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WO2024166840A1 - Cleaning agent composition - Google Patents

Cleaning agent composition Download PDF

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Publication number
WO2024166840A1
WO2024166840A1 PCT/JP2024/003614 JP2024003614W WO2024166840A1 WO 2024166840 A1 WO2024166840 A1 WO 2024166840A1 JP 2024003614 W JP2024003614 W JP 2024003614W WO 2024166840 A1 WO2024166840 A1 WO 2024166840A1
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WO
WIPO (PCT)
Prior art keywords
component
less
mass
cleaning
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2024/003614
Other languages
French (fr)
Japanese (ja)
Inventor
渉 上野
宏紀 小島
敏正 久米
勝也 齊川
雅弥 福田
大輝 石炭
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to AU2024218057A priority Critical patent/AU2024218057A1/en
Priority to CN202480010949.1A priority patent/CN120641545A/en
Publication of WO2024166840A1 publication Critical patent/WO2024166840A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86Mixtures of anionic, cationic, and non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers

Definitions

  • the present invention relates to a cleaning composition.
  • Japanese Patent Laid-Open Publication No. 7-286195 discloses a method for producing a granular nonionic detergent composition, in which (a) a nonionic surfactant, (b) a porous inorganic powder containing 50% by weight or more of SiO2 , and (c) a soap are uniformly kneaded and mixed in predetermined amounts to form a solid detergent, and then an inorganic powder is added as a grinding aid to crush the solid detergent into powdery or granular detergent particles.
  • a high bulk density granular nonionic detergent composition containing (a) a nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, (d) a specified polymer chelate builder, and (e) a positively charged nitrogen atom-containing compound which has a positively charged nitrogen atom in its molecule, is at least partially dissolved in the nonionic surfactant (a), and is adsorbed to the clay mineral (b).
  • 2004-10681 discloses a granular detergent composition which contains (a) a specified amine compound, (b) a sulfonate salt, (c) a specified nonionic compound, and (d) a water-soluble inorganic salt, and has a surfactant equivalent content according to JIS K3362:1998 of 10 to 60 mass %.
  • the present invention provides a detergent composition which has excellent cleaning properties, rinsing properties and finish properties for textile products and further imparts antibacterial properties to the textile products.
  • the finish quality refers to reducing the amount of undissolved cleaning composition and reducing streaks remaining on the item to be cleaned.
  • the present invention comprises the following component (A) in an amount of 5% by mass or more and 40% by mass or less, the following component (B) in an amount of 20% by mass or more and 80% by mass or less, the following component (C) in an amount of 5% by mass or more and 40% by mass or less, the following component (D) in an amount of 0.1% by mass or more and 5.0% by mass or less, and the following component (E) in an amount of 0.1% by mass or more and 10% by mass or less, a mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more and 0.5 or less; a mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) component is 0.2 or more and 0.8 or less; a mass ratio (C)/[(B)+(C)] of the content of the (C) component to
  • the present invention provides a detergent composition that has excellent cleaning, rinsing and finishing properties for textile products, and further imparts antibacterial properties to the textile products.
  • the mechanism by which the detergent composition of the present invention has excellent cleaning properties, rinsing properties and finishing properties for textile products and further imparts antibacterial properties to the textile products is not clear, but is presumed to be as follows. It is presumed that the cleaning ability of the detergent composition of the present invention against sebum stains is improved by using a nonionic surfactant as component (a1), an anionic surfactant as component (a2), and an alkaline agent as component (b1) in combination. It is also presumed that the cleaning power of the detergent composition of the present invention against muddy soils is improved by the combined use of component (a2) and the anionic polymer (E).
  • the cleaning composition of the present invention achieves both rinsability and finish by containing a specific component (A) and further by controlling the ratio of the water-soluble inorganic salt of component (B) to the water-insoluble inorganic salt of component (C) within a specific range.
  • the finish in the present invention refers to reducing the amount of undissolved part of the cleaning composition and reducing streaks on the washed object.
  • the combination of components (A) to (E) in the cleaning composition of the present invention provides excellent cleaning properties, rinsing properties and finishing properties for textile products without impairing the antibacterial activity of component (D).
  • the action mechanism of the cleaning composition of the present invention is not limited to the above-mentioned mechanism.
  • the cleaning composition of the present invention contains the following components (A), (B), (C), (D) and (E) in given amounts.
  • the component (A) is one or more surfactants selected from the group consisting of (a1) nonionic surfactants and (a2) anionic surfactants.
  • the component (A) may be a surfactant containing one or more surfactants selected from the component (a1) and, optionally, one or more surfactants selected from the component (a2).
  • the component (a1) is a nonionic surfactant, and from the viewpoint of cleaning performance, the component (a1) can be one or more selected from the group consisting of polyoxyalkylene alkyl or alkenyl ethers, alkyl (poly)glycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, compounds in which an alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, fatty acid monoglycerides, and sucrose fatty acid esters.
  • (a1-1) a nonionic surfactant containing alkyleneoxy groups and having an average added mole number of alkyleneoxy groups of 1 or more and 30 or less (hereinafter referred to as component (a1-1)).
  • the alkyleneoxy group of the component (a1-1) is preferably one or more groups selected from alkyleneoxy groups having from 2 to 4 carbon atoms, and more preferably one or more groups selected from an ethyleneoxy group and a propyleneoxy group.
  • the average number of moles of alkyleneoxy groups added in the component (a1-1) is, from the viewpoint of cleansing ability against sebum stains, 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the component (a1-1) is preferably a nonionic surfactant represented by the following general formula (a1-1).
  • R 1a is an aliphatic hydrocarbon group having 8 to 18 carbon atoms
  • R 2a is a hydrogen atom or a methyl group.
  • CO is a carbonyl group
  • m is the number of 0 or 1.
  • the A 1a O group is one or more selected from alkyleneoxy groups having 2 to 4 carbon atoms.
  • n is the average number of moles added of the A 1a O groups, and is a number of 1 to 30.
  • R 1a is an aliphatic hydrocarbon group, preferably a group selected from an alkyl group and an alkenyl group.
  • the A 1a O group is one or more selected from alkyleneoxy groups having from 2 to 4 carbon atoms, preferably one or more selected from alkyleneoxy groups having from 2 to 3 carbon atoms, more preferably an ethyleneoxy group.
  • the different alkyleneoxy groups may be bonded in a block manner or a random manner.
  • n is the average number of moles of A 1a O groups added and is a number of 1 to 30.
  • n is 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less, from the viewpoint of cleansing ability against sebum stains.
  • m is preferably 0 from the viewpoint of cleaning properties.
  • R 2a is preferably a hydrogen atom from the viewpoint of cleaning properties.
  • nonionic surfactants that do not have an alkyleneoxy group other than component (a1-1) include one or more selected from sucrose fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, alkyl glycosides, and glyceryl monoethers.
  • the component (a2) is an anionic surfactant.
  • the component (a2) is preferably one or more selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, alkanesulfonic acid type surfactants, olefinsulfonic acid type surfactants, sulfosuccinic acid alkyl ester type surfactants, sulfo fatty acid ester type surfactants, and fatty acids and their salts, more preferably one or more selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, sulfosuccinic acid alkyl ester type surfactants, and fatty acids and their salts, and even more preferably one or more selected from alkylarylsulfonic acid type surfactants, and fatty acids and their salts.
  • component (a2) is a salt
  • examples of the salt include inorganic salts such as sodium salt, potassium salt, ammonium salt, magnesium salt, etc., and organic salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, morpholine salt, etc.
  • the salt of component (a2) is preferably an inorganic salt selected from alkali metal salts such as sodium salt, potassium salt, etc. and alkaline earth metal salts such as magnesium salt, etc., more preferably an alkali metal salt, and even more preferably a sodium salt.
  • the component (a2) examples include one or more compounds selected from the compounds represented by the following general formula (a2-1) (hereinafter referred to as the component (a2-1)), the compounds represented by the general formula (a2-2) (hereinafter referred to as the component (a2-2)), the compounds represented by the general formula (a2-3) (hereinafter referred to as the component (a2-3)), and the compounds represented by the general formula (a2-4) (hereinafter referred to as the component (a2-4)).
  • the component (a2) is preferably one or more selected from the components (a2-1), (a2-2), and (a2-3), and more preferably one or more selected from the components (a2-1) and (a2-2).
  • R 3a -B-SO 3 M (a2-1) [In formula (a2-1), R 3a represents an alkyl group having 9 to 14 carbon atoms, B represents a benzene ring, the carbon atom of R 3a bonded to the carbon atom of B is a secondary carbon atom, and M represents a cation.
  • R 4a -COOM (a2-2) [In formula (a2-2), R 4a represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, and M represents a cation.]
  • R 5a -O-(AO) n -SO 3 M (a2-3) [In formula (a2-3), R 5a is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group, n is a number of 0 to 20, and M is a cation.]
  • R 6a -CH(SO 3 M) COOR 7a (a2-4) [In formula (a2-4), R 6a represents an alkyl group having 8 to 18 carbon atoms, R 7a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents
  • R 3a represents an alkyl group having 9 or more carbon atoms, preferably 10 or more carbon atoms, and preferably 14 or less, more preferably 13 or less carbon atoms.
  • M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion.
  • the organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine.
  • M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and more preferably a sodium ion.
  • the component (a2-1) is preferably a p-alkylbenzenesulfonate in which the alkyl group has from 10 to 14 carbon atoms, and more preferably a sodium p-alkylbenzenesulfonate in which the alkyl group has from 10 to 14 carbon atoms. That is, the component (a2-1) is preferably a compound in which, in general formula (a2-1), R 3a is an alkyl group having from 10 to 14 carbon atoms, and M is a sodium ion.
  • R 4a is an alkyl group or alkenyl group having 10 or more, preferably 11 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 13 or less.
  • R 4a can be one or more groups selected from a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group, and is preferably a linear alkyl group.
  • M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion.
  • the organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine.
  • M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and more preferably a sodium ion.
  • the component (a2-2) is preferably one or more selected from lauric acid, myristic acid, isostearic acid, palmitic acid, isopalmitic acid, oleic acid, and salts thereof, more preferably one or more selected from lauric acid, myristic acid, palmitic acid, and salts thereof, and even more preferably one or more selected from lauric acid, myristic acid, and salts thereof.
  • the component (a2-2) is preferably a compound in which, in general formula (a2-2), R 4a is an alkyl group having from 10 to 16 carbon atoms and M is a cation, and more preferably a compound in which M is a hydrogen ion or a sodium ion.
  • R 5a is an aliphatic hydrocarbon group having an integer of preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less.
  • R 5a is a linear or branched aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkyl group.
  • the AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group.
  • the AO group contains an ethyleneoxy group and a propyleneoxy group
  • the ethyleneoxy group and the propyleneoxy group may be in a block bond or a random bond. From the viewpoint of improving cleaning properties, it is preferable that the AO group is a group containing an ethyleneoxy group.
  • n is the average number of moles of AO groups added, and is a number between 0 and 20. From the viewpoint of improving cleaning performance, n is 0 or more, and from the viewpoint of improving cleaning performance, n is 20 or less, preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and even more preferably 4 or less.
  • the average number of moles of the propyleneoxy group added when AO contains a propyleneoxy group, the average number of moles of the propyleneoxy group added is preferably 4 or less, more preferably 3 or less, and preferably 0 or more. In the general formula (a2-3), the average number of moles of the propyleneoxy group added may be 0. In the general formula (a2-3), when AO contains an ethyleneoxy group, the average number of moles of the ethyleneoxy group added is preferably 0 or more and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
  • M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion.
  • the organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine.
  • M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and is more preferably a sodium ion.
  • R 6a is preferably an alkyl group having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less.
  • R 7a is preferably an alkyl group having 1 or more carbon atoms and preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.
  • M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion.
  • the organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine.
  • M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and is more preferably a sodium ion.
  • the component (a2-4) is preferably an ⁇ -sulfofatty acid methyl ester sodium salt, in which, in general formula (a2-4), R 6a is an alkyl group having 11 to 14 carbon atoms, R 7a is a methyl group, and M is a sodium ion.
  • the component (B) is one or more water-soluble inorganic salts selected from the components (b1) and (b2).
  • the component (B) may be a water-soluble inorganic salt containing one or more water-soluble inorganic salts selected from the component (b1) and one or more water-soluble inorganic salts selected from the component (b2).
  • the water-soluble inorganic salt in component (B) refers to an inorganic salt that dissolves in an amount of 1 g or more in 100 g of water at 20°C.
  • the component (b1) is a water-soluble inorganic salt, and a 0.1 g/L aqueous solution of the water-soluble inorganic salt has a pH of 9.0 or higher at 20° C.
  • the component (b2) is a water-soluble inorganic salt, and the pH of a 0.1 g/L aqueous solution of the water-soluble inorganic salt at 20° C. is less than 9.0.
  • the cleaning composition of the present invention by using the components (b1) and (b2) in an appropriate ratio, it is possible to prevent the cleaning composition from remaining undissolved in water and to prevent a decrease in cleaning properties, even if the cleaning composition contains the water-insoluble inorganic component (C) described below.
  • a composite electrode for pH measurement e.g., glass-laid sleeve type, manufactured by Horiba, Ltd.
  • a saturated potassium chloride aqueous solution 3.33 mol/L
  • a pH meter e.g., pH/ion meter F-23, manufactured by Horiba, Ltd.
  • a pH 4.01 standard solution phthalate standard solution
  • a pH 6.86 standard solution neutral phosphate standard solution
  • a pH 9.18 standard solution borate standard solution
  • the pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and calibration operations are performed in the order of pH 6.86 ⁇ pH 9.18 ⁇ pH 4.01.
  • a 0.1 g/L aqueous solution of the (b1) or 0.1 g/L aqueous solution of the (b2) component to be measured is adjusted to 20°C, and the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.
  • the component (b1) is a water-soluble inorganic salt having a pH of 9.0 or more at 20° C. in a 0.1 g/L aqueous solution.
  • the component (b1) may be an alkaline agent.
  • Examples of the component (b1) include one or more alkaline agents selected from alkali metal carbonates, alkali metal silicates, tripolyphosphates, alkali metal sulfites, alkali metal hydroxides, alkali metal perborates, and alkali metal percarbonates.
  • the alkali metal carbonate may be at least one selected from sodium carbonate, potassium carbonate, and sodium sesquicarbonate, with sodium carbonate being preferred.
  • the alkali metal silicate may be at least one selected from sodium silicate, potassium silicate, sodium metasilicate, and potassium metasilicate.
  • Tripolyphosphates include alkali metal salts of tripolyphosphate.
  • Alkali metal sulfites include sodium sulfite.
  • the alkali metal hydroxide may be at least one selected from sodium hydroxide and potassium hydroxide.
  • Alkali metal perborates include sodium perborate.
  • the alkali metal percarbonate includes sodium percarbonate.
  • the component (b1) is preferably one or more selected from alkali metal carbonates, more preferably one or more selected from sodium carbonate and potassium carbonate, and even more preferably sodium carbonate.
  • Component (b2) is a water-soluble inorganic salt having a pH of less than 9.0 in a 0.1 g/L aqueous solution at 20° C.
  • Component (b2) may be one or more compounds selected from inorganic sulfates, inorganic halogen compounds, and alkali metal hydrogen carbonates.
  • Component (b2) preferably contains one or more water-soluble inorganic salts selected from inorganic sulfates and alkali metal hydrogen carbonates.
  • the component (b2) may be one or more compounds selected from sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium hydrogen carbonate, and potassium hydrogen carbonate.
  • the component (b2) may be a hydrate or anhydrous.
  • the component (C) is a water-insoluble inorganic component.
  • the component (C) may be a water-insoluble carrier.
  • water-insoluble means that 1 g or more of the component does not dissolve in 100 g of water at 20°C.
  • the component (C) may be one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicates, and amorphous aluminosilicates, and is preferably one or more selected from clay minerals and crystalline aluminosilicates.
  • the component (C) when used in a specific ratio with the component (B), has the effect of suppressing the amount of dissolution of the detergent composition after washing of the items to be washed and reducing the turbidity of the rinse water.
  • the average primary particle diameter of component (C) is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less.
  • the average primary particle diameter of component (C) is measured using a laser diffraction/scattering type particle size distribution measuring device (e.g., HORIBA, LA-950). This average primary particle diameter is the D50 (median diameter) of the cumulative particle size distribution based on volume.
  • component (C) examples include amorphous aluminosilicates (oil absorption capacity: 285 mL/100 g) described in JP-A-9-132794, JP-A-7-10526, JP-A-6-227811, and JP-A-8-119622.
  • the calcium silicate of component (C) may be Fluorite R (manufactured by Tokuyama Corp., oil absorption capacity: 400 to 500 mL/100 g), the amorphous silica of component (C) may be Tokusil NR (manufactured by Tokuyama Corp., oil absorption capacity: 210 to 270 mL/100 g) or Silopure (manufactured by Fuji Silysia Chemical Ltd., oil absorption capacity: 240 to 280 mL/100 g), and the amorphous aluminosilicate of component (C) may be TIXOREX25 (manufactured by Korea-Futsu Chemical Co., Ltd., 220 to 270 mL/100 g).
  • the crystalline aluminosilicate may be zeolite.
  • zeolites include crystalline aluminosilicates such as A-type, X-type, and P-type zeolites.
  • the crystalline aluminosilicate is preferably A-type zeolite (for example, trade name "Toyobuilder" manufactured by Tosoh Corporation, oil absorption capacity according to JIS K 5101 method: 40 mL/100 g or more).
  • P-type zeolite for example, trade names "Doucil A24", “ZSEO64”, etc.; both manufactured by Crosfield; oil absorption capacity 60 to 150 mL/100 g
  • X-type for example, trade name "WessalithXD” manufactured by Degussa; oil absorption capacity 80 to 100 mL/100 g
  • WO 98/4262 zeolite The hybrid zeolite described in No. 2 is also suitable.
  • the clay mineral of component (C) is bentonite.
  • the bentonite preferably has an ion exchange capacity of 50 to 100 meq/100 g.
  • the bentonite may be one or more selected from the group consisting of alkali metal or alkaline earth metal montmorillonite, saponite or hectorite, smectitic clay, illite, attapulgite and kaolinite. Powdered or granulated bentonite may be used. For example, see JP 2008-189719 A for the granulated clay mineral.
  • the component (D) is a cationic surfactant.
  • the component (D) may be a quaternary ammonium salt type surfactant.
  • the component (D) may have one or more functions selected from a bactericidal action, an antibacterial action, and a disinfecting action.
  • the quaternary ammonium salt surfactant of the component (D) is preferably at least one selected from the group consisting of compounds represented by the following general formula (d1) and compounds represented by the following general formula (d2):
  • R 1d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms
  • R 2d is a group selected from an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, an alkyl group having from 1 to 3 carbon atoms, and a hydroxyalkyl group having from 1 to 3 carbon atoms
  • R 3d and R 4d are each independently a group selected from an alkyl group having from 1 to 3 carbon atoms, and a hydroxyalkyl group having from 1 to 3 carbon atoms
  • X ⁇ is an anion.
  • R 5d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms
  • R 6d and R 7d are each independently a group selected from an alkyl group having from 1 to 3 carbon atoms and a hydroxyalkyl group having from 1 to 3 carbon atoms
  • X ⁇ is an anion.
  • the number of carbon atoms in R 1d is preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less.
  • R 1d is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • R 2d is a group selected from an aliphatic hydrocarbon group having 8 to 18 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms.
  • R 2d is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, from the viewpoint of detergency, R 2d is preferably an alkyl or alkenyl group having 8 or more and preferably 14 or less, more preferably 12 or less, and more preferably an alkyl group.
  • R 3d and R 4d 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. It is preferable that R 3d and R 4d are each independently a group selected from an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • X- is an anion.
  • the anion include one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
  • the halogen ion include a chloride ion, a bromide ion, and an iodide ion.
  • the alkyl sulfate ion having 1 to 3 carbon atoms include a methyl sulfate ion, an ethyl sulfate ion, and a propyl sulfate ion.
  • R 5d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms. From the viewpoint of antibacterial performance, the number of carbon atoms in R 5d is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less. R 5d is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • R 6d and R 7d 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. It is preferable that R 6d and R 7d are each independently a group selected from an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
  • X- is an anion.
  • the anion include one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
  • the halogen ion include a chloride ion, a bromide ion, and an iodide ion.
  • the alkyl sulfate ion having 1 to 3 carbon atoms include a methyl sulfate ion, an ethyl sulfate ion, and a propyl sulfate ion.
  • the compound of general formula (d2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetra ...
  • the examples include one or more compounds selected from the group consisting of ammonium salts, N-pentadecyl-N,N-diethyl-N-benzyl ammonium salts, N-hexadecyl-N,N-diethyl-N-benzyl ammonium salts, N-dodecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-tridecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-tetradecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-pentadecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, and N-hexadecyl-N-methyl-N-ethyl-N-benzyl ammonium salts.
  • the component (D) is preferably one or more selected from benzalkonium chloride and alkyltrimethylammonium chloride.
  • the benzalkonium chloride is preferably a compound represented by the general formula (d2) above.
  • the alkyltrimethylammonium chloride is preferably a compound represented by the general formula (d1) above.
  • the component (E) is an anionic polymer.
  • the component (E) include a polymer having a carboxylic acid group or a salt thereof and having a weight average molecular weight of 3,000 or more.
  • Examples of the component (E) include one or more polymers selected from polyacrylic acid and its salts, copolymers of acrylic acid and maleic acid and their salts, and polymaleic acid and its salts (hereinafter referred to as component (E1)).
  • the polyacrylic acid and salts thereof include at least one selected from polyacrylic acid, sodium polyacrylate, potassium polyacrylate, and the like, and preferably at least one selected from sodium polyacrylate and potassium polyacrylate.
