon atoms and three groups selected from an alkyl group having from 1 to 3 carbon atoms and a hydroxyalkyl group having from 2 to 3 carbon atoms. Component (h2): A quaternary ammonium compound having two aliphatic hydrocarbon groups having from 8 to 10 carbon atoms and two groups selected from an alkyl group having from 1 to 3 carbon atoms and a hydroxyalkyl group having from 2 to 3 carbon atoms. The aliphatic hydrocarbon groups of the components (h1) and (h2) may be alkyl groups, and examples of the alkyl group having from 1 to 3 carbon atoms include methyl, ethyl, and propyl groups. Examples of the hydroxyalkyl group having from 2 to 3 carbon atoms include hydroxyethyl and hydroxypropyl groups. Examples of the counter ion include chloride ions, methyl sulfate ions, and ethyl sulfate ions.

[0071] The detergent of the present invention may be either a solid detergent or a liquid detergent. From the viewpoint of solubility, the detergent of the present invention is preferably one or more solid detergents selected from powder, granules, and granular forms.

[0072] The solid detergent can be produced by a known method, such as spray drying, dry neutralization, dry granulation, dry blending, fluidized bed drying, thin film drying, extrusion granulation, tumbling granulation, stirring granulation, compaction granulation, surfactant immobilization, or a combination of methods selected from these.

[0073] When the cleaning agent of the present invention is a liquid cleaning agent, it may contain water. The water may be deionized water (sometimes called ion-exchanged water) or water to which sodium hypochlorite has been added in an amount of 1 mg / kg to 5 mg / kg based on the ion-exchanged water. Tap water may also be used.

[0074] When the cleaning agent of the present invention contains water, the content of water in the cleaning agent is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less.

[0075] The cleaning agent of the present invention may contain other components known in the field of laundry detergents, such as bleaching agents (perborates, bleach activators, etc.), anti-redeposition agents, reducing agents (sulfites, etc.), fluorescent brightening agents, foam suppressors (silicones, etc.), organic solvents, fragrances, colorants, antibacterial agents, etc. (excluding those corresponding to components (a) to (h)).

[0076] The pH at 25°C of the laundry detergent of the present invention, when dissolved in 1 L of ion-exchanged water, is 9.0 or more, preferably 9.5 or more, more preferably 10 or more, from the viewpoint of further enhancing the cleaning effect or the dye transfer inhibiting effect, and is 12.0 or less, preferably 11.5 or less, more preferably 11.0 or less. The pH is measured according to the pH measurement method described below.

[0077] <pH Measurement Method> A pH measurement composite electrode (HORIBA pH / Ion Meter F-23) is connected to a pH meter and powered on. A saturated potassium chloride aqueous solution (3.33 mol / L) is used as the pH electrode internal solution. Next, a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution), and a pH 9.18 standard solution (borate standard solution) are each filled into 100 mL beakers and immersed in a thermostatic bath at 25°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solutions for 3 minutes, and calibration is performed in the order of pH 9.18 → pH 4.01 → pH 6.86. The sample to be measured is adjusted to 25°C, the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

[0078] The clothing to be washed in the present invention includes denim pants and jackets, batik, undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, etc., and is particularly useful in embodiments where dye-migratory clothing is to be washed. Examples of fibers constituting the clothing include hydrophobic fibers such as acrylic, polyester, and nylon, and hydrophilic fibers such as cotton.

[0079] [Method for washing clothing] The present invention provides a method for washing clothing, which involves contacting clothing with a washing solution containing the following components (a), (b), (c), and (d), and water, and having a pH of 9.0 to 12.0 at 25°C: Component (a): a water-soluble aluminum salt Component (b): an enzyme Component (c): a polymer having a carboxy group or a salt thereof (excluding those corresponding to component (a)) Component (d): one or more surfactants selected from anionic surfactants and nonionic surfactants Furthermore, the present invention relates to the above-mentioned washing method, which is used for washing clothing, particularly clothing that is dye-transferable.

[0080] In the present invention, as described above, clothing with dye migration properties refers to clothing that may be discolored, and may be clothing in which different parts of a single clothing have different colors, or a group of clothing in which multiple clothing items have different colors, or a combination thereof. From the viewpoint of further achieving the dye migration suppression effect of the present invention, it is preferable that at least one of the different colors is white. Furthermore, from the viewpoint of further achieving the dye migration suppression effect, it is preferable to use multiple groups of clothing including clothing with colored parts and white clothing as clothing to be washed with the clothing detergent.