  • the copolymer of acrylic acid and maleic acid and its salt may be one or more selected from the copolymer of acrylic acid and maleic acid, the sodium salt of the copolymer of acrylic acid and maleic acid, and the potassium salt of the copolymer of acrylic acid and maleic acid, and preferably one or more selected from the sodium salt of the copolymer of acrylic acid and maleic acid and the potassium salt of the copolymer of acrylic acid and maleic acid.
  • the molar ratio of the copolymer of acrylic acid and maleic acid, in terms of the mole number of acrylic acid/the mole number of maleic acid, is preferably 1/99 or more, more preferably 10/90 or more, and preferably 99/1 or less, more preferably 90/10 or less.
  • the polymaleic acid and salts thereof include at least one selected from polymaleic acid, sodium polymaleate, potassium polymaleate, and the like, and preferably at least one selected from sodium polymaleate and potassium polymaleate.
  • the (E1) component may be a copolymer containing a monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid, so long as it does not interfere with the manifestation of the effects of the present invention.
  • the monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid include one or more selected from vinyl monomers, acrylic monomers, and styrene monomers, and more specifically, one or more selected from methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene.
  • the molar ratio of the monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid in the (E1) component is preferably 0 mol% or more, and preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 0 mol%. Therefore, the polyacrylic acid and its salts, the copolymer of acrylic acid and maleic acid and its salts, and the polymaleic acid and its salts of the present invention may be polymers or copolymers that contain, among all constituent monomers, monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and/or maleic acid in the range of 0 mol % to 5 mol %.
  • the weight average molecular weight of component (E) is preferably 3,000 or more, more preferably 3,500 or more, even more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, still more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 25,000 or less, and still more preferably 15,000 or less.
  • the weight average molecular weight can be measured according to the following method for measuring weight average molecular weight.
  • the weight average molecular weight of component (E) can be measured by GPC (gel permeation chromatography), and the weight average molecular weight (Mw) can be determined using a conversion standard substance.
  • GPC gel permeation chromatography
  • Mw weight average molecular weight
  • the cleaning composition of the present invention contains the component (A) in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and even more preferably 11% by mass or more in terms of detergency, and 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less in terms of rinsing ability.
  • the present invention contains the component (a2) as the component (A), the mass of the component (a2) is expressed as a value converted into a sodium salt.
  • the mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more, preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more, from the viewpoint of cleaning performance, and is 0.5 or less, preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less, from the viewpoint of rinsing performance and antibacterial performance.
  • the detergent composition of the present invention contains component (B) in an amount of 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more in terms of cleaning performance, and 80% by mass or less, preferably 70% by mass or less, more preferably 65% by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less in terms of suppressing residual dissolution.
  • the mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) components is 0.2 or more, preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.40 or more, from the viewpoints of suppressing residual dissolution and antibacterial performance, and is 0.8 or less, preferably 0.7 or less, more preferably 0.65 or less, even more preferably 0.60 or less, even more preferably 0.55 or less, and even more preferably 0.50 or less, from the viewpoints of cleaning performance and antibacterial performance.
  • the detergent composition of the present invention contains component (C) in an amount of 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, in terms of suppressing residual dissolution, and 40% by mass or less, preferably 35% by mass or less, more preferably 32.5% by mass or less, and even more preferably 30% by mass or less, in terms of suppressing formation of residual streaks.
  • the mass ratio (C)/[(B)+(C)] of the content of the (C) component to the total content of the (B) component and the (C) component is greater than 0, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.15 or more, even more preferably 0.20 or more, even more preferably 0.25 or more, even more preferably 0.30 or more, from the viewpoint of suppressing the formation of residual streaks, and is 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less, even more preferably 0.38 or less.
  • the detergent composition of the present invention contains component (D) in an amount of 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, even more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, and the upper limit is not particularly limited, but may be, for example, 5.0% by mass or less, further 4.0% by mass or less, further 3.5% by mass or less, and further 3.0% by mass or less.
  • the detergent composition of the present invention contains component (E) in an amount of 0.1% by mass or more, preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, and 10% by mass or less, preferably 8.0% by mass or less, more preferably 6.0% by mass or less, even more preferably 5.0% by mass or less.
  • the ratio of the content of component (A) to the total content of surfactants contained in the cleaning composition, (A)/(total content of surfactants), is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, and even more preferably 80 mass% or more, from the viewpoint of cleaning performance, and is preferably 98 mass% or less, more preferably 96 mass% or less, and even more preferably 94 mass% or less, from the viewpoint of antibacterial performance.
  • the total surfactants contained in the cleaning composition may be the total content of component (A), component (D), and the following component (F).
  • the cleaning composition of the present invention may contain, as component (F), any surfactant other than components (A) and (D).
  • the surfactant other than the components (A) and (D) may be one or more selected from amphoteric surfactants.
  • the amphoteric surfactant may be one or more selected from N-alkanoylaminopropyl-N,N-dimethylamine oxide, N-alkyl-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxys
  • the cleaning composition of the present invention contains component (F)
  • the cleaning composition of the present invention contains component (F) in an amount of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.2% by mass or less, in terms of cleaning performance and foaming.
  • the cleaning composition of the present invention may optionally contain, as the component (G), a polyalkylene glycol having a weight average molecular weight of 100 or more and 100,000 or less.
  • the component (G) may be one or more selected from polyethylene glycol and polypropylene glycol.
  • the weight average molecular weight of component (G) is 100 or more, preferably 1,000 or more, more preferably 5,000 or more, and 100,000 or less, preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the weight average molecular weight herein is a value determined by gel permeation chromatography using polystyrene as a standard substance.
  • the cleaning composition of the present invention contains component (G), from the viewpoint of stability, contains component (G) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably 1% by mass or less.
  • the cleaning composition of the present invention may optionally contain, as component (H), one or more enzymes selected from proteases, lipases and amylases.
  • Proteases include, for example, serine proteases (EC 3.4.21) and metalloproteases (EC 3.4.17 or EC 3.4.24).
  • suitable proteases include neutral or alkaline serine proteases such as subtilisin (EC 3.4.21.62).
  • lipases examples include 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), and lipoprotein lipase (EC 3.1.1.34).
  • amylases examples include ⁇ -amylase (EC 3.2.1.1), ⁇ -amylase (EC 3.2.1.2) and/or glucoamylase (EC 3.2.1.3), etc.
  • Suitable examples of amylases include neutral or alkaline ⁇ -amylases, preferably of microbial origin, such as bacteria or fungi.
  • the detergent composition of the present invention contains component (H)
  • the detergent composition of the present invention contains component (H) in an amount, in terms of cleaning performance, of preferably 0.002 mass % or more, more preferably 0.004 mass % or more, even more preferably 0.008 mass % or more, and preferably 0.12 mass % or less, more preferably 0.1 mass % or less, even more preferably 0.08 mass % or less, and still more preferably 0.04 mass % or less, in terms of the amount of enzyme protein in the detergent composition.
  • the mass of the component (H) is calculated as the amount of enzyme protein.
  • the enzyme protein can be quantified, for example, using a protein assay kit, Lowry kit, manufactured by Nacalai Tesque, Inc., in accordance with the instruction manual.
  • the cleaning composition of the present invention may optionally contain (I) a chelating agent (hereinafter referred to as "component (I)").
  • component (I) include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof; and these can be used in combination with one or more of them.
  • salts of component (I) include alkali metal salts such as sodium salts and potassium salts, and salts with lower amines such as monoethanolamine, diethanolamine and triethanolamine.
  • the detergent composition of the present invention contains component (I)
  • the detergent composition of the present invention contains component (I) in an amount of preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more in terms of cleaning performance, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less in terms of formulation.
  • the cleaning composition of the present invention may contain water.
  • water examples include ion-exchanged water, purified water, and distilled water. Water is used as the remainder other than components (A) to (I) and any optional components. Water also includes water used to add the components of the cleaning composition.
  • the cleaning composition of the present invention may optionally contain other components known in the field of laundry detergents, such as bleaching agents (such as bleach activators), anti-redeposition agents, organic reducing agents, fluorescent brightening agents, foam inhibitors (such as silicones), organic solvents, fragrances, colorants, antibacterial agents (such as triclosan), etc. (excluding those that fall under components (A) to (I)).
  • the cleaning composition of the present invention may be a solid cleaning composition.
  • the cleaning composition of the present invention may be in the form of a tablet, powder, granule, granules, or paste. From the viewpoint of solubility, the cleaning composition of the present invention is preferably a cleaning composition selected from a tablet, powder, granule, granule, and paste, and more preferably a cleaning composition selected from a tablet, powder, and paste.
  • the cleaning composition of the present invention may be a powder cleaning composition.
  • the cleaning composition of the present invention can be produced by a known method.
  • it can be produced by applying a spray drying method, a dry neutralization method, a dry granulation method, a dry blend method, a fluidized bed drying method, a thin film drying method, an extrusion granulation method, a rolling granulation method, a stirring granulation method, a compaction granulation method, a surfactant carrying method, or a combination of methods selected from these.
  • the bulk density of the cleaning composition of the present invention will vary depending on the production method, but is preferably 0.2 g/ cm3 or more, more preferably 0.3 g/ cm3 or more, even more preferably 0.35 g/ cm3 or more, and is preferably 1 g/ cm3 or less, more preferably 0.95 g/ cm3 or less, even more preferably 0.9 g/ cm3 or less.
  • the average particle size of the cleaning composition of the present invention is preferably 100 ⁇ m or more, more preferably 150 ⁇ m or more, even more preferably 200 ⁇ m or more, and preferably 800 ⁇ m or less, more preferably 750 ⁇ m or less, even more preferably 700 ⁇ m or less.
  • This average particle size is determined by vibrating a standard sieve according to JIS Z 8801 for 5 minutes and then calculating the mass fraction based on the size of the sieve openings.
  • the present invention provides a cleaning agent article comprising the cleaning agent composition of the present invention and a water-soluble film for packaging the cleaning agent composition.
  • the present invention provides a cleaning agent article comprising the cleaning agent composition of the present invention and a water-soluble film, in which the cleaning agent composition is packaged in the water-soluble film.
  • the cleaning article of the present invention may be a cleaning article comprising the cleaning composition of the present invention packaged in a water-soluble film. That is, the cleaning composition of the present invention may be a cleaning composition packaged in a water-soluble film.
  • water-soluble refers to a water-soluble film in which 500 g of 30° C. ion-exchanged water is placed in a 1-liter glass beaker, a Teflon (registered trademark) stirrer having a diameter of 8 cm is placed in the beaker, 1 g of the film to be evaluated is placed in the beaker, and the film is stirred at 100 rpm for 30 minutes, after which no insoluble matter is apparent.
  • Teflon registered trademark
  • the thickness of the water-soluble film is preferably 1 ⁇ m or more, more preferably 10 ⁇ m or more, even more preferably 50 ⁇ m or more, and preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, even more preferably 100 ⁇ m or less.
  • the water-soluble film is preferably composed of a polymer.
  • the water-soluble film can be obtained by methods known in the art, such as casting, blow molding, extrusion, injection molding of polymers, etc.
  • Non-limiting examples of polymers for producing water-soluble films include polyvinyl alcohol (PVA), vinyl alcohol copolymers, polyvinylpyrrolidone, polyalkylene oxides, (modified) cellulose, (modified) cellulose-ethers or -esters or -amides, polycarboxylic acids and their salts such as polyacrylates, maleic acid/acrylic acid copolymers, polyamino acids or peptides, polyamides such as polyacrylamides, polysaccharides such as starch and gelatin, natural gums such as xanthan and carragum.
  • PVA polyvinyl alcohol
  • vinyl alcohol copolymers polyvinylpyrrolidone
  • polyalkylene oxides polyalkylene oxides
  • Vinyl alcohol copolymers are copolymers of vinyl alcohol with other monomers, such as ethylene, acrylic acid.
  • the water-soluble film comprises a polymer selected from the group consisting of polyacrylates and water-soluble acrylates, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, maltodextrin, polymethacrylates, polyvinyl alcohol, vinyl alcohol copolymers, hydroxypropylmethylcellulose (HPMC), and combinations thereof.
  • the water-soluble film comprises a polymer selected from polyvinyl alcohol, vinyl alcohol copolymers, and hydroxypropylmethylcellulose.
  • the water-soluble film comprises polyvinyl alcohol, for example, Solvron available from Aicello Co., Ltd. Suitable polymers for producing water-soluble films are described, for example, in U.S. Pat. No. 6,995,126.
  • the total area of the water-soluble film in contact with the detergent composition of the present invention is, from the viewpoint of further enhancing product stability, preferably 10 cm2 or more, more preferably 20 cm2 or more, even more preferably 30 cm2 or more, and still more preferably 40 cm2 or more, and from the same viewpoint, preferably 100 cm2 or less, more preferably 70 cm2 or less, even more preferably 60 cm2 or less, and still more preferably 45 cm2 or less.
  • the cleaning articles of the present invention can be made by any suitable process known in the art, such as known detergent pouch making processes. Exemplary pouch making processes are described in U.S. Patent Nos. 6,995,126, 7,127,874, 8,156,713, 7,386,971, 7,439,215, and U.S. Patent Application Publication No. 2009/199877.
  • the amount of contents per cleaning article of the present invention is preferably 5 g or more, more preferably 8 g or more, even more preferably 10 g or more, and preferably 50 g or less, more preferably 30 g or less, even more preferably 25 g or less.
  • each of the cleaning articles of the present invention is, for example, a quadrilateral, with the length of one side preferably being 1 cm or more and 5 cm or less, and the thickness preferably being 1 cm or more and 5 cm or less, more preferably being 1 cm or more and 4 cm or less.
  • the mass of each of the cleaning articles of the present invention is preferably 5 g or more, more preferably 10 g or more, even more preferably 15 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less.
  • each of the cleaning articles of the present invention is, for example, a rectangular parallelepiped shape, with a vertical length of preferably 5 cm to 20 cm, a horizontal length of preferably 1 cm to 4 cm, and a thickness of preferably 1 cm to 5 cm, more preferably 1 cm to 4 cm.
  • the mass of each of the cleaning articles of the present invention is preferably 5 g or more, more preferably 10 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less, even more preferably 20 g or less.
  • the detergent article of the present invention may be, for example, a detergent article in which the detergent composition of the present invention is packaged in a water-soluble film, the major axis diameter of the maximum projected area of the detergent article is 30 mm or more and 200 mm or less, the aspect ratio between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter (major axis diameter/minor axis diameter) is 5 or more, and the burst strength is 300 N or more.
  • the detergent article of the present invention may be a detergent article consisting of the detergent composition of the present invention and a water-soluble film, the detergent composition is packaged in the water-soluble film, the major axis diameter of the maximum projected area of the detergent article is 30 mm or more and 200 mm or less, the aspect ratio between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter (major axis diameter/minor axis diameter) is 5 or more, and the burst strength is 300 N or more.
  • the aspect ratio (major axis diameter/minor axis diameter) of the major axis diameter of the maximum projected area of the detergent article of the present invention to the minor axis diameter perpendicular to the major axis diameter is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and still more preferably 8 or more, from the viewpoint of suppressing a decrease in detergency, and is preferably 20 or less, more preferably 16 or less, even more preferably 13 or less, and still more preferably 10 or less, from the viewpoints of ease of use and storage.
  • the major axis diameter of the maximum projected area of the cleaning article of the present invention is preferably 30 mm or more, more preferably 50 mm or more, even more preferably 80 mm or more, and preferably 200 mm or less, more preferably 160 mm or less, even more preferably 120 mm or less.
  • the minor axis diameter of the maximum projected area of the cleaning article of the present invention is preferably 5 mm or more, more preferably 10 mm or more, even more preferably 12 mm or more, still more preferably 14 mm or more, and is preferably 25 mm or less, more preferably 23 mm or less, and even more preferably 20 mm or less.
  • the maximum projected area is the area of the projection that has the maximum horizontal projected area when the cleaning article is projected horizontally from all sides.
  • "Projection” is the same as “projection” used in mathematics, that is, it means projecting a parallel light beam horizontally onto an object and projecting the shadow onto a flat surface.
  • the method for measuring the major axis diameter and minor axis diameter of the maximum projected area of the detergent article is as follows: when the shape of the maximum projected area of the detergent article is elliptical, the major axis diameter and minor axis diameter are measured as they are.
  • the maximum projected area of the cleaning article includes the water-soluble film that packages the cleaning composition, and also includes overlapping portions of the water-soluble films, such as sealed portions.
  • the ratio of the contact area of the water-soluble film with the detergent composition to the total area of the surface facing the other water-soluble film per water-soluble film is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, and less than 100%.
  • the contact area of the water-soluble film with the detergent composition may be the area of the water-soluble film surface that forms the space for accommodating the detergent composition.
  • the detergent article may have an end of a water-soluble film packaging a detergent composition connected in a detachable manner to an end of a water-soluble film packaging another detergent composition.
  • the aspect ratio (long axis diameter/short axis diameter) between the major axis diameter of the maximum projected area of the detergent article and the minor axis diameter perpendicular to the major axis diameter is measured based on the calculated maximum projected area by calculating the maximum projected area of the detergent article for each water-soluble film packaging a detergent composition.
  • the aspect ratio is measured by cutting off the connected portion of the water-soluble film packaging the detergent composition.
  • a line dividing each packaged detergent composition into equal parts can be regarded as the connected portion.
  • the cleaning composition and cleaning article of the present invention can be suitably used for textile products, for hard surfaces such as tableware, or for automatic dishwashers, and is preferably used for textile products.
  • the fiber to be cleaned may be either a hydrophobic fiber or a hydrophilic fiber.
  • hydrophobic fibers include protein fibers (milk protein casein fiber, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride/polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene
  • hydrophilic fibers examples include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.). From the viewpoint of finishing quality, the fiber is preferably a fiber containing cotton fiber.
  • the content of cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 40% by mass or more, still more preferably 60% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.
  • textile products refer to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics that use the hydrophobic and hydrophilic fibers described above, and products obtained using them, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, and tights.
  • the present invention provides a method for cleaning textile products, in which textile products are cleaned with a cleaning liquid obtained by mixing the cleaning composition of the present invention with water (hereinafter referred to as the cleaning liquid of the present invention).
  • the cleaning composition of the present invention can be used in the form of a cleaning article obtained by packaging the cleaning composition of the present invention in a water-soluble film. That is, the present invention provides a method for cleaning textile products, in which textile products are cleaned with a cleaning liquid obtained by mixing the cleaning article of the present invention with water (hereinafter referred to as the cleaning liquid of the present invention as above).
  • the embodiments described in relation to the detergent composition of the present invention and the detergent article of the present invention can be appropriately applied.
  • the detergent composition of the present invention and water may be charged into a washing tank in advance and mixed to prepare the cleaning liquid of the present invention, and then the textile product to be washed is charged therein to wash the textile product.
  • a method is preferred in which the detergent composition of the present invention, water and the textile product are charged into a washing tank, and the detergent composition of the present invention is dissolved in the water while the cleaning liquid of the present invention is prepared and the textile product is washed at the same time.
  • the detergent article of the present invention can be used in the method for cleaning textile products of the present invention. In that case, the cleaning liquid can be prepared in the above-mentioned method by substituting the detergent composition of the present invention for the detergent article of the present invention.
  • the amount of water used when mixing the cleaning composition of the present invention with water is adjusted so that the total amount of the cleaning composition of the present invention 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 per 1 L of water, from the viewpoints of environmental consideration and cleaning performance.
  • the cleaning solution of the present invention contains component (A) in an amount of preferably 15 ppm or more, more preferably 30 ppm or more, and even more preferably 45 ppm or more in terms of cleaning performance, and preferably 300 ppm or less, more preferably 250 ppm or less, and even more preferably 200 ppm or less in terms of rinsing.
  • the cleaning solution of the present invention contains component (B) in an amount of preferably 50 ppm or more, more preferably 100 ppm or more, and even more preferably 150 ppm or more in terms of cleaning performance, and preferably 800 ppm or less, more preferably 700 ppm or less, and even more preferably 600 ppm or less in terms of the residue in cold water.