[0081] The details of the components (a), (b), (c), and (d) are the same as those described for the cleaning agent of the present invention, and specific embodiments thereof are also the same. For example, in terms of cleaning effect, the component (c) in the cleaning method of the present invention is preferably one or more polymers selected from the components (c1) and (c2). In addition, in terms of cleaning effect, the component (a) is preferably the inorganic water-soluble aluminum salt. In addition, in terms of cleaning effect, the component (b) is preferably one or more enzymes selected from the proteases and amylases.

[0082] The same applies to the optional components (e), (f), (g), (h) and other optional components.

[0083] The amounts of the respective components can be the same as those of the cleaning agent of the present invention, except for the amount of water. For example, the mass ratio of the content of the component (c2) to the content of the component (c1) in the cleaning solution (content of component (c2) / content of component (c1)) is, from the viewpoint of cleaning effect, preferably 0 or more, more preferably 0.05 or more, even more preferably 0.1 or more, even more preferably 0.2 or more, still more preferably 0.3 or more, and preferably 3.0 or less, more preferably 1.5 or less, even more preferably 1.3 or less, still more preferably 1.0 or less, still more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.7 or less, and still more preferably 0.6 or less. Furthermore, in the cleaning solution, the mass ratio of the content of the anionic surfactant in the component (d) to the content of the component (d) (content of anionic surfactant in the component (d) / content of the component (d)) is, from the viewpoint of cleaning effect, preferably 0.5 or more, more preferably 0.55 or more, even more preferably 0.6 or more, still more preferably 0.65 or more, and preferably 1 or less.

[0084] A preferred embodiment of the cleaning method of the present invention is as follows: The component (a) is aluminum sulfate, the component (b) is the protease, the component (c) is one or more polymers selected from the components (c1) and (c2), and the component (d) is one or more surfactants selected from the group consisting of one or more anionic surfactants selected from the components (d1-1) and (d1-3) and the nonionic surfactants represented by the general formula (d2-1).

[0085] In the method for washing clothes of the present invention, the cleaning liquid of the present invention is preferably obtained by mixing the detergent of the present invention with water. That is, the present invention provides a method for washing clothes in which clothing is washed with a cleaning liquid obtained by mixing a detergent with water (referred to as the "cleaning liquid of the present invention" in this specification). The aspects described for the detergent of the present invention can be applied as appropriate to the method for washing clothes of the present invention.

[0086] In the method for washing clothing of the present invention, the detergent of the present invention and water may be first charged into a washing tank and mixed to prepare the washing solution of the present invention, and then the clothing to be washed is charged and the clothing washed. However, from the viewpoint of enjoying the effects of the present invention, it is preferable to charge the detergent of the present invention, water, and clothing into a washing tank, and wash the clothing while dissolving the detergent of the present invention in the water to prepare the washing solution of the present invention.

[0087] In the cleaning solution of the present invention, the amount of water used when mixing the detergent of the present invention with water is adjusted so that the total amount of the detergent of the present invention per 1 L of water is preferably 0.01 g or more, more preferably 0.1 g or more, even more preferably 0.3 g or more, and preferably 10 g or less, more preferably 1 g or less, even more preferably 0.5 g or less, from the viewpoints of environmental considerations and cleaning ability for complex soils containing protein.

[0088] In the cleaning solution of the present invention, the hardness of water to be mixed with the detergent of the present invention is, from the viewpoint of the stability of the surfactant and the enzyme, preferably 0.01° dH or more, more preferably 0.1° dH or more, even more preferably 1° dH or more, and preferably 20° dH or less, more preferably 10° dH or less, even more preferably 5° dH or less on the German hardness scale. The hardness of the cleaning solution may be within the above range.

[0089] Here, the German hardness (° dH) in this specification refers to the concentration of calcium and magnesium in water expressed as CaCO ３ This refers to the equivalent concentration expressed as 1 mg / L (mg / kg) = approximately 0.056°dH (1°dH = 17.8 mg / kg). The calcium and magnesium concentrations for this German hardness are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.

[0090] The specific method for measuring the German hardness of water in this specification is described below. <Method for measuring the German hardness of water> [Reagents] 0.01 mol / L EDTA.2Na solution: 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH) Universal BT indicator (product name: Universal BT, manufactured by Dojindo Laboratories) Ammonia buffer solution for hardness measurement (solution prepared by dissolving 67.5 g of ammonium chloride in 570 mL of 28 w / v % ammonia water, and adding ion-exchanged water to make up to 1000 mL in total)

[0091] [Hardness Measurement] (1) Using a volumetric pipette, place 20 mL of sample water into a conical beaker. (2) Add 2 mL of ammonia buffer solution for hardness measurement. (3) Add 0.5 mL of Universal BT indicator. Confirm that the solution is reddish purple after addition. (4) While shaking the conical beaker well, add 0.01 mol / L EDTA 2Na solution dropwise from a burette. The endpoint of the titration is when the sample water turns blue. (5) Calculate hardness using the following formula: Hardness (°dH) = T x 0.01 x F x 56.0774 x 100 / A T: Titration volume (mL) of 0.01 mol / L EDTA 2Na solution A: Sample volume (20 mL, volume of sample water) F: Factor of 0.01 mol / L EDTA 2Na solution

[0092] The hardness of the water used in the washing method, such as the water used to prepare the washing solution and the water used for rinsing, can also be selected from the preferred range of hardness of water containing hardness components described in the method for washing clothes of the present invention. The water hardness can also be measured in the same manner as the water hardness described above.

[0093] In the cleaning solution of the present invention, the mass ratio of component (a) to the amount of enzyme protein of component (b), specifically, the parts by mass of component (a) per part by mass of the enzyme protein of component (b), is preferably within the same range as described for the cleaning agent of the present invention.

[0094] The temperature of the cleaning solution of the present invention is preferably 0°C or higher, more preferably 5°C or higher, and even more preferably 10°C or higher, from the viewpoint of further enhancing the cleaning effect, and is preferably 60°C or lower, more preferably 50°C or lower, even more preferably 40°C or lower, and even more preferably 30°C or lower, from the viewpoint of further enhancing the dye transfer suppression effect.

[0095] The pH of the cleaning solution of the present invention at 25°C is 9.0 or more, preferably 9.5 or more, and 12.0 or less, preferably 11.5 or less, more preferably 11.0 or less, from the viewpoint of further enhancing the cleaning effect or the dye migration inhibiting effect. The pH of the cleaning solution at 25°C can be measured according to the above-mentioned pH measurement method.

[0096] In recent years, washing machines have become larger, and the value of the liquor ratio, which is the ratio of the mass of clothes (kg) to the amount of water in the wash solution (liters), i.e., the amount of water in the wash solution (liters) / mass of clothes (kg) (hereinafter, this ratio may be referred to as the liquor ratio), tends to decrease. When a household washing machine is used, a small liquor ratio can make dye migration more likely to occur, and from the viewpoint of more effectively suppressing dye migration, the liquor ratio is preferably 5 or more, more preferably 10 or more, and even more preferably 20 or more, and from the viewpoint of washing efficiency, it is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and even more preferably 20 or less.

[0097] In the method for washing clothes of the present invention, the washing time is preferably 1 minute or more, more preferably 3 minutes or more, and even more preferably 5 minutes or more, from the viewpoint of further enhancing the washing effect, and is preferably 1 hour or less, more preferably 45 minutes or less, even more preferably 30 minutes or less, and even more preferably 10 minutes or less, from the viewpoint of further enhancing the dye transfer suppression effect.

[0098] The method for washing clothes of the present invention is suitable for a rotary washing method, which involves immersing the clothes in a washing solution while feeding the fibers with a roller or the like. The rotary washing method refers to a washing method in which clothes that are not fixed to a rotating device rotate around a rotating shaft together with the washing solution. The rotary washing method can be performed using a rotary washing machine. Therefore, in the present invention, it is preferable to wash clothes using a rotary washing machine in order to achieve a cleaner finish for the clothes. Specific examples of rotary washing machines include drum washing machines, pulsator washing machines, and agitator washing machines. These rotary washing machines can each be commercially available for home use.

[0099] 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 are not intended to limit the scope of the present invention. Note that "normal pressure" refers to 101.3 kPa, and "normal temperature" refers to 25°C.