  • the cleaning solution of the present invention contains component (C) in an amount of preferably 30 ppm or more, more preferably 60 ppm or more, and even more preferably 100 ppm or more in terms of preventing residual dissolution, and preferably 160 ppm or less, more preferably 150 ppm or less, and even more preferably 140 ppm or less in terms of preventing streaking.
  • the cleaning solution of the present invention contains component (D) in an amount of preferably 3 ppm or more, more preferably 5 ppm or more, even more preferably 8 ppm or more, and for example, 50 ppm or less, in terms of antibacterial performance.
  • the cleaning solution of the present invention contains component (E) in an amount of preferably 5 ppm or more, more preferably 10 ppm or more, even more preferably 15 ppm or more, and, for example, 100 ppm or less, in terms of cleaning performance against particulate soiling.
  • the cleaning solution of the present invention contains component (F)
  • the cleaning solution contains component (F) in an amount of preferably 0.5 ppm or more, more preferably 1.0 ppm or more, and even more preferably 1.5 ppm or more in terms of cleaning performance and foaming performance, and preferably 20 ppm or less, more preferably 18 ppm or less, and even more preferably 16 ppm or less in terms of rinsing performance.
  • the cleaning solution of the present invention contains component (G), from the viewpoints of stability and dispersibility of hydrophobic particles, the cleaning solution contains component (G) preferably at 0.5 ppm or more, more preferably at 1 ppm or more, even more preferably at 1.5 ppm or more, and for example, at 50 ppm or less.
  • the amount of component (H) in the cleaning solution is preferably 0.02 ppm or more, more preferably 0.04 ppm or more, and even more preferably 0.06 ppm or more in terms of the cleaning performance, and is preferably 1.2 ppm or less, more preferably 1.0 ppm or less, and even more preferably 0.80 ppm or less in terms of skin irritation.
  • the cleaning solution of the present invention contains component (I), from the viewpoint of cleaning performance, the cleaning solution contains component (I) preferably at 1 ppm or more, more preferably at 2.5 ppm or more, even more preferably at 5 ppm or more, and for example, at 100 ppm or less.
  • the bath ratio which is the ratio of the mass of the textile product (kg) to the amount of water in the cleaning solution (liters), i.e., the amount of water in the cleaning solution (liters) / mass of the textile product (kg) (hereinafter, this ratio may be referred to as the bath ratio).
  • the bath ratio When using a domestic washing machine, if the bath ratio becomes small, the textile products may rub against each other more strongly due to agitation during washing, which may impair the finish of the textile product.
  • the bath 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, and even more preferably 30 or less.
  • the method for washing textile products of the present invention is suitable for a rotary washing method, a method in which the textile products are immersed in a liquid used for scouring while being fed with a roller or the like.
  • the rotary washing method refers to a washing method in which a textile product that is not fixed to a rotating device rotates around a rotating shaft together with the washing liquid.
  • the rotary washing method can be carried out by a rotary washing machine. Therefore, in the present invention, in order to give the textile products a neater finish, it is preferable to wash the textile products using a rotary washing machine.
  • Specific examples of rotary washing machines include drum washing machines, pulsator washing machines, and agitator washing machines. For these rotary washing machines, those commercially available for home use can be used.
  • the present invention discloses the following aspects.
  • the composition contains the following component (A) in an amount of 5% by mass or more and 40% by mass or less, the following component (B) in an amount of 20% by mass or more and 80% by mass or less, the following component (C) in an amount of 5% by mass or more and 40% by mass or less, the following component (D) in an amount of 0.1% by mass or more and 5.0% by mass or less, and the following component (E) in an amount of 0.1% by mass or more and 10% by mass or less, a mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more and 0.5 or less; a mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) component is 0.2 or more and 0.8 or less; a mass ratio (C)/[(B)+(C)] of the content of the (C)
  • R 1a is an aliphatic hydrocarbon group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, preferably a group selected from an alkyl group and an alkenyl group
  • R 2a is a hydrogen atom or a methyl group, preferably a hydrogen atom.
  • CO is a carbonyl group
  • m is a number of 0 or 1, preferably 0.
  • a 1a O group is one or more selected from alkyleneoxy groups having 2 to 4 carbon atoms, preferably one or more selected from alkyleneoxy groups having 2 to 3 carbon atoms, more preferably an ethyleneoxy group.
  • n is the average number of moles added of A 1a O group, and is a number of 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the component (a2) is one or more compounds selected from a compound represented by the following general formula (a2-1) (hereinafter referred to as the component (a2-1)), a compound represented by general formula (a2-2) (hereinafter referred to as the component (a2-2)), a compound represented by general formula (a2-3) (hereinafter referred to as the component (a2-3)), and a compound represented by general formula (a2-4) (hereinafter referred to as the component (a2-4)), preferably one or more compounds selected from the component (a2-1), the component (a2-2), and the component (a2-3), and more preferably one or more compounds selected from the component (a2-1) and the component (a2-2).
  • a2-1 compound represented by the following general formula (a2-1)
  • a compound represented by general formula (a2-2) hereinafter referred to as the component (a2-2)
  • a compound represented by general formula (a2-3) hereinafter referred to as the component (a2-3)
  • a compound represented by general formula (a2-4) hereinafter
  • R 3a -B-SO 3 M (a2-1) [In formula (a2-1), R 3a represents an alkyl group having 9 or more, preferably 10 or more, and preferably 14 or less, more preferably 13 or less carbon atoms; B represents a benzene ring; the carbon atom of R 3a bonded to the carbon atom of B is a secondary carbon atom; M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, more preferably a sodium ion.
  • R 3a represents an alkyl group having 9 or more, preferably 10 or more, and preferably 14 or less, more preferably 13 or less carbon atoms
  • B represents a benzene ring
  • the carbon atom of R 3a bonded to the carbon atom of B is a secondary carbon atom
  • R 4a represents an alkyl or alkenyl group having 10 or more, preferably 11 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 13 or less carbon atoms, preferably one or more groups selected from a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group, more preferably a linear alkyl group
  • M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, more preferably a sodium ion.
  • ⁇ 4> The cleaning composition according to any one of the above ⁇ 1> to ⁇ 3>, wherein the component (b1) is preferably one or more selected from alkali metal carbonates, more preferably one or more selected from sodium carbonate and potassium carbonate, and even more preferably sodium carbonate.
  • the component (b2) is one or more compounds selected from inorganic sulfates, inorganic halogen compounds, and alkali metal bicarbonates, and is preferably a water-soluble inorganic salt containing one or more compounds selected from inorganic sulfates and alkali metal bicarbonates.
  • ⁇ 6> The cleaning composition according to any one of ⁇ 1> to ⁇ 4> above, wherein the component (b2) is one or more compounds selected from sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium hydrogen carbonate, and potassium hydrogen carbonate.
  • the component (b2) is one or more compounds selected from sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium hydrogen carbonate, and potassium hydrogen carbonate.
  • ⁇ 7> The cleaning composition according to any one of the above ⁇ 1> to ⁇ 6>, wherein the component (C) is one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicates, and amorphous aluminosilicates, preferably one or more selected from clay minerals, and crystalline aluminosilicates.
  • the component (C) is one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicates, and amorphous aluminosilicates, preferably one or more selected from clay minerals, and crystalline aluminosilicates.
  • R 1d is an aliphatic hydrocarbon group having 8 or more, preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and 18 or less, preferably 16 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group;
  • R 2d is a group selected from an aliphatic hydrocarbon group having 8 to 18 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms;
  • R 3d and R 4d 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, preferably a group selected from an alkyl group having 1 to 3 carbon atoms;
  • X ⁇ is an anion, preferably one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
  • R 5d is an aliphatic hydrocarbon group having 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group
  • R 6d and R 7d 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, preferably a group selected from an alkyl group having 1 to 3 carbon atoms
  • X ⁇ is an anion, preferably one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.
  • ⁇ 9> The cleaning composition according to any one of ⁇ 1> to ⁇ 8> above, wherein the component (D) is at least one selected from the group consisting of benzalkonium chloride and alkyltrimethylammonium chloride.
  • the component (E) is a polymer having a carboxylic acid group or a salt thereof and having a weight-average molecular weight of 3,000 or more, preferably one or more polymers selected from polyacrylic acid and salts thereof, copolymers of acrylic acid and maleic acid and salts thereof, and polymaleic acid and salts thereof, and has a weight-average molecular weight of preferably 3,000 or more, more preferably 3,500 or more, even more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, still more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 25,000 or less, and still more preferably 15,000 or less.
  • the cleaning composition contains the component (A) in an amount of 5 mass% or more, preferably 7 mass% or more, more preferably 9 mass% or more, even more preferably 11 mass% or more, and 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, even more preferably 20 mass% or less.
  • a mass ratio (a2)/[(a1)+(a2)] of the content of the component (a2) to the total content of the components (a1) and (a2) in the cleaning composition is 0 or more, preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.15 or more, and is 0.5 or less, preferably 0.45 or less, more preferably 0.40 or less, even more preferably 0.35 or less.
  • the cleaning agent composition according to any one of ⁇ 1> to ⁇ 12> above, wherein the cleaning agent composition contains the component (B) in an amount of 20 mass% or more, preferably 25 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, and 80 mass% or less, preferably 70 mass% or less, more preferably 65 mass% or less, even more preferably 60 mass% or less, and still more preferably 55 mass% or less.
  • a mass ratio (b2)/[(b1)+(b2)] of the content of the component (b2) to the total content of the component (b1) and the component (b2) in the cleaning composition is 0.2 or more, preferably 0.30 or more, more preferably 0.35 or more, even more preferably 0.40 or more, and is 0.8 or less, preferably 0.7 or less, more preferably 0.65 or less, even more preferably 0.60 or less, still more preferably 0.55 or less, and still more preferably 0.50 or less.
  • the cleaning agent composition according to any one of ⁇ 1> to ⁇ 14> above, wherein the cleaning agent composition contains the component (C) in an amount of 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, still more preferably 25 mass% or more, and 40 mass% or less, preferably 35 mass% or less, more preferably 32.5 mass% or less, and even more preferably 30 mass% or less.
  • a mass ratio (C)/[(B)+(C)] of the content of the component (C) to the total content of the component (B) and the component (C) in the cleaning composition exceeds 0, and is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.15 or more, still more preferably 0.20 or more, still more preferably 0.25 or more, still more preferably 0.30 or more, and is 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.38 or less.
  • the cleaning agent composition according to any one of ⁇ 1> to ⁇ 16>, wherein the cleaning agent composition contains the component (D) in an amount of 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 0.7 mass% or more, even more preferably 1.0 mass% or more, still more preferably 2.0 mass% or more, and 5.0 mass% or less, further 4.0 mass% or less, further 3.5 mass% or less, and further 3.0 mass% or less.
  • the cleaning agent composition contains the component (E) in an amount of 0.1 mass% or more, preferably 1.0 mass% or more, more preferably 2.0 mass% or more, even more preferably 3.0 mass% or more, still more preferably 4.0 mass% or more, and 10 mass% or less, preferably 8.0 mass% or less, more preferably 6.0 mass% or less, and even more preferably 5.0 mass% or less.
  • a ratio of the content of the component (A) to the total content of surfactants contained in the cleaning agent composition, (A)/(total content of surfactants), is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more, and is preferably 98 mass% or less, more preferably 96 mass% or less, and even more preferably 94 mass% or less.
  • the cleaning agent composition according to any one of ⁇ 1> to ⁇ 20> above which is for textile products, for hard surfaces, or for automatic dishwashing machines, preferably for textile products.
  • a cleaning agent article comprising the cleaning agent composition according to any one of ⁇ 1> to ⁇ 21> above and a water-soluble film, wherein the cleaning agent composition is packaged in the water-soluble film.
  • a method for cleaning textile products comprising washing the textile products with a cleaning liquid obtained by mixing the detergent composition according to any one of ⁇ 1> to ⁇ 21> above with water.
  • a method for cleaning textile products comprising cleaning the textile products with a cleaning liquid obtained by mixing the detergent article according to ⁇ 22> with water.
  • Component (B)> [Component (b1)] Sodium carbonate: light ash, bulk density 600 g/L, average particle size 100 ⁇ m, manufactured by Central Glass Co., Ltd. [component (b2)] Sodium sulfate: anhydrous neutral Glauber's salt, manufactured by Shikoku Kasei Co., Ltd. Sodium chloride: Nacl N, manufactured by Nankai Salt Industry Co., Ltd.
  • the cleaning compositions shown in Table 1 were prepared by the following method. Sodium sulfate, 110 kg of sodium carbonate, 40% sodium polyacrylate, sodium chloride, and 93 kg of zeolite were mixed in a mixing tank to prepare a slurry. The slurry was pumped into a spray-drying tower (countercurrent type), and the slurry was sprayed from a pressure spray nozzle installed near the top of the tower to obtain spray-dried particles.
  • Example 1-3 dry neutralization using component (a2) was not carried out, and alkyl sulfate granules were finally mixed with the enzyme and flavor in a blend.
  • the mass% of the blended components other than component (H) are all values based on the active ingredient, and the blended amount (mass%) of component (H) is shown as a solid form.
  • the blended amount (mass%) of component (a2) in the table is shown after dry neutralization, i.e., as a sodium salt.
  • A Model sebum soil (used in amounts such that the mass percentages in the artificial soil were 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 mass% palmitic acid, 0.44 mass% heptadecanoic acid, 1.60 mass% stearic acid, 7.91 mass% oleic acid, 2.22 mass% n-hexadecyl palmitate, and 6.66 mass% squalene)
  • B Hard water obtained by weighing out 105 mg of calcium chloride dihydrate and dissolving it in distilled water to make 1,000 mL.
  • E Egg white lecithin liquid crystals 1.98% by mass (egg white lecithin liquid crystals obtained by dissolving 11.37 g of arginine hydrochloride, 4.20 g of histidine, and 2.44 g of serine in 80 mL of distilled water, adjusting the pH to 5.0 with concentrated hydrochloric acid, and then thoroughly mixing this solution with egg white lecithin in a mixer).
  • D Kanuma red soil 8.11% by mass
  • E 0.025% by mass of carbon black
  • the specific washing conditions were as follows: four pieces of artificially soiled cloth and 0.30 g of each detergent composition shown in Table 1 were placed in the tergotometer, 600 mL of water was poured in, and a washing solution was prepared while dissolving the detergent composition in water, and at the same time, the artificially soiled cloth was washed at 100 rpm for 10 minutes.
  • the water temperature of each washing solution was 20° C.
  • the stained cloth was rinsed with city water (20° C.) for 1 minute, and then dehydrated for 3 minutes using a two-layer washing machine, and then left to dry for 5 hours under conditions of 20° C. and 50% RH.
  • the cleaning rate (%) was calculated based on the following formula (1) and the average value of the four pieces was calculated.
  • a detergent composition rated as "0" in the evaluation of foam remaining is a cleaning composition with excellent rinsing properties.
  • Evaluation index of remaining foam 0 The remaining amount of foam is less than 1/4 of the washing tub 1: The remaining amount of foam is 1/4 or more of the washing tub
  • Turbidity evaluation index 0 The letters attached to the bottom of the tub were recognizable. 1: The letters attached to the bottom of the tub could not be recognized.
  • Antibacterial Test Method Preparation of Fabric for Antibacterial Test 30 g of cotton fabric (cotton #2003, Tanigashira Shoten Co., Ltd.) and 600 mL of cleaning solution containing 0.3 g of each detergent composition listed in Table 1 were placed in a tergotometer, and the fabric was washed at 85 rpm for 10 minutes and rinsed for 3 minutes for a total of five cycles to prepare a test fabric. Boiled and sterilized tap water was used for all water.
  • Antibacterial Test Using Moraxella osloensis isolated from worn clothing, an antibacterial test was carried out in accordance with JIS L 1902. Specifically, the test was carried out as follows.
  • test cloth prepared by the method in (1) above was cut into test pieces of 2 cm square (each piece had a mass of approximately 0.4 g) to be used as specimens.
  • Moraxella osloensis isolated from worn clothing was streaked on a plate with SCD-LP agar medium, and the resulting cultured specimen was scraped off with a platinum loop and placed in 10 mL of nutrient (NT) medium and pre-cultured for 24 hours at 37°C and 110 rpm.
  • the concentration of the pre-cultured culture solution was estimated by spectrophotometry, and the bacterial concentration was adjusted to about 1 x 10 8 cells/mL.
  • test bacteria liquid was taken with a pipette, and each specimen or untreated standard cloth (JIS L 1902 standard cloth) was contacted with the liquid at several points, placed in a vial, and cultured at 37° C. for 18 hours with the lid closed. Inoculation with the test bacteria liquid and culture were performed multiple times for each of the specimens and standard cloth.
  • Bacteriostatic activity value Log B - Log C A: The average number of bacteria recovered from the control cloth immediately after inoculation. B: The average number of bacteria recovered from the control cloth after 18 hours of culture. C: The average number of bacteria recovered from the specimen after 18 hours of culture. However, this must satisfy the test validity condition, that is, Log B - Log A must exceed 1.5.
  • the residual dissolution property of each of the cleaning compositions of the Examples and Comparative Examples in Table 1 was evaluated based on the presence or absence of streaks on the cleaned object and the diameter of the residual dissolution property of the cleaning composition that remained after cleaning.
  • the residual dissolution property was evaluated by the following method. 40 g of each detergent composition in Table 1 was placed on a black cotton cloth (black dyed cotton broadcloth 40, purchased from Tanigashira Shoten) cut to 15 cm x 15 cm, and the detergent composition was wrapped around the cloth and woven.
  • the following is an example of a detergent article including the detergent composition of the present invention and a water-soluble film for packaging the detergent composition.
  • the detergent article can have a burst strength of 300 N or more in the burst strength measurement shown below, and can suppress a decrease in detergency even when the detergent composition is packaged in a water-soluble film in the cleaning performance evaluation shown below.
  • ⁇ Preparation of cleaning article> For each reference example, two sheets of 76 ⁇ m water-soluble film (M8685, manufactured by Kuraray Co., Ltd.) cut to a predetermined rectangular size were stacked, and a heat sealer (manufactured by Fuji Impulse Co., Ltd.) was used to set the sealing conditions of the heat sealer to 8, and three sides of the water-soluble film were fused by the heat sealer at a width of 2 mm from the edge of each side to prepare a bag with only one side open. 15 g of the detergent composition of Examples 1-4 in Table 1 was placed in this bag for each reference example.
  • a heat sealer manufactured by Fuji Impulse Co., Ltd.
  • each cylindrical detergent article in which the detergent composition was encapsulated in the water-soluble film was fused and closed with a heat sealer to obtain each cylindrical detergent article in which the detergent composition was encapsulated in the water-soluble film.
  • the maximum projected area of each of the obtained detergent articles was rectangular, and the major axis diameter of the maximum projected area and the aspect ratio (major axis diameter/minor axis diameter) between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter were as shown in Table 2.
  • the total area of the water-soluble film in contact with the detergent composition was 48 cm 2 .
  • the area of the sealed portion of the water-soluble film is included in the maximum projected area.
  • the total area of the water-soluble film in contact with the detergent composition is calculated as twice the product of the length of the major axis diameter of the detergent article excluding the sealed portion (4 mm) and the length of the minor axis diameter of the detergent article excluding the sealed portion (4 mm), and is 30.4 cm 2 , 34.2 cm 2 , 35.6 cm 2 , 37.1 cm 2 , and 38.6 cm 2 for Reference Examples 1 to 5, respectively.
  • Burst strength is measured for each of the detergent articles in Table 2. Under the conditions of room temperature (20°C)/relative humidity of about 50%, a compression tester (AUTOGRAPH AG-X, Shimadzu Science Co., Ltd.) is used to place each detergent article so that the surface with the maximum projected area is in contact with a fixed platen (not a spherical type, and having an area larger than the maximum projected area of each detergent article) of the compression tester, and a compressive force of 300N is applied at a speed of 200mm/min to perform evaluation. This measurement shows that none of the detergent articles of each reference example bursts at a compressive force of 300N, indicating that the burst strength is 300N or more.
  • a compression tester AUTOGRAPH AG-X, Shimadzu Science Co., Ltd.
  • Model Sebum soil having the following composition is prepared and used to prepare an artificial soiled cloth containing the model sebum soil.
  • Model sebum stain composition 0.44% by mass of lauric acid, 3.15% by mass of myristic acid, 2.35% by mass of pentadecanoic acid, 6.31% by mass of palmitic acid, 0.44% by mass of heptadecanoic acid, 1.6% by mass of stearic acid, 7.91% by mass of oleic acid, 13.33% by mass of triolein, 2.22% by mass of n-hexadecyl palmitate, 6.66% by mass of squalene, and the balance being water (total 100% by mass)
  • washing method Four artificially soiled cloths were sewn onto the chest of a cotton T-shirt (Gunze Co., Ltd.). A vertical washing machine (NA-F70PB1, Panasonic Co., Ltd.) was used. The detergent article of each Reference Example in Table 2 was placed at the bottom of the washing tub, and then the cotton T-shirt (Gunze Co., Ltd.) was added so that the total weight was 2 kg. In each of the reference examples, water was added so that the concentration of the detergent composition contained in the detergent article in the washing tub was 0.5 g/L, and the washing was performed for 9 minutes, 1 rinse, and 7 minutes spin-dry time. The temperature of the water used for washing and rinsing was 20° C. In addition, instead of each detergent article, the detergent composition of Example 1-4 in Table 1 that is not packaged in a water-soluble film is put into the washing tub, and the same washing method as above is carried out. This is used as a reference example.
  • the four pieces of artificially soiled cloth sewn onto the cotton T-shirt were removed, and the cleaning rate was measured by the following method, and the average value of the four pieces was calculated.
  • the reflectance at 550 nm of the unsoiled raw cloth and the artificially soiled cloth before and after washing was measured using a spectrophotometer (SE-2000, manufactured by Nippon Denshoku Co., Ltd.).
  • the cleaning rate (%) was calculated using the following formula, and the average value of the four pieces was calculated.
  • Cleaning rate (%) 100 x [(reflectance after cleaning - reflectance before cleaning) / (reflectance of original fabric - reflectance before cleaning)]
  • the cleaning rate of each Reference Example is calculated by taking the cleaning rate of a Reference Example using a cleaning composition not packaged in a water-soluble film as 100%, and calculating the relative cleaning rate (%) to the Reference Example.
  • Each of the cleaning articles in Table 2 can increase the relative cleaning rate, and can suppress a decrease in cleaning power even when the cleaning composition is packaged in a water-soluble film.

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  • Detergent Compositions (AREA)

Abstract

Provided is a cleaning agent composition that has excellent cleaning, rinsing, and finishing performance on textile products and also imparts antibacterial properties to textile products. The cleaning agent composition contains, in prescribed amounts, the (A) component described below, the (B) component described below, (C) a water-insoluble inorganic component, (D) a cationic surfactant, and (E) an anionic polymer, and the mass ratio of the (B) content to the total (B) and (C) content is higher than 0 and no higher than 0.50. (A) component: a surfactant containing a predetermined ratio of (a1) a nonionic surfactant and optionally (a2) an anionic surfactant. (B) component: a water-soluble inorganic salt containing a predetermined ratio of the following (b1) component and (b2) component. (b1) component: a water-soluble inorganic salt wherein the pH of a 0.1 g/L aqueous solution of said salt is 9.0 or higher. (b2) component: a water-soluble inorganic salt wherein the pH of a 0.1 g/L aqueous solution of said salt is less than 9.0.

Description

洗浄剤組成物Cleaning composition

 本発明は、洗浄剤組成物に関する。 The present invention relates to a cleaning composition.

背景技術
 近年、環境負荷低減や持続可能な社会システムへの観点、すなわちエコ・サステナブルの観点から、洗浄剤組成物の使用量、特に界面活性剤の量を低減することが求められている。
 一方で、最近では夜洗濯や部屋干しなどが増加しており、それに伴って菌由来の洗濯物のニオイ悩みも増加してきている。更には近年のコロナウイルスの影響で衛生意識がより高まってきており、洗剤の基本機能として菌に対する効果は必須となってきている。
2. Background Art In recent years, from the viewpoint of reducing the environmental load and creating a sustainable social system, that is, from the viewpoint of eco-sustainability, there has been a demand to reduce the amount of detergent compositions used, in particular the amount of surfactants.
On the other hand, the recent increase in washing clothes at night and drying them indoors has led to an increase in the number of people complaining about odors caused by bacteria. Furthermore, hygiene awareness has increased due to the recent coronavirus outbreak, and the effectiveness of detergents against bacteria has become an essential basic function.