[0100] <Ingredients> The following ingredients were used in the Examples, Comparative Examples, and Formulation Examples. [Component (a)] (a-1): Aluminum sulfate (aluminum sulfate 14-18 hydrate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) [Component (b)] (b-1): Protease (Savinase 8.0T, manufactured by Novozymes) [Component (c)] (c1-1): Carboxymethyl cellulose (weight average molecular weight: 500,000, degree of carboxymethyl group substitution: 0.5) (c1-2): Carboxymethyl cellulose (weight average molecular weight: 3,000,000, degree of carboxymethyl group substitution: 0.7) (c1-3): Carboxymethyl cellulose (weight average molecular weight: 3,000,000, degree of carboxymethyl group substitution: 0.9) (c2-1): Sodium polyacrylate (weight average molecular weight: 10,000) (c2-2): Sodium polyacrylate (weight average molecular weight: 25,000) (c2-3): Sodium acrylate / sodium maleate copolymer (copolymerization molar ratio of sodium acrylate and sodium maleate = 71 / 29, weight average molecular weight: 25,000) [Component (d)] (d-1): Sodium alkylbenzenesulfonate (Neopelex G-65, manufactured by Kao Corporation) (d-2): Polyoxyethylene lauryl ether (average number of moles of oxyethylene groups added: 6.5) [Component (e)] (e-1): Sodium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (e-2): Zeolite (e-3): Sodium hydrogencarbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (e-4): Sodium tripolyphosphate (e-5): Sodium silicate [Component (f)] (f-1): Sodium sulfate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0101] Examples 1 to 15, 20 to 26 and Comparative Examples 1 to 5 <Preparation of Detergents> Using the above-mentioned ingredients, the laundry detergents shown in Tables 1, 2, 3, and 4 were prepared by the following method. When component (d) was a nonionic surfactant (polyoxyethylene alkyl ether), component (d) was mixed with component (e) and adsorbed, and then components (a), (b), and (c) were added and stirred to prepare various powdered solid detergents. When component (d) was an anionic surfactant (LAS, AS, AES), a 65% aqueous solution of component (d) was prepared, mixed with component (e), dried, and adsorbed, and then components (a), (b), (c), and (f) were added and stirred to prepare powdered laundry detergents. The pH of each laundry detergent was measured using the above-mentioned method.

[0102] <Preparing concentrated hard water (5000°DH)> Weigh out 92.25 g of calcium chloride dihydrate and 54.46 g of magnesium chloride hexahydrate, and add ion-exchanged water to make 1 L. Stir with a magnetic stirrer to completely dissolve. Calcium chloride dihydrate (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Magnesium chloride hexahydrate (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0103] <Preparing concentrated alkaline solution (alkalinity 30,000)> Weigh out 58.3 g of sodium bicarbonate and 25 g of 1N hydrochloric acid, and add ion-exchanged water to bring the total volume to 1 L. Stir with a magnetic stirrer until completely dissolved. - Sodium bicarbonate (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) - 1N hydrochloric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., for volumetric analysis)

[0104] [Evaluation of cleaning power] 1. Preparation of artificially soiled cloth The artificially soiled cloth for the collar and sleeve protein model stain was a C-10 soiled cloth (6 cm x 6 cm, Center For Test materials BV, manufactured by CFT). The white cloth used to measure the cleaning rate was a white cloth (6 cm x 6 cm) manufactured by CFT. The composition of the collar and sleeve protein model stain contained in the artificially soiled cloth is as follows: Composition of collar and sleeve protein model stain: peanut oil, pigment, high-concentration milk

[0105] <Cleaning test> 2g of detergent was added to 1L of ion-exchanged water adjusted to 30°C, and completely dissolved using a magnetic stirrer. This was transferred to the cup of a tergotometer (cleaning power tester), and 2ml each of hard water concentrate and alkaline concentrate was added and gently stirred. Four soiled cloths were added to this, and treatment was carried out at a rotation speed of 100 rpm for 10 minutes. After treatment was complete, the soiled cloths were lightly rinsed with running water and dried in a high-temperature press. Equipment used: tergotometer (Ueshima Tergotometer MS-8212)

[0106] <Measurement of reflectance of soiled cloth> The cleaning rate was calculated by measuring the reflectance of the soiled cloth before and after cleaning using the following formula. Cleaning rate (%): (R w -R s ) / (R0-R s )*100 ※R w : Reflectance after cleaning; R s : Reflectance before cleaning: R0: Reflectance of white cloth (raw cloth) Measuring equipment: Spectrophotometer SE7700 (manufactured by NIPPON DENSHOKU) Light source: D65; Measurement wavelength: 380-780nm The higher the cleaning rate value, the better the cleaning ability.

[0107] [Evaluation of dye transfer inhibition] <Preparation of indigo dispersion> 0.2 g of indigo and 0.02 g of Emulgen 108 were weighed out on a precision balance, and ion-exchanged water was added to bring the total to 100 g, followed by stirring until the indigo was completely dispersed. If the indigo was not completely dispersed, Emulgen 108 was added in small amounts until it was completely dispersed. - Indigo (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) - Emulgen 108 (manufactured by Kao Corporation)

[0108] <Color Transfer Test> 1.2 g of detergent was added to 600 ml of ion-exchange water adjusted to 30°C and completely dissolved using a magnetic stirrer. This was transferred to the cup of a Tergotometer (detergency tester), and 1.2 ml each of hard water concentrate and alkaline concentrate were added and gently stirred. 6 ml of indigo dispersion was then added, followed by 20 g of white cloth (cotton knit, unspun, manufactured by Tanigashira Shoten, cut into 6 cm x 6 cm pieces). The mixture was then treated at 100 rpm for 10 minutes. After treatment, the treated white cloth was lightly rinsed with running water and dried in a high-temperature press.

[0109] <Measuring reflectance of white cloth> Color transfer was evaluated by measuring the reflectance of the white cloth before and after treatment and calculating ΔE* using the following formula: ΔE* from white cloth before treatment: ((Lw-Lc)+(aw-ac)+(bw-bc))^(1 / 2) *Lw, aw, bw: L*a*b* values ​​of the white cloth before treatment; Lc, ac, bc: L*a*b* values ​​of the white cloth after treatment Measuring equipment: Spectrophotometer SE7700 (NIPPON DENSHOKU) Light source: D65; Measurement wavelength: 380-780nm The lower the ΔE* from the white cloth before treatment, the better the dye transfer prevention properties.

[0110]

[0111]

[0112]

[0113] Looking at Comparative Example 1 and Examples 1 to 5, by using the aluminum salt (component (a)) in combination with the enzyme (component (b)), the cleaning rate is improved even when the enzyme content is constant. As in Example 5, the cleaning power of the enzyme slightly decreases when a certain ratio is exceeded. Visually inspecting the color transfer evaluation of Examples 1, 4, and 5, Example 1 was comparable to Example 2, while Examples 4 and 5 showed slightly more color transfer than Example 2. However, the color transfer was still at an acceptable level in Examples 4 and 5, although it was still more slight. Looking at Examples 7 to 11, the dye transfer inhibition effect improves as the proportion of the polysaccharide polymer (component (c1)) having a carboxy group increases within the (c) component. From the viewpoint of achieving both high cleaning power and dye transfer inhibition at an appropriate level, the range (C1 / C2 ratio) of Examples 9 to 11 is most preferable.

[0114]

[0115] Examples 20 and 21 showed that the combined use of an anionic surfactant and a nonionic surfactant resulted in higher detergency. Examples 22 to 26 showed that the use of various polymers as component (c) could simultaneously achieve both detergency and color transfer inhibition. Furthermore, Example 26 showed that the use of various alkali agents or builders as component (d) could simultaneously achieve both detergency and color transfer inhibition.

[0116] Formulation Example 1: A clothing detergent was prepared using the composition of Example 4, except that the amount of component (e-1) was reduced from 33.0% by mass to 3.0% by mass, and the amount of component (f-1) was increased by 30% by mass. The pH of this clothing detergent was 9.0. It was predicted that this clothing detergent would be satisfactory in both cleaning performance and dye transfer prevention properties.

[0117] The laundry detergent of the present invention can be used as a detergent for washing clothes.

Claims

1. A laundry detergent containing the following components (a), (b), (c), and (d), wherein the pH at 25°C when 2 g of the laundry detergent is dissolved in 1 L of ion-exchanged water is 9.0 or more and 12.0 or less: Component (a): a water-soluble aluminum salt; Component (b): an enzyme; Component (c): a polymer having a carboxy group or a salt thereof (excluding those corresponding to component (a)); Component (d): one or more surfactants selected from anionic surfactants and nonionic surfactants.

2. The laundry detergent according to claim 1, wherein the component (c) is one or more polymers selected from the following components (c1) and (c2): Component (c1): a polysaccharide polymer having a carboxy group or a salt thereof, and Component (c2): a vinyl polymer having a carboxy group or a salt thereof.