 特開平7-286195号公報には、(a)非イオン界面活性剤、(b)SiO分を50重量%以上含む多孔質無機粉体、(c)石鹸、を所定の量で均一に捏和・混合して固形洗剤を形成し、ついで無機質粉体を粉砕助剤として添加し該固形洗剤を破砕して粉粒状ないしは顆粒の洗剤粒子とする粒状非イオン洗剤組成物の製造方法が開示されている。
 特開平10-158697号公報には、(a)ノニオン界面活性剤、(b)粘土鉱物、(c)吸油性担体、(d)所定の高分子キレートビルダー、及び(e)陽荷電窒素原子を分子内に有し、前記ノニオン界面活性剤(a)に少なくとも部分的に溶解するとともに、前記粘土鉱物(b)に吸着されている陽荷電窒素原子含有化合物、を含有する、高嵩密度粒状ノニオン洗剤組成物が開示されている。
 特開2004-10681号公報には、(a)所定のアミン化合物、(b)スルホン酸塩、(c)所定の非イオン性化合物、及び(d)水溶性無機塩を含有し、JIS K3362:1998記載の界面活性剤相当分が10~60質量%である粒状洗浄剤組成物が開示されている。
Japanese Patent Laid-Open Publication No. 7-286195 discloses a method for producing a granular nonionic detergent composition, in which (a) a nonionic surfactant, (b) a porous inorganic powder containing 50% by weight or more of SiO2 , and (c) a soap are uniformly kneaded and mixed in predetermined amounts to form a solid detergent, and then an inorganic powder is added as a grinding aid to crush the solid detergent into powdery or granular detergent particles.
Japanese Patent Application Laid-Open No. 10-158697 discloses a high bulk density granular nonionic detergent composition containing (a) a nonionic surfactant, (b) a clay mineral, (c) an oil-absorbing carrier, (d) a specified polymer chelate builder, and (e) a positively charged nitrogen atom-containing compound which has a positively charged nitrogen atom in its molecule, is at least partially dissolved in the nonionic surfactant (a), and is adsorbed to the clay mineral (b).
Japanese Patent Application Laid-Open No. 2004-10681 discloses a granular detergent composition which contains (a) a specified amine compound, (b) a sulfonate salt, (c) a specified nonionic compound, and (d) a water-soluble inorganic salt, and has a surfactant equivalent content according to JIS K3362:1998 of 10 to 60 mass %.

発明の概要
 エコ・サステナブルの観点から、洗浄剤組成物には、少ない基剤量で高い洗浄性能が求められる。また、環境への配慮からすすぎの回数は少ないことが望ましい。
 本発明は、繊維製品の優れた洗浄性、すすぎ性及び仕上がり性を有し、更に繊維製品に抗菌性を付与する洗浄剤組成物を提供する。
 本発明における仕上がり性は、洗浄剤組成物の溶け残りを低減すること、被洗浄物におけるスジ残りを低減することをいう。
From the viewpoint of eco-sustainability, cleaning compositions are required to have high cleaning performance with a small amount of base. Also, from the viewpoint of environmental friendliness, it is desirable to have a small number of rinsing cycles.
The present invention provides a detergent composition which has excellent cleaning properties, rinsing properties and finish properties for textile products and further imparts antibacterial properties to the textile products.
In the present invention, the finish quality refers to reducing the amount of undissolved cleaning composition and reducing streaks remaining on the item to be cleaned.

 本発明は、下記(A)成分を5質量%以上40質量%以下、下記(B)成分を20質量%以上80質量%以下、下記(C)成分を5質量%以上40質量%以下、下記(D)成分を0.1質量%以上5.0質量%以下、下記(E)成分を0.1質量%以上10質量%以下含有し、
 (a2)成分の含有量と、(a1)成分と(a2)成分の合計含有量との質量比(a2)/[(a1)+(a2)]が0以上0.5以下、
 (b2)成分の含有量と、(b1)成分と(b2)成分の合計含有量との質量比(b2)/[(b1)+(b2)]が0.2以上0.8以下、
 (C)成分の含有量と、(B)成分と(C)成分の合計含有量との質量比(C)/[(B)+(C)]が0を超え0.50以下である、
洗浄剤組成物に関する。
(A)成分:下記(a1)成分及び下記(a2)成分から選ばれる1種以上
(a1)成分:ノニオン界面活性剤
(a2)成分:アニオン界面活性剤
(B)成分:下記(b1)成分及び下記(b2)成分から選ばれる1種以上
(b1)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩
(b2)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩
(C)成分:水不溶性無機成分
(D)成分:カチオン界面活性剤
(E)成分:アニオン性ポリマー
The present invention comprises the following component (A) in an amount of 5% by mass or more and 40% by mass or less, the following component (B) in an amount of 20% by mass or more and 80% by mass or less, the following component (C) in an amount of 5% by mass or more and 40% by mass or less, the following component (D) in an amount of 0.1% by mass or more and 5.0% by mass or less, and the following component (E) in an amount of 0.1% by mass or more and 10% by mass or less,
a mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more and 0.5 or less;
a mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) component is 0.2 or more and 0.8 or less;
a mass ratio (C)/[(B)+(C)] of the content of the (C) component to the total content of the (B) component and the (C) component is greater than 0 and is not greater than 0.50;
The present invention relates to a cleaning composition.
Component (A): one or more selected from the following component (a1) and component (a2): Component (a1): a nonionic surfactant Component (a2): an anionic surfactant Component (B): one or more selected from the following component (b1) and component (b2): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b1): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b2): a water-soluble inorganic salt having a pH of less than 9.0 at 20°C in a 0.1 g/L aqueous solution of the component (C): a water-insoluble inorganic component Component (D): a cationic surfactant Component (E): an anionic polymer

 本発明によれば、繊維製品の優れた洗浄性、すすぎ性及び仕上がり性を有し、更に繊維製品に抗菌性を付与する洗浄剤組成物が提供される。 The present invention provides a detergent composition that has excellent cleaning, rinsing and finishing properties for textile products, and further imparts antibacterial properties to the textile products.

発明を実施するための形態
 本発明の洗浄剤組成物が、繊維製品の優れた洗浄性、すすぎ性及び仕上がり性を有し、更に繊維製品に抗菌性を付与する機構は定かではないが、以下のように推察される。
 本発明の洗浄剤組成物は、(a1)成分のノニオン界面活性剤と、(a2)成分のアニオン界面活性剤及び(b1)成分のアルカリ剤を併用することで、皮脂汚れの洗浄性が向上すると推察される。
 また、本発明の洗浄剤組成物は、(a2)成分と(E)成分のアニオン性ポリマーとの併用により、泥汚れの洗浄力が向上すると推察される。
 また、本発明の洗浄剤組成物は、所定の(A)成分を含み、更に(B)成分の水溶性無機塩と(C)成分の水不溶性無機塩の割合を所定の範囲とすることで、すすぎ性と仕上がり性の両立が達成できたものと推察される。なお、本発明における仕上がり性は、洗浄剤組成物の溶け残りを低減すること、被洗浄物におけるスジ残りを低減することをいう。
 更に、本発明の洗浄剤組成物は、(A)成分~(E)成分を組み合わせることで、(D)成分の抗菌性能を損なうことなく、繊維製品の優れた洗浄性、すすぎ性及び仕上がり性が得られたものと推察される。
 なお、本発明の洗浄剤組成物は、上記の作用機構になんら限定されるものではない。
Mode for Carrying Out the Invention The mechanism by which the detergent composition of the present invention has excellent cleaning properties, rinsing properties and finishing properties for textile products and further imparts antibacterial properties to the textile products is not clear, but is presumed to be as follows.
It is presumed that the cleaning ability of the detergent composition of the present invention against sebum stains is improved by using a nonionic surfactant as component (a1), an anionic surfactant as component (a2), and an alkaline agent as component (b1) in combination.
It is also presumed that the cleaning power of the detergent composition of the present invention against muddy soils is improved by the combined use of component (a2) and the anionic polymer (E).
It is also believed that the cleaning composition of the present invention achieves both rinsability and finish by containing a specific component (A) and further by controlling the ratio of the water-soluble inorganic salt of component (B) to the water-insoluble inorganic salt of component (C) within a specific range. Note that the finish in the present invention refers to reducing the amount of undissolved part of the cleaning composition and reducing streaks on the washed object.
Furthermore, it is presumed that the combination of components (A) to (E) in the cleaning composition of the present invention provides excellent cleaning properties, rinsing properties and finishing properties for textile products without impairing the antibacterial activity of component (D).
The action mechanism of the cleaning composition of the present invention is not limited to the above-mentioned mechanism.

[洗浄剤組成物]
 本発明の洗浄剤組成物は、下記の(A)成分、(B)成分、(C)成分、(D)成分、及び(E)成分を所定量含有する。
(A)成分:下記(a1)成分及び下記(a2)成分から選ばれる1種以上
(a1)成分:ノニオン界面活性剤
(a2)成分:アニオン界面活性剤
(B)成分:下記(b1)成分及び下記(b2)成分から選ばれる1種以上
(b1)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩
(b2)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩
(C)成分:水不溶性無機成分
(D)成分:カチオン界面活性剤
(E)成分:アニオン性ポリマー
[Cleaning agent composition]
The cleaning composition of the present invention contains the following components (A), (B), (C), (D) and (E) in given amounts.
Component (A): one or more selected from the following component (a1) and component (a2): Component (a1): a nonionic surfactant Component (a2): an anionic surfactant Component (B): one or more selected from the following component (b1) and component (b2): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b1): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b2): a water-soluble inorganic salt having a pH of less than 9.0 at 20°C in a 0.1 g/L aqueous solution of the component (C): a water-insoluble inorganic component Component (D): a cationic surfactant Component (E): an anionic polymer

<(A)成分>
 (A)成分は、(a1)ノニオン界面活性剤及び(a2)アニオン界面活性剤から選ばれる1種以上の界面活性剤である。(A)成分は、(a1)成分から選ばれる1種以上の界面活性剤と、任意に(a2)成分から選ばれる1種以上の界面活性剤と、を含む界面活性剤であってよい。
<Component (A)>
The component (A) is one or more surfactants selected from the group consisting of (a1) nonionic surfactants and (a2) anionic surfactants. The component (A) may be a surfactant containing one or more surfactants selected from the component (a1) and, optionally, one or more surfactants selected from the component (a2).

<(a1)成分>
 (a1)成分は、ノニオン界面活性剤である。(a1)成分は、洗浄性能の観点から、ポリオキシアルキレンアルキル又はアルケニルエーテル、アルキル(ポリ)グリコシド(グリコシド型ノニオン界面活性剤)、ソルビタン系ノニオン界面活性剤、長鎖脂肪酸アルキルエステルのエステル結合間にアルキレンオキサイドが付加した化合物、脂肪酸モノグリセライド、及び蔗糖脂肪酸エステルから選ばれる1種以上を挙げることができる。
<Component (a1)>
The component (a1) is a nonionic surfactant, and from the viewpoint of cleaning performance, the component (a1) can be one or more selected from the group consisting of polyoxyalkylene alkyl or alkenyl ethers, alkyl (poly)glycosides (glycoside-type nonionic surfactants), sorbitan-based nonionic surfactants, compounds in which an alkylene oxide is added between the ester bonds of long-chain fatty acid alkyl esters, fatty acid monoglycerides, and sucrose fatty acid esters.

 (a1)成分のノニオン界面活性剤としては、(a1-1)アルキレンオキシ基を含み、アルキレンオキシ基の平均付加モル数が1以上30以下である、ノニオン界面活性剤(以下、(a1-1)成分という)が好ましい。
 (a1-1)成分のアルキレンオキシ基は、炭素数2以上4以下のアルキレンオキシ基から選ばれる1種以上の基が好ましく、エチレンオキシ基及びプロピレンオキシ基から選ばれる1種以上の基がより好ましい。
 (a1-1)成分のアルキレンオキシ基の平均付加モル数は、皮脂汚れに対する洗浄性の観点から、1以上、好ましくは6以上、より好ましくは8以上、そして、30以下、好ましくは25以下、より好ましくは20以下、更に好ましくは15以下である。
As the nonionic surfactant of the component (a1), (a1-1) a nonionic surfactant containing alkyleneoxy groups and having an average added mole number of alkyleneoxy groups of 1 or more and 30 or less (hereinafter referred to as component (a1-1)).
The alkyleneoxy group of the component (a1-1) is preferably one or more groups selected from alkyleneoxy groups having from 2 to 4 carbon atoms, and more preferably one or more groups selected from an ethyleneoxy group and a propyleneoxy group.
The average number of moles of alkyleneoxy groups added in the component (a1-1) is, from the viewpoint of cleansing ability against sebum stains, 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.

 (a1-1)成分は、下記一般式(a1-1)で表されるノニオン界面活性剤が好ましい。
  R1a(CO)O-(A1aO)-R2a (a1-1)
〔式中、R1aは炭素数8以上18以下の脂肪族炭化水素基であり、R2aは水素原子又はメチル基である。COはカルボニル基であり、mは0又は1の数である。A1aO基は炭素数2以上4以下のアルキレンオキシ基から選ばれる1種以上である。nはA1aO基の平均付加モル数であって、1以上30以下の数である。〕
The component (a1-1) is preferably a nonionic surfactant represented by the following general formula (a1-1).
R 1a (CO) m O-(A 1a O) n -R 2a (a1-1)
[In the formula, R 1a is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 2a is a hydrogen atom or a methyl group. CO is a carbonyl group, and m is the number of 0 or 1. The A 1a O group is one or more selected from alkyleneoxy groups having 2 to 4 carbon atoms. n is the average number of moles added of the A 1a O groups, and is a number of 1 to 30.]

 一般式(a1-1)中、R1aの炭素数は、皮脂に対する洗浄性の観点から、8以上、好ましくは10以上、より好ましくは12以上、そして、18以下、好ましくは16以下、より好ましくは14以下である。
1aは、脂肪族炭化水素基であり、好ましくはアルキル基及びアルケニル基から選ばれる基である。
In general formula (a1-1), the number of carbon atoms in R 1a is 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, from the viewpoint of cleansing ability against sebum.
R 1a is an aliphatic hydrocarbon group, preferably a group selected from an alkyl group and an alkenyl group.

 一般式(a1-1)中、A1aO基は、炭素数2以上4以下のアルキレンオキシ基から選ばれる1種以上、好ましくは炭素数2以上3以下のアルキレンオキシ基から選ばれる1種以上、より好ましくはエチレンオキシ基である。A1aO基が、異なる複数のアルキレンオキシ基を含む場合、異なるアルキレンオキシ基は、ブロック型結合でもランダム型結合であってもよい。 In general formula (a1-1), the A 1a O group is one or more selected from alkyleneoxy groups having from 2 to 4 carbon atoms, preferably one or more selected from alkyleneoxy groups having from 2 to 3 carbon atoms, more preferably an ethyleneoxy group. When the A 1a O group contains a plurality of different alkyleneoxy groups, the different alkyleneoxy groups may be bonded in a block manner or a random manner.

 一般式(a1-1)中、nは、A1aO基の平均付加モル数であって、1以上30以下の数である。一般式(a1-1)中、nは、皮脂汚れに対する洗浄性の観点から、1以上、好ましくは6以上、より好ましくは8以上、そして、30以下、好ましくは25以下、より好ましくは20以下、更に好ましくは15以下である。
 一般式(a1-1)中、mは、洗浄性の観点から0が好ましい。
 一般式(a1-1)中、R2aは、洗浄性の観点から、水素原子が好ましい。
In general formula (a1-1), n is the average number of moles of A 1a O groups added and is a number of 1 to 30. In general formula (a1-1), n is 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less, from the viewpoint of cleansing ability against sebum stains.
In formula (a1-1), m is preferably 0 from the viewpoint of cleaning properties.
In general formula (a1-1), R 2a is preferably a hydrogen atom from the viewpoint of cleaning properties.

 (a1-1)成分以外のアルキレンオキシ基を有さないノニオン界面活性剤の具体例としては、蔗糖脂肪酸エステル、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、アルキルグリコシド、及びグリセリルモノエーテルから選ばれる1種以上が挙げられる。 Specific examples of nonionic surfactants that do not have an alkyleneoxy group other than component (a1-1) include one or more selected from sucrose fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, alkyl glycosides, and glyceryl monoethers.

<(a2)成分>
 (a2)成分は、アニオン界面活性剤である。(a2)成分は、粒子汚れの洗浄性能の観点から、アルキルアリールスルホン酸型界面活性剤、硫酸エステル型界面活性剤、アルカンスルホン酸型界面活性剤、オレフィンスルホン酸型界面活性剤、スルホコハク酸アルキルエステル型界面活性剤、スルホ脂肪酸エステル型界面活性剤、並びに脂肪酸及びその塩から選ばれる1種以上が好ましく、アルキルアリールスルホン酸型界面活性剤、硫酸エステル型界面活性剤、スルホコハク酸アルキルエステル型界面活性剤、並びに脂肪酸及びその塩から選ばれる1種以上がより好ましく、アルキルアリールスルホン酸型界面活性剤、並びに脂肪酸及びその塩から選ばれる1種以上が更に好ましい。
 なお、(a2)成分が塩の場合、(a2)成分の塩は、ナトリウム塩、カリウム塩、アンモニウム塩、マグネシウム塩等の無機塩、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩、モルホリン塩等の有機塩が挙げられる。(a2)成分の塩は、好ましくはナトリウム塩、カリウム塩等のアルカリ金属塩及びマグネシウム塩等のアルカリ土類金属塩から選ばれる無機塩であり、より好ましくはアルカリ金属塩、更に好ましくはナトリウム塩である。
<Component (a2)>
The component (a2) is an anionic surfactant. From the viewpoint of cleaning performance for particle soils, the component (a2) is preferably one or more selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, alkanesulfonic acid type surfactants, olefinsulfonic acid type surfactants, sulfosuccinic acid alkyl ester type surfactants, sulfo fatty acid ester type surfactants, and fatty acids and their salts, more preferably one or more selected from alkylarylsulfonic acid type surfactants, sulfate ester type surfactants, sulfosuccinic acid alkyl ester type surfactants, and fatty acids and their salts, and even more preferably one or more selected from alkylarylsulfonic acid type surfactants, and fatty acids and their salts.
When component (a2) is a salt, examples of the salt include inorganic salts such as sodium salt, potassium salt, ammonium salt, magnesium salt, etc., and organic salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, morpholine salt, etc. The salt of component (a2) is preferably an inorganic salt selected from alkali metal salts such as sodium salt, potassium salt, etc. and alkaline earth metal salts such as magnesium salt, etc., more preferably an alkali metal salt, and even more preferably a sodium salt.