3. A laundry detergent as described in claim 2, wherein the mass ratio of the content of the (c2) component to the content of the (c1) component (content of the (c2) component / content of the (c1) component) is 0 or more and 3.0 or less.

4. A laundry detergent according to any one of claims 1 to 3, wherein the mass ratio of the content of the anionic surfactant in the component (d) to the content of the component (d) (content of the anionic surfactant in the component (d) / content of the component (d)) is 0.5 or more and 1 or less.

5. A laundry detergent according to any one of claims 1 to 4, wherein component (a) is an inorganic water-soluble aluminum salt.

6. The laundry detergent according to any one of claims 1 to 5, wherein component (b) is one or more enzymes selected from proteases and amylases.

7. The laundry detergent according to any one of claims 1 to 6, wherein the component (a) is aluminum sulfate, the component (b) is a protease, the component (c) is one or more polymers selected from the following components (c1) and (c2), and the component (c1) is a polysaccharide polymer having a carboxy group or a salt thereof, the component (c2) is a vinyl polymer having a carboxy group or a salt thereof, and the component (d) is one or more surfactants selected from the following components (d1-1) and (d1-3), and nonionic surfactants represented by the following general formula (d2-1): Component (d1-1): alkyl or alkenyl sulfate ester, and component (d1-3): anionic surfactant having a sulfonate group. R ４ (CO) ｍ O-(AO) ｎ -R ５ (d2-1) [In the formula, R ４ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R ５ is a hydrogen atom or a methyl group; CO is a carbonyl group, and m is the number 0 or 1; AO is an alkyleneoxy group containing an ethyleneoxy group and having 2 to 4 carbon atoms; and n is the average number of moles added, which is a number of 1 to 30.

8. The laundry detergent according to any one of claims 1 to 7, which is one or more solid detergents selected from powder, granules and particulates.

9. A method for washing clothes, comprising contacting the clothes with a washing solution containing the following components (a), (b), (c), and (d) and water, and having a pH of 9.0 to 12.0 at 25°C: Component (a): a water-soluble aluminum salt; Component (b): an enzyme; Component (c): a polymer having a carboxy group or a salt thereof (excluding those falling under component (a)); Component (d): one or more surfactants selected from anionic surfactants and nonionic surfactants.

10. The cleaning method according to claim 9, wherein the component (c) is one or more polymers selected from the following components (c1) and (c2): component (c1): a polysaccharide polymer having a carboxy group or a salt thereof, and component (c2): a vinyl polymer having a carboxy group or a salt thereof.

11. The cleaning method according to claim 10, wherein the mass ratio of the content of the component (c2) to the content of the component (c1) in the cleaning solution (content of the component (c2) / content of the component (c1)) is 0 or more and 3.0 or less.

12. The cleaning method according to any one of claims 9 to 11, wherein the mass ratio of the content of the anionic surfactant in the component (d) to the content of the component (d) in the cleaning solution (content of anionic surfactant in the component (d) / content of the component (d)) is 0.5 or more and 1 or less.

13. A cleaning method according to any one of claims 9 to 12, wherein component (a) is an inorganic water-soluble aluminum salt.

14. The cleaning method according to any one of claims 9 to 13, wherein the component (b) is one or more enzymes selected from proteases and amylases.

15. The cleaning method according to any one of claims 9 to 14, wherein the component (a) is aluminum sulfate, the component (b) is a protease, the component (c) is one or more polymers selected from the following components (c1) and (c2), and wherein: component (c1) is a polysaccharide polymer having a carboxy group or a salt thereof, and component (c2) is a vinyl polymer having a carboxy group or a salt thereof, and the component (d) is one or more surfactants selected from the following components (d1-1) and (d1-3), and nonionic surfactants represented by the following general formula (d2-1): Component (d1-1): alkyl or alkenyl sulfate ester Component (d1-3): anionic surfactant having a sulfonate group R ４ (CO) ｍ O-(AO) ｎ -R ５ (d2-1) [In the formula, R ４ is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R ５ is a hydrogen atom or a methyl group; CO is a carbonyl group; and m is the number 0 or 1. AO is an alkyleneoxy group containing an ethyleneoxy group and having 2 to 4 carbon atoms, and n is the average number of moles added, which is a number of 1 to 30.

16. The cleaning method according to any one of claims 9 to 15, wherein the clothing is dye-transferable clothing.

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