 (a2)成分としては、下記一般式(a2-1)で表される化合物〔以下、(a2-1)成分という〕、一般式(a2-2)で表される化合物〔以下、(a2-2)成分という〕、一般式(a2-3)で表される化合物〔以下、(a2-3)成分という〕及び一般式(a2-4)で表される化合物〔以下、(a2-4)成分という〕から選ばれる1種以上の化合物が挙げられる。(a2)成分は、粒子汚れの洗浄性能の観点から、(a2-1)成分、(a2-2)成分、及び(a2-3)成分から選ばれる1種以上が好ましく、(a2-1)成分、及び(a2-2)成分から選ばれる1種以上がより好ましい。
 R3a-B-SOM   (a2-1)
〔式(a2-1)中、R3aは炭素数9以上14以下のアルキル基を示し、Bはベンゼン環を示し、Bの炭素原子と結合するR3aの炭素原子が第2級炭素原子であり、Mは陽イオンを示す。Bに結合するR3aに対して、スルホン酸基はオルト、メタ又はパラ位に結合している。〕
 R4a-COOM   (a2-2)
〔式(a2-2)中、R4aは炭素数10以上18以下のアルキル基又はアルケニル基を示し、Mは陽イオンを示す。〕
 R5a-O-(AO)-SOM   (a2-3)
〔式(a2-3)中、R5aは炭素数10以上18以下の脂肪族炭化水素基であり、AO基はエチレンオキシ基及びプロピレンオキシ基から選ばれる1種以上のアルキレンオキシ基であり、nは0以上20以下の数であり、Mは陽イオンである。〕
 R6a-CH(SOM)COOR7a   (a2-4)
〔式(a2-4)中、R6aは炭素数8以上18以下のアルキル基を示し、R7aは、水素原子又は炭素数1以上5以下のアルキル基を示し、Mは陽イオンを示す。〕
Examples of the component (a2) include one or more compounds selected from the compounds represented by the following general formula (a2-1) (hereinafter referred to as the component (a2-1)), the compounds represented by the general formula (a2-2) (hereinafter referred to as the component (a2-2)), the compounds represented by the general formula (a2-3) (hereinafter referred to as the component (a2-3)), and the compounds represented by the general formula (a2-4) (hereinafter referred to as the component (a2-4)). From the viewpoint of cleaning performance for particulate soils, the component (a2) is preferably one or more selected from the components (a2-1), (a2-2), and (a2-3), and more preferably one or more selected from the components (a2-1) and (a2-2).
R 3a -B-SO 3 M (a2-1)
[In formula (a2-1), R 3a represents an alkyl group having 9 to 14 carbon atoms, B represents a benzene ring, the carbon atom of R 3a bonded to the carbon atom of B is a secondary carbon atom, and M represents a cation. The sulfonic acid group is bonded to the ortho, meta, or para position relative to R 3a bonded to B.]
R 4a -COOM (a2-2)
[In formula (a2-2), R 4a represents an alkyl group or an alkenyl group having 10 to 18 carbon atoms, and M represents a cation.]
R 5a -O-(AO) n -SO 3 M (a2-3)
[In formula (a2-3), R 5a is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group, n is a number of 0 to 20, and M is a cation.]
R 6a -CH(SO 3 M) COOR 7a (a2-4)
[In formula (a2-4), R 6a represents an alkyl group having 8 to 18 carbon atoms, R 7a represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents a cation.]

 一般式(a2-1)中、R3aは、炭素数9以上、好ましくは10以上、そして、好ましくは14以下、より好ましくは13以下のアルキル基である。
 一般式(a2-1)中、Mは、好ましくは水素イオン、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン、マグネシウムイオン、カルシウムイオン等のアルカリ土類金属(1/2原子)イオン、又は有機アンモニウムイオンである。有機アンモニウム塩は、モノエタールアミン、ジエタノールアミン、トリエタノールアミン等のアミンによる塩であってよい。Mは、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオンであり、より好ましくはナトリウムイオンである。
In general formula (a2-1), R 3a represents an alkyl group having 9 or more carbon atoms, preferably 10 or more carbon atoms, and preferably 14 or less, more preferably 13 or less carbon atoms.
In general formula (a2-1), M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and more preferably a sodium ion.

 (a2-1)成分としては、アルキル基の炭素数が10以上14以下のp-アルキルベンゼンスルホン酸塩が好ましく、アルキル基の炭素数が10以上14以下のp-アルキルベンゼンスルホン酸ナトリウム塩がより好ましい。すなわち、(a2-1)成分は、一般式(a2-1)中、R3aが炭素数10以上14以下のアルキル基、Mがナトリウムイオンである化合物が好ましい。 The component (a2-1) is preferably a p-alkylbenzenesulfonate in which the alkyl group has from 10 to 14 carbon atoms, and more preferably a sodium p-alkylbenzenesulfonate in which the alkyl group has from 10 to 14 carbon atoms. That is, the component (a2-1) is preferably a compound in which, in general formula (a2-1), R 3a is an alkyl group having from 10 to 14 carbon atoms, and M is a sodium ion.

 一般式(a2-2)中、R4aは、炭素数10以上、好ましくは11以上、そして、18以下、好ましくは16以下、より好ましくは14以下、更に好ましくは13以下のアルキル基又はアルケニル基である。R4aは、直鎖のアルキル基、分岐鎖のアルキル基、直鎖のアルケニル基及び分岐鎖のアルケニル基から選ばれる1種以上の基が挙げられ、直鎖のアルキル基が好ましい。
 一般式(a2-2)中、Mは、好ましくは水素イオン、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン、マグネシウムイオン、カルシウムイオン等のアルカリ土類金属(1/2原子)イオン、又は有機アンモニウムイオンである。有機アンモニウム塩は、モノエタールアミン、ジエタノールアミン、トリエタノールアミン等のアミンによる塩であってよい。Mは、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオンであり、より好ましくはナトリウムイオンである。
In general formula (a2-2), R 4a is an alkyl group or alkenyl group having 10 or more, preferably 11 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 13 or less. R 4a can be one or more groups selected from a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group, and is preferably a linear alkyl group.
In general formula (a2-2), M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and more preferably a sodium ion.

 (a2-2)成分としては、ラウリン酸、ミリスチン酸、イソステアリン酸、パルミチン酸、イソパルミチン酸、オレイン酸及びこれらの塩から選ばれる1種以上が好ましく、より好ましくはラウリン酸、ミリスチン酸、パルミチン酸及びこれらの塩から選ばれる1種以上、更に好ましくはラウリン酸、ミリスチン酸及びこれらの塩から選ばれる1種以上である。
 (a2-2)成分は、一般式(a2-2)中、R4aが炭素数10以上16以下のアルキル基、Mが陽イオンである化合物が好ましく、Mが水素イオン又はナトリウムイオンである化合物がより好ましい。
The component (a2-2) is preferably one or more selected from lauric acid, myristic acid, isostearic acid, palmitic acid, isopalmitic acid, oleic acid, and salts thereof, more preferably one or more selected from lauric acid, myristic acid, palmitic acid, and salts thereof, and even more preferably one or more selected from lauric acid, myristic acid, and salts thereof.
The component (a2-2) is preferably a compound in which, in general formula (a2-2), R 4a is an alkyl group having from 10 to 16 carbon atoms and M is a cation, and more preferably a compound in which M is a hydrogen ion or a sodium ion.

 一般式(a2-3)中、R5aは、好ましくは10以上、より好ましくは11以上、更に好ましくは12以上、そして、好ましくは18以下、より好ましくは16以下、更に好ましくは14以下の脂肪族炭化水素基である。R5aは、直鎖又は分岐鎖の脂肪族炭化水素基であり、好ましくは直鎖の脂肪族炭化水素基であり、より好ましくは直鎖アルキル基である。 In general formula (a2-3), R 5a is an aliphatic hydrocarbon group having an integer of preferably 10 or more, more preferably 11 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, even more preferably 14 or less. R 5a is a linear or branched aliphatic hydrocarbon group, preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkyl group.

 一般式(a2-3)中、AO基は、エチレンオキシ基及びプロピレンオキシ基から選ばれる1種以上のアルキレンオキシ基である。AO基が、エチレンオキシ基及びプロピレンオキシ基を含む場合は、エチレンオキシ基とプロピレンオキシ基は、ブロック型結合でもランダム型結合であっても良い。AO基は、洗浄性向上の観点から、エチレンオキシ基を含む基であることが好ましい。 In general formula (a2-3), the AO group is one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group. When the AO group contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be in a block bond or a random bond. From the viewpoint of improving cleaning properties, it is preferable that the AO group is a group containing an ethyleneoxy group.

 一般式(a2-3)中、nは、AO基の平均付加モル数であって、0以上20以下の数である。nは、洗浄性向上の観点から、0以上、そして、洗浄性向上の観点から、20以下、好ましくは16以下、より好ましくは12以下、更に好ましくは8以下、より更に好ましくは4以下である。 In general formula (a2-3), n is the average number of moles of AO groups added, and is a number between 0 and 20. From the viewpoint of improving cleaning performance, n is 0 or more, and from the viewpoint of improving cleaning performance, n is 20 or less, preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and even more preferably 4 or less.

 一般式(a2-3)中、AOがプロピレンオキシ基を含む場合、プロピレンオキシ基の平均付加モル数は、好ましくは4以下、より好ましくは3以下、そして、好ましくは0以上である。一般式(a2-3)中、プロピレンオキシ基の平均付加モル数は、0であってもよい。
 一般式(a2-3)中、AOがエチレンオキシ基を含む場合、エチレンオキシ基の平均付加モル数は、好ましくは0以上、そして、好ましくは10以下、より好ましくは5以下、更に好ましくは4以下である。
In the general formula (a2-3), when AO contains a propyleneoxy group, the average number of moles of the propyleneoxy group added is preferably 4 or less, more preferably 3 or less, and preferably 0 or more. In the general formula (a2-3), the average number of moles of the propyleneoxy group added may be 0.
In the general formula (a2-3), when AO contains an ethyleneoxy group, the average number of moles of the ethyleneoxy group added is preferably 0 or more and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.

 一般式(a2-3)中、Mは、好ましくは水素イオン、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン、マグネシウムイオン、カルシウムイオン等のアルカリ土類金属(1/2原子)イオン、又は有機アンモニウムイオンである。有機アンモニウム塩は、モノエタールアミン、ジエタノールアミン、トリエタノールアミン等のアミンによる塩であってよい。Mは、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオンであり、より好ましくはナトリウムイオンである。 In general formula (a2-3), M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and is more preferably a sodium ion.

 一般式(a2-4)中、R6aは、好ましくは炭素数8以上、より好ましくは10以上、更に好ましくは12以上、そして、好ましくは18以下、より好ましくは16以下のアルキル基である。
一般式(a2-4)中、R7aは、好ましくは炭素数1以上、そして、好ましくは5以下、より好ましくは4以下、更に好ましくは3以下のアルキル基である。
In general formula (a2-4), R 6a is preferably an alkyl group having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less.
In general formula (a2-4), R 7a is preferably an alkyl group having 1 or more carbon atoms and preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less.

 一般式(a2-4)中、Mは、好ましくは水素イオン、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン、マグネシウムイオン、カルシウムイオン等のアルカリ土類金属(1/2原子)イオン、又は有機アンモニウムイオンである。有機アンモニウム塩は、モノエタールアミン、ジエタノールアミン、トリエタノールアミン等のアミンによる塩であってよい。Mは、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオンであり、より好ましくはナトリウムイオンである。 In general formula (a2-4), M is preferably a hydrogen ion, an alkali metal ion such as a sodium ion or a potassium ion, an alkaline earth metal (1/2 atom) ion such as a magnesium ion or a calcium ion, or an organic ammonium ion. The organic ammonium salt may be a salt with an amine such as monoethanolamine, diethanolamine, or triethanolamine. M is preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, and is more preferably a sodium ion.

 (a2-4)成分としては、一般式(a2-4)中、R6a炭素数が11以上14以下のアルキル基、R7aがメチル基、Mがナトリウムイオンである、α-スルホ脂肪酸メチルエステルナトリウム塩が好ましい。 The component (a2-4) is preferably an α-sulfofatty acid methyl ester sodium salt, in which, in general formula (a2-4), R 6a is an alkyl group having 11 to 14 carbon atoms, R 7a is a methyl group, and M is a sodium ion.

<(B)成分>
 (B)成分は、(b1)成分及び(b2)成分から選ばれる1種以上の水溶性無機塩である。
 (B)成分は、(b1)成分から選ばれる1種以上の水溶性無機塩と、(b2)成分から選ばれる1種以上の水溶性無機塩と、を含む水溶性無機塩であってよい。
<Component (B)>
The component (B) is one or more water-soluble inorganic salts selected from the components (b1) and (b2).
The component (B) may be a water-soluble inorganic salt containing one or more water-soluble inorganic salts selected from the component (b1) and one or more water-soluble inorganic salts selected from the component (b2).

 本発明において、(B)成分における水溶性無機塩とは、20℃の水100gに1g以上溶解する無機塩をいう。
 (b1)成分は、水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩である。
 (b2)成分は、水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩である。
In the present invention, the water-soluble inorganic salt in component (B) refers to an inorganic salt that dissolves in an amount of 1 g or more in 100 g of water at 20°C.
The component (b1) is a water-soluble inorganic salt, and a 0.1 g/L aqueous solution of the water-soluble inorganic salt has a pH of 9.0 or higher at 20° C.
The component (b2) is a water-soluble inorganic salt, and the pH of a 0.1 g/L aqueous solution of the water-soluble inorganic salt at 20° C. is less than 9.0.

 本発明の洗浄剤組成物において、(b1)成分と(b2)成分を適した割合で用いることで、後述する水不溶性無機成分である(C)成分を含んでいても、当該洗浄剤組成物の水への溶け残りの抑制と洗浄性の低下を抑制することができる。 In the cleaning composition of the present invention, by using the components (b1) and (b2) in an appropriate ratio, it is possible to prevent the cleaning composition from remaining undissolved in water and to prevent a decrease in cleaning properties, even if the cleaning composition contains the water-insoluble inorganic component (C) described below.

<pHの測定法>
 (b1)成分及び(b2)成分の0.1g/L水溶液の20℃におけるpHは、具体的には、下記pHの測定方法で測定される。
 pHメーター(例えば、株式会社堀場製作所製、pH/イオンメーター F-23)にpH電極内部液を飽和塩化カリウム水溶液(3.33モル/L)としたpH測定用複合電極(例えば、株式会社堀場製作所製、ガラス摺り合わせスリーブ型)を接続する。次に、pH4.01標準液(フタル酸塩標準液)、pH6.86(中性リン酸塩標準液)、pH9.18標準液(ホウ酸塩標準液)をそれぞれ100mLビーカーに充填し、20℃の恒温槽に30分間浸漬する。恒温に調整された標準液にpH測定用電極を3分間浸し、pH6.86→pH9.18→pH4.01の順に校正操作を行う。測定対象となる(b1)の0.1g/L水溶液又は(b2)成分の0.1g/L水溶液を20℃に調整し、前記のpHメーターの電極をサンプルに浸漬し、1分後のpHを測定する。
<Method of measuring pH>
Specifically, the pH of a 0.1 g/L aqueous solution of the components (b1) and (b2) at 20° C. is measured by the pH measurement method described below.
A composite electrode for pH measurement (e.g., glass-laid sleeve type, manufactured by Horiba, Ltd.) with a saturated potassium chloride aqueous solution (3.33 mol/L) as the pH electrode internal solution is connected to a pH meter (e.g., pH/ion meter F-23, manufactured by Horiba, Ltd.). 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 filled into a 100 mL beaker, and immersed in a thermostatic bath at 20°C for 30 minutes. The pH measurement electrode is immersed in the thermostatically adjusted standard solution for 3 minutes, and calibration operations are performed in the order of pH 6.86 → pH 9.18 → pH 4.01. A 0.1 g/L aqueous solution of the (b1) or 0.1 g/L aqueous solution of the (b2) component to be measured is adjusted to 20°C, and the electrode of the pH meter is immersed in the sample, and the pH is measured after 1 minute.

<(b1)成分>
 (b1)成分は、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩である。(b1)成分は、アルカリ剤であってよい。(b1)成分は、アルカリ金属炭酸塩、アルカリ金属ケイ酸塩、トリポリリン酸塩、アルカリ金属亜硫酸塩、アルカリ金属水酸化物、アルカリ金属の過ホウ酸塩、及びアルカリ金属の過炭酸塩から選ばれる1種以上のアルカリ剤が挙げられる。
 アルカリ金属炭酸塩としては、炭酸ナトリウム、炭酸カリウム、及びセスキ炭酸ナトリウムから選ばれる1種以上が挙げられ、炭酸ナトリウムが好ましい。
 アルカリ金属ケイ酸塩としては、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、及びメタケイ酸カリウムから選ばれる1種以上が挙げられる。
 トリポリリン酸塩としては、トリポリリン酸のアルカリ金属塩が挙げられる。
 アルカリ金属亜硫酸塩としては、亜硫酸ナトリウムが挙げられる。
 アルカリ金属水酸化物としては、水酸化ナトリウム、及び水酸化カリウムから選ばれる1種以上が挙げられる。
 アルカリ金属の過ホウ酸塩としては、過ホウ酸ナトリウムが挙げられる。
 アルカリ金属の過炭酸塩としては、過炭酸ナトリウムが挙げられる。
<Component (b1)>
The component (b1) is a water-soluble inorganic salt having a pH of 9.0 or more at 20° C. in a 0.1 g/L aqueous solution. The component (b1) may be an alkaline agent. Examples of the component (b1) include one or more alkaline agents selected from alkali metal carbonates, alkali metal silicates, tripolyphosphates, alkali metal sulfites, alkali metal hydroxides, alkali metal perborates, and alkali metal percarbonates.
The alkali metal carbonate may be at least one selected from sodium carbonate, potassium carbonate, and sodium sesquicarbonate, with sodium carbonate being preferred.
The alkali metal silicate may be at least one selected from sodium silicate, potassium silicate, sodium metasilicate, and potassium metasilicate.
Tripolyphosphates include alkali metal salts of tripolyphosphate.
Alkali metal sulfites include sodium sulfite.
The alkali metal hydroxide may be at least one selected from sodium hydroxide and potassium hydroxide.
Alkali metal perborates include sodium perborate.
The alkali metal percarbonate includes sodium percarbonate.

 (b1)成分は、洗浄性能の観点から、好ましくはアルカリ金属炭酸塩から選ばれる1種以上、より好ましくは炭酸ナトリウム及び炭酸カリウムから選ばれる1種以上、更に好ましくは炭酸ナトリウムである。 From the viewpoint of cleaning performance, the component (b1) is preferably one or more selected from alkali metal carbonates, more preferably one or more selected from sodium carbonate and potassium carbonate, and even more preferably sodium carbonate.

<(b2)成分>
 (b2)成分は、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩である。(b2)成分は、無機硫酸塩、無機ハロゲン化合物、及びアルカリ金属炭酸水素塩から選ばれる1種以上の化合物であってよい。(b2)成分は、無機硫酸塩及びアルカリ金属炭酸水素塩から選ばれる1種以上の水溶性無機塩を含むことが好ましい。
 (b2)成分は、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、硫酸カリウム、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、炭酸水素ナトリウム、及び炭酸水素カリウムから選ばれる1種以上の化合物が挙げられる。(b2)成分は、水和物であっても無水物であっても良い。
<Component (b2)>
Component (b2) is a water-soluble inorganic salt having a pH of less than 9.0 in a 0.1 g/L aqueous solution at 20° C. Component (b2) may be one or more compounds selected from inorganic sulfates, inorganic halogen compounds, and alkali metal hydrogen carbonates. Component (b2) preferably contains one or more water-soluble inorganic salts selected from inorganic sulfates and alkali metal hydrogen carbonates.
The component (b2) may be one or more compounds selected from sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium hydrogen carbonate, and potassium hydrogen carbonate. The component (b2) may be a hydrate or anhydrous.

<(C)成分>
 (C)成分は、水不溶性無機成分である。(C)成分は、水不溶性担体であってよい。(C)成分について、「水不溶性」とは、20℃の水100gに1g以上溶解しないことをいう。
 (C)成分は、非晶質シリカ、ケイ酸カルシウム、粘土鉱物、結晶性アルミノケイ酸塩及び非晶質アルミノケイ酸塩から選ばれる1種以上であってよく、好ましくは粘土鉱物、及び結晶性アルミノケイ酸塩から選ばれる1種以上である。(C)成分は、前記(B)成分と特定の割合で用いることで、当該洗浄剤組成物を用いた被洗物の洗浄後の溶け残りの抑制と、すすぎ水が濁りを低減する作用を有する。
<Component (C)>
The component (C) is a water-insoluble inorganic component. The component (C) may be a water-insoluble carrier. With respect to the component (C), "water-insoluble" means that 1 g or more of the component does not dissolve in 100 g of water at 20°C.
The component (C) may be one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicates, and amorphous aluminosilicates, and is preferably one or more selected from clay minerals and crystalline aluminosilicates. The component (C), when used in a specific ratio with the component (B), has the effect of suppressing the amount of dissolution of the detergent composition after washing of the items to be washed and reducing the turbidity of the rinse water.

 (C)成分の平均一次粒子径は、好ましくは0.1μm以上、より好ましくは1μm以上、そして、好ましくは10μm以下、より好ましくは5μm以下である。(C)成分の平均一次粒子径は、レーザー回折/散乱式粒子径分布測定装置(例えば、HORIBA社、LA-950)により測定されたものである。この平均一次粒子径は、体積基準による累積粒度分布のD50(メジアン径)である。 The average primary particle diameter of component (C) is preferably 0.1 μm or more, more preferably 1 μm or more, and preferably 10 μm or less, more preferably 5 μm or less. The average primary particle diameter of component (C) is measured using a laser diffraction/scattering type particle size distribution measuring device (e.g., HORIBA, LA-950). This average primary particle diameter is the D50 (median diameter) of the cumulative particle size distribution based on volume.

 (C)成分としては、具体的には、特開平9-132794号公報、特開平7-10526号公報、特開平6-227811号公報、特開平8-119622号公報などに記載されている非晶質アルミノシリケート(吸油能:285mL/100g)等を挙げることができる。
 更に具体的には、(C)成分のケイ酸カルシウムとして、フローライトR((株)トクヤマ製、吸油能:400~500mL/100g)、(C)成分の非晶質シリカとして、トクシールNR((株)トクヤマ製、吸油能:210~270mL/100g)、サイロピュア(富士シリシア化学(株)社製、吸油能:240~280mL/100g)、(C)成分の非晶質アルミノケイ酸塩として、TIXOREX25(韓仏化学社製、220~270mL/100g)、等を用いることができる。
Specific examples of the component (C) include amorphous aluminosilicates (oil absorption capacity: 285 mL/100 g) described in JP-A-9-132794, JP-A-7-10526, JP-A-6-227811, and JP-A-8-119622.
More specifically, the calcium silicate of component (C) may be Fluorite R (manufactured by Tokuyama Corp., oil absorption capacity: 400 to 500 mL/100 g), the amorphous silica of component (C) may be Tokusil NR (manufactured by Tokuyama Corp., oil absorption capacity: 210 to 270 mL/100 g) or Silopure (manufactured by Fuji Silysia Chemical Ltd., oil absorption capacity: 240 to 280 mL/100 g), and the amorphous aluminosilicate of component (C) may be TIXOREX25 (manufactured by Korea-Futsu Chemical Co., Ltd., 220 to 270 mL/100 g).

 また、結晶性アルミノケイ酸塩は、ゼオライトが挙げられる。具体的なゼオライトとして、A型、X型、P型ゼオライト等の結晶性アルミノケイ酸塩が挙げられる。結晶性アルミノケイ酸塩は、A型ゼオライト(例えば、商品名「トヨビルダー」:東ソー(株)製、JIS K 5101法による吸油能:40mL/100g以上)が好ましい。その他に、P型(例えば、商品名「Doucil A24」、「ZSEO64」等;いずれもCrosfield社製;吸油能60~150mL/100g)、X型(例えば、商品名「WessalithXD」、;Degussa社製;吸油能80~100mL/100g)、国際公開第98/4262
2号記載のハイブリッドゼオライトも好適なものとして挙げられる。
Further, the crystalline aluminosilicate may be zeolite. Specific examples of zeolites include crystalline aluminosilicates such as A-type, X-type, and P-type zeolites. The crystalline aluminosilicate is preferably A-type zeolite (for example, trade name "Toyobuilder" manufactured by Tosoh Corporation, oil absorption capacity according to JIS K 5101 method: 40 mL/100 g or more). Other examples include P-type zeolite (for example, trade names "Doucil A24", "ZSEO64", etc.; both manufactured by Crosfield; oil absorption capacity 60 to 150 mL/100 g), X-type (for example, trade name "WessalithXD" manufactured by Degussa; oil absorption capacity 80 to 100 mL/100 g), and WO 98/4262 zeolite.
The hybrid zeolite described in No. 2 is also suitable.

 (C)成分の粘土鉱物としては、ベントナイトが挙げられる。ベントナイトは、50~100meq/100gのイオン交換能力を有するものが好ましい。ベントナイトは、アルカリ金属又はアルカリ土類金属モンモリロナイト、サポナイト又はヘクトライトからなる群から選択されるモンモリロン石群鉱物粘土(smectitic clay)、イライト、アタパルジャイト(attapulgite)及びカオリナイトから選ばれる1種以上が挙げられる。ベントナイトは、粉末化したもの、粒状化したものを用いることができる。例えば、特開2008-189719号公報の粘土鉱物の造粒物を参照することができる。 An example of the clay mineral of component (C) is bentonite. The bentonite preferably has an ion exchange capacity of 50 to 100 meq/100 g. The bentonite may be one or more selected from the group consisting of alkali metal or alkaline earth metal montmorillonite, saponite or hectorite, smectitic clay, illite, attapulgite and kaolinite. Powdered or granulated bentonite may be used. For example, see JP 2008-189719 A for the granulated clay mineral.

<(D)成分>
 (D)成分は、カチオン界面活性剤である。(D)成分は、4級アンモニウム塩型界面活性剤が挙げられる。(D)成分は、殺菌作用、抗菌作用及び除菌作用から選ばれる1以上の作用を有するものであってよい。
 (D)成分の4級アンモニウム塩型界面活性剤としては、下記一般式(d1)で表される化合物、及び下記一般式(d2)で表される化合物から選ばれる1種以上が好ましい。
<Component (D)>
The component (D) is a cationic surfactant. The component (D) may be a quaternary ammonium salt type surfactant. The component (D) may have one or more functions selected from a bactericidal action, an antibacterial action, and a disinfecting action.
The quaternary ammonium salt surfactant of the component (D) is preferably at least one selected from the group consisting of compounds represented by the following general formula (d1) and compounds represented by the following general formula (d2):

Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001

〔式中、R1dは、炭素数8以上18以下の脂肪族炭化水素基であり、R2dは、炭素数8以上18以下の脂肪族炭化水素基、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基であり、R3d及びR4dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基であり、Xは陰イオンである。〕 [In the formula, R 1d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, R 2d is a group selected from an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, an alkyl group having from 1 to 3 carbon atoms, and a hydroxyalkyl group having from 1 to 3 carbon atoms, R 3d and R 4d are each independently a group selected from an alkyl group having from 1 to 3 carbon atoms, and a hydroxyalkyl group having from 1 to 3 carbon atoms, and X is an anion.]

Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002

〔式中、R5dは、炭素数8以上18以下の脂肪族炭化水素基であり、R6d及びR7dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基であり、Xは陰イオンである。〕 [In the formula, R 5d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, R 6d and R 7d are each independently a group selected from an alkyl group having from 1 to 3 carbon atoms and a hydroxyalkyl group having from 1 to 3 carbon atoms, and X is an anion.]

 一般式(d1)において、R1dの炭素数は、洗浄力の観点から、好ましくは9以上、より好ましくは10以上、更に好ましくは12以上、そして、好ましくは16以下である。R1dは、アルキル基又はアルケニル基が好ましく、アルキル基が好ましい。
 一般式(d1)において、R2dは、炭素数8以上18以下の脂肪族炭化水素基、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基である。
 R2dが、炭素数8以上18以下の脂肪族炭化水素基である場合、R2dは、洗浄力の観点から、好ましくは8以上、そして、好ましくは14以下、より好ましくは12以下のアルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。
In general formula (d1), from the viewpoint of detergency, the number of carbon atoms in R 1d is preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less. R 1d is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
In general formula (d1), R 2d is a group selected from an aliphatic hydrocarbon group having 8 to 18 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms.
When R 2d is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, from the viewpoint of detergency, R 2d is preferably an alkyl or alkenyl group having 8 or more and preferably 14 or less, more preferably 12 or less, and more preferably an alkyl group.

 一般式(d1)において、R3d及びR4dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基である。R3d及びR4dは、それぞれ独立に、炭素数1以上3以下のアルキル基から選ばれる基であることが好ましい。炭素数1以上3以下のアルキル基としては、メチル基、エチル基、プロピル基が挙げられる。炭素数1以上3以下のヒドロキシアルキル基としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基が挙げられる。 In general formula (d1), R 3d and R 4d 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. It is preferable that R 3d and R 4d are each independently a group selected from an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

 一般式(d1)において、Xは陰イオンである。陰イオンとしては、ハロゲンイオン、及び炭素数1以上3以下のアルキル硫酸イオンから選ばれる1種以上の陰イオンが挙げられる。ハロゲンイオンとしては、例えば塩化物イオン、臭化物イオン及びヨウ化物イオンが挙げられる。また、炭素数1以上3以下のアルキル硫酸イオンとしては、例えばメチル硫酸イオン、エチル硫酸イオン及びプロピル硫酸イオンが挙げられる。 In general formula (d1), X- is an anion. Examples of the anion include one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms. Examples of the halogen ion include a chloride ion, a bromide ion, and an iodide ion. Examples of the alkyl sulfate ion having 1 to 3 carbon atoms include a methyl sulfate ion, an ethyl sulfate ion, and a propyl sulfate ion.

 一般式(d2)において、R5dは、炭素数8以上18以下の脂肪族炭化水素基である。R5dの炭素数は、抗菌性能の観点から、好ましくは8以上、より好ましくは10以上、更に好ましくは12以上、そして、好ましくは18以下、より好ましくは16以下である。R5dは、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。 In general formula (d2), R 5d is an aliphatic hydrocarbon group having from 8 to 18 carbon atoms. From the viewpoint of antibacterial performance, the number of carbon atoms in R 5d is preferably 8 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less. R 5d is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.

 一般式(d2)において、R6d及びR7dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基である。R6d及びR7dは、それぞれ独立に、炭素数1以上3以下のアルキル基から選ばれる基であることが好ましい。炭素数1以上3以下のアルキル基としては、メチル基、エチル基、プロピル基が挙げられる。炭素数1以上3以下のヒドロキシアルキル基としては、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基が挙げられる。 In general formula (d2), R 6d and R 7d 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. It is preferable that R 6d and R 7d are each independently a group selected from an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the hydroxyalkyl group having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

 一般式(d2)において、Xは陰イオンである。陰イオンとしては、ハロゲンイオン、及び炭素数1以上3以下のアルキル硫酸イオンから選ばれる1種以上の陰イオンが挙げられる。ハロゲンイオンとしては、例えば塩化物イオン、臭化物イオン及びヨウ化物イオンが挙げられる。また、炭素数1以上3以下のアルキル硫酸イオンとしては、例えばメチル硫酸イオン、エチル硫酸イオン及びプロピル硫酸イオンが挙げられる。 In general formula (d2), X- is an anion. Examples of the anion include one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms. Examples of the halogen ion include a chloride ion, a bromide ion, and an iodide ion. Examples of the alkyl sulfate ion having 1 to 3 carbon atoms include a methyl sulfate ion, an ethyl sulfate ion, and a propyl sulfate ion.

 一般式(d2)の化合物の具体例としては、N-ドデシル-N,N-ジメチル-N-ベンジルアンモニウム塩、N-トリデシル-N,N-ジメチル-N-ベンジルアンモニウム塩、N-テトラデシル-N,N-ジメチル-N-ベンジルアンモニウム塩、N-ペンタデシル-N,N-ジメチル-N-ベンジルアンモニウム塩、N-ヘキサデシル-N,N-ジメチル-N-ベンジルアンモニウム塩、N-ドデシル-N,N-ジエチル-N-ベンジルアンモニウム塩、N-トリデシル-N,N-ジエチル-N-ベンジルアンモニウム塩、N-テトラデシル-N,N-ジエチル-N-ベンジルアンモニウム塩、N-ペンタデシル-N,N-ジエチル-N-ベンジルアンモニウム塩、N-ヘキサデシル-N,N-ジエチル-N-ベンジルアンモニウム塩、N-ドデシル-N-メチル-N-エチル-N-ベンジルアンモニウム塩、N-トリデシル-N-メチル-N-エチル-N-ベンジルアンモニウム塩、N-テトラデシル-N-メチル-N-エチル-N-ベンジルアンモニウム塩、N-ペンタデシル-N-メチル-N-エチル-N-ベンジルアンモニウム塩、及びN-ヘキサデシル-N-メチル-N-エチル-N-ベンジルアンモニウム塩から選ばれる1種以上の化合物が挙げられる。 Specific examples of the compound of general formula (d2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetra ... The examples include one or more compounds selected from the group consisting of ammonium salts, N-pentadecyl-N,N-diethyl-N-benzyl ammonium salts, N-hexadecyl-N,N-diethyl-N-benzyl ammonium salts, N-dodecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-tridecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-tetradecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, N-pentadecyl-N-methyl-N-ethyl-N-benzyl ammonium salts, and N-hexadecyl-N-methyl-N-ethyl-N-benzyl ammonium salts.

 (D)成分は、塩化ベンザルコニウム及びアルキルトリメチルアンモニウムクロライドから選ばれる1種以上が好ましい。塩化ベンザルコニウムとしては、前記一般式(d2)で表される化合物が好ましい。また、アルキルトリメチルアンモニウムクロライドは、前記一般式(d1)で表される化合物が好ましい。 The component (D) is preferably one or more selected from benzalkonium chloride and alkyltrimethylammonium chloride. The benzalkonium chloride is preferably a compound represented by the general formula (d2) above. The alkyltrimethylammonium chloride is preferably a compound represented by the general formula (d1) above.

<(E)成分>
 (E)成分は、アニオン性ポリマーである。(E)成分としては、カルボン酸基又はその塩を有し、重量平均分子量が3,000以上のポリマーが挙げられる。
 (E)成分としては、ポリアクリル酸及びその塩、アクリル酸とマレイン酸のコポリマー及びその塩、並びにポリマレイン酸及びその塩から選ばれる1種以上のポリマー(以下、(E1)成分という)が挙げられる。
 ポリアクリル酸及びその塩としては、ポリアクリル酸、ポリアクリル酸ナトリウム、及びポリアクリル酸カリウム等から選ばれる1種以上が挙げられ、好ましくはポリアクリル酸ナトリウム、及びポリアクリル酸カリウムから選ばれる1種以上が挙げられる。
 アクリル酸とマレイン酸のコポリマー及びその塩としては、アクリル酸とマレイン酸のコポリマー、アクリル酸とマレイン酸のコポリマーのナトリウム塩、及びアクリル酸とマレイン酸のコポリマーのカリウム塩等から選ばれる1種以上が挙げられ、好ましくはアクリル酸とマレイン酸のコポリマーのナトリウム塩、及びアクリル酸とマレイン酸のコポリマーのカリウム塩から選ばれる1種以上が挙げられる。アクリル酸とマレイン酸のコポリマーのモル比は、アクリル酸のモル数/マレイン酸のモル数として、好ましくは1/99以上、より好ましくは10/90以上、そして、好ましくは99/1以下、より好ましくは90/10以下である。
 ポリマレイン酸及びその塩としては、ポリマレイン酸、ポリマレイン酸ナトリウム、及びポリマレイン酸カリウム等から選ばれる1種以上が挙げられ、好ましくはポリマレイン酸ナトリウム、及びポリマレイン酸カリウムから選ばれる1種以上が挙げられる。
<Component (E)>
The component (E) is an anionic polymer. Examples of the component (E) include a polymer having a carboxylic acid group or a salt thereof and having a weight average molecular weight of 3,000 or more.
Examples of the component (E) include one or more polymers selected from polyacrylic acid and its salts, copolymers of acrylic acid and maleic acid and their salts, and polymaleic acid and its salts (hereinafter referred to as component (E1)).
The polyacrylic acid and salts thereof include at least one selected from polyacrylic acid, sodium polyacrylate, potassium polyacrylate, and the like, and preferably at least one selected from sodium polyacrylate and potassium polyacrylate.
The copolymer of acrylic acid and maleic acid and its salt may be one or more selected from the copolymer of acrylic acid and maleic acid, the sodium salt of the copolymer of acrylic acid and maleic acid, and the potassium salt of the copolymer of acrylic acid and maleic acid, and preferably one or more selected from the sodium salt of the copolymer of acrylic acid and maleic acid and the potassium salt of the copolymer of acrylic acid and maleic acid. The molar ratio of the copolymer of acrylic acid and maleic acid, in terms of the mole number of acrylic acid/the mole number of maleic acid, is preferably 1/99 or more, more preferably 10/90 or more, and preferably 99/1 or less, more preferably 90/10 or less.
The polymaleic acid and salts thereof include at least one selected from polymaleic acid, sodium polymaleate, potassium polymaleate, and the like, and preferably at least one selected from sodium polymaleate and potassium polymaleate.

 (E1)成分は、本発明の効果の発現を妨げない程度であれば、アクリル酸及びマレイン酸以外のモノマーであって、アクリル酸及び/又はマレイン酸と共重合可能なモノマーを含んだコポリマーであってもよい。アクリル酸及びマレイン酸以外のモノマーであって、アクリル酸及び/又はマレイン酸と共重合可能なモノマーとしては、ビニル系モノマー、アクリル系モノマー、及びスチレン系モノマー等から選ばれる1種以上が挙げられ、より具体的にはメタクリル酸、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、及びスチレン等から選ばれる1種以上が挙げられる。アクリル酸及びマレイン酸以外のモノマーであって、アクリル酸及び/又はマレイン酸と共重合可能なモノマーの(E1)成分中のモル比は、(E1)成分中に、好ましくは0モル%以上、そして、好ましくは5モル%以下、より好ましくは3モル%以下であり、0モル%であることが更に好ましい。従って、本発明のポリアクリル酸及びその塩、アクリル酸とマレイン酸のコポリマー及びその塩は、及びポリマレイン酸及びその塩は、全構成モノマー中、アクリル酸及びマレイン酸以外のモノマーであって、アクリル酸及び/又はマレイン酸と共重合可能なモノマーを、0モル%以上5モル%以下の範囲で含むポリマー又はコポリマーであってよい。 The (E1) component may be a copolymer containing a monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid, so long as it does not interfere with the manifestation of the effects of the present invention. Examples of the monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid include one or more selected from vinyl monomers, acrylic monomers, and styrene monomers, and more specifically, one or more selected from methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene. The molar ratio of the monomer other than acrylic acid and maleic acid that is copolymerizable with acrylic acid and/or maleic acid in the (E1) component is preferably 0 mol% or more, and preferably 5 mol% or less, more preferably 3 mol% or less, and even more preferably 0 mol%. Therefore, the polyacrylic acid and its salts, the copolymer of acrylic acid and maleic acid and its salts, and the polymaleic acid and its salts of the present invention may be polymers or copolymers that contain, among all constituent monomers, monomers other than acrylic acid and maleic acid that are copolymerizable with acrylic acid and/or maleic acid in the range of 0 mol % to 5 mol %.

 (E)成分の重量平均分子量は、好ましくは3,000以上、より好ましくは3,500以上、更に好ましくは4,000以上、より更に好ましくは5,000以上、より更に好ましくは6,000以上、より更に好ましくは7,000以上、より更に好ましくは8,000以上、より更に好ましくは9,000以上、より更に好ましくは10,000以上、そして、好ましくは100,000以下、より好ましくは50,000以下、更に好ましくは25,000以下、より更に好ましくは15,000以下である。
この重量平均分子量は、下記の重量平均分子量の測定方法に従って測定することができる。
<重量平均分子量の測定方法>
(E)成分の重量平均分子量は、GPC(ゲル浸透クロマトグラフィー)により測定を行い、換算標準物質により重量平均分子量(Mw)を求めることができる。
以下に、GPCの測定条件を示す。
・カラム:東ソー(株)製、商品名:TSK-GEL guard PWXL
東ソー(株)製、商品名:TSK-GEL G4000 PWXL
東ソー(株)製、商品名:TSK-GEL G2500 PWXL
・移動相:0.1mol/Lリン酸二水素カリウム及び0.1mol/Lリン酸二水素ナトリウムの水溶液/アセトニトリル=90/10(体積比)
・検出器:示差屈折率検出器
・カラム温度:40℃
・流速:1.0mL/min
・換算標準物質:ポリアクリル酸〔アメリカン・スタンダード・コーポレーション(AMERICANSTANDARDCORP)社製〕
・試料:固形分0.8gを含む重合体水溶液にイオン交換水を添加し、総液量が200mLとなるように調製し、この調製液から10μLを分取してカラムに注入する。
The weight average molecular weight of component (E) is preferably 3,000 or more, more preferably 3,500 or more, even more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, still more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 25,000 or less, and still more preferably 15,000 or less.
The weight average molecular weight can be measured according to the following method for measuring weight average molecular weight.
<Method for measuring weight average molecular weight>
The weight average molecular weight of component (E) can be measured by GPC (gel permeation chromatography), and the weight average molecular weight (Mw) can be determined using a conversion standard substance.
The GPC measurement conditions are as follows.
Column: Tosoh Corporation, product name: TSK-GEL guard PWXL
Manufactured by Tosoh Corporation, Product name: TSK-GEL G4000 PWXL
Manufactured by Tosoh Corporation, Product name: TSK-GEL G2500 PWXL
Mobile phase: 0.1 mol/L aqueous solution of potassium dihydrogen phosphate and 0.1 mol/L sodium dihydrogen phosphate/acetonitrile = 90/10 (volume ratio)
Detector: Differential refractive index detector Column temperature: 40°C
・Flow rate: 1.0mL/min
Conversion standard material: Polyacrylic acid (American Standard Corporation)
Sample: Ion-exchanged water is added to an aqueous polymer solution containing 0.8 g of solids to prepare a total liquid volume of 200 mL, and 10 μL of this prepared solution is dispensed and injected into the column.

<組成等>
 本発明の洗浄剤組成物は、(A)成分を、洗浄力の観点から、前記洗浄剤組成物中、5質量%以上、好ましくは7質量%以上、より好ましくは9質量%以上、更に好ましくは11質量%以上、そして、すすぎ性の観点から、40質量%以下、好ましくは30質量%以下、より好ましくは25質量%以下、更に好ましくは20質量%以下含有する。なお、本発明において(A)成分として(a2)成分を含む場合、(a2)成分の質量は、ナトリウム塩に換算した値を用いるものとする。
<Composition, etc.>
The cleaning composition of the present invention contains the component (A) in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and even more preferably 11% by mass or more in terms of detergency, and 40% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less in terms of rinsing ability. When the present invention contains the component (a2) as the component (A), the mass of the component (a2) is expressed as a value converted into a sodium salt.

 本発明の洗浄剤組成物中、(a2)成分の含有量と、(a1)成分と(a2)成分の合計含有量との質量比(a2)/[(a1)+(a2)]は、洗浄性能の観点から、0以上、好ましくは0.05以上、より好ましくは0.10以上、更に好ましくは0.15以上、そして、すすぎ性能、及び抗菌性能の観点から、0.5以下、好ましくは0.45以下、より好ましくは0.40以下、更に好ましくは0.35以下である。 In the detergent composition of the present invention, the mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more, preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0.15 or more, from the viewpoint of cleaning performance, and is 0.5 or less, preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.35 or less, from the viewpoint of rinsing performance and antibacterial performance.

 本発明の洗浄剤組成物は、(B)成分を、洗浄性能の観点から、前記洗浄剤組成物中、20質量%以上、好ましくは25質量%以上、より好ましくは30質量%以上、更に好ましくは40質量%以上、そして、溶け残りの抑制の観点から、80質量%以下、好ましくは70質量%以下、より好ましくは65質量%以下、更に好ましくは60質量%以下、より更に好ましくは55質量%以下含有する。 The detergent composition of the present invention contains component (B) in an amount of 20% by mass or more, preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more in terms of cleaning performance, and 80% by mass or less, preferably 70% by mass or less, more preferably 65% by mass or less, even more preferably 60% by mass or less, and even more preferably 55% by mass or less in terms of suppressing residual dissolution.

 本発明の洗浄剤組成物中、(b2)成分の含有量と、(b1)成分と(b2)成分の合計含有量との質量比(b2)/[(b1)+(b2)]は、溶け残りの抑制、及び抗菌性能の観点から、0.2以上、好ましくは0.30以上、より好ましくは0.35以上、更に好ましくは0.40以上、そして、洗浄性能、及び抗菌性能の観点から、0.8以下、好ましくは0.7以下、より好ましくは0.65以下、更に好ましくは0.60以下、より更に好ましくは0.55以下、より更に好ましくは0.50以下である。 In the cleaning composition of the present invention, the mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) components is 0.2 or more, preferably 0.30 or more, more preferably 0.35 or more, and even more preferably 0.40 or more, from the viewpoints of suppressing residual dissolution and antibacterial performance, and is 0.8 or less, preferably 0.7 or less, more preferably 0.65 or less, even more preferably 0.60 or less, even more preferably 0.55 or less, and even more preferably 0.50 or less, from the viewpoints of cleaning performance and antibacterial performance.

 本発明の洗浄剤組成物は、(C)成分を、溶け残りの抑制の観点から、前記洗浄剤組成物中、5質量%以上、好ましくは10質量%以上、より好ましくは15質量%以上、更に好ましくは20質量%以上、より更に好ましくは25質量%以上、そして、スジ残りの生成抑制の観点から、40質量%以下、好ましくは35質量%以下、より好ましくは32.5質量%以下、更に好ましくは30質量%以下含有する。 The detergent composition of the present invention contains component (C) in an amount of 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, in terms of suppressing residual dissolution, and 40% by mass or less, preferably 35% by mass or less, more preferably 32.5% by mass or less, and even more preferably 30% by mass or less, in terms of suppressing formation of residual streaks.

 本発明の洗浄剤組成物中、(C)成分の含有量と、(B)成分と(C)成分の合計含有量との質量比(C)/[(B)+(C)]は、溶け残りの抑制の観点から、0を超え、好ましくは0.05以上、より好ましくは0.1以上、更に好ましくは0.15以上、より更に好ましくは0.20以上、より更に好ましくは0.25以上、より更に好ましくは0.30以上、そして、スジ残りの生成抑制の観点から、0.50以下、好ましくは0.45以下、より好ましくは0.40以下、更に好ましくは0.38以下である。 In the cleaning composition of the present invention, the mass ratio (C)/[(B)+(C)] of the content of the (C) component to the total content of the (B) component and the (C) component is greater than 0, preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.15 or more, even more preferably 0.20 or more, even more preferably 0.25 or more, even more preferably 0.30 or more, from the viewpoint of suppressing the formation of residual streaks, and is 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less, even more preferably 0.38 or less.

 本発明の洗浄剤組成物は、(D)成分を、抗菌性能の観点から、前記洗浄剤組成物中、0.1質量%以上、好ましくは0.5質量%以上、より好ましくは0.7質量%以上、更に好ましくは1.0質量%以上、より更に好ましくは2.0質量%以上、そして、その上限は特に限定するものではないが、例えば5.0質量%以下、更には4.0質量%以下、更には3.5質量%以下、更には3.0質量%以下含有する。 From the viewpoint of antibacterial performance, the detergent composition of the present invention contains component (D) in an amount of 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, even more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more, and the upper limit is not particularly limited, but may be, for example, 5.0% by mass or less, further 4.0% by mass or less, further 3.5% by mass or less, and further 3.0% by mass or less.

 本発明の洗浄剤組成物は、(E)成分を、粒子汚れの洗浄性能の観点から、前記洗浄剤組成物中、0.1質量%以上、好ましくは1.0質量%以上、より好ましくは2.0質量%以上、更に好ましくは3.0質量%以上、より更に好ましくは4.0質量%以上、そして、10質量%以下、好ましくは8.0質量%以下、より好ましくは6.0質量%以下、更に好ましくは5.0質量%以下含有する。 From the viewpoint of cleaning performance against particulate soils, the detergent composition of the present invention contains component (E) in an amount of 0.1% by mass or more, preferably 1.0% by mass or more, more preferably 2.0% by mass or more, even more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, and 10% by mass or less, preferably 8.0% by mass or less, more preferably 6.0% by mass or less, even more preferably 5.0% by mass or less.

 本発明の洗浄剤組成物において、前記洗浄剤組成物中に含まれる界面活性剤の合計含有量に対する、(A)成分の含有量の割合(A)/(界面活性剤の合計含有量)は、洗浄性能の観点から、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上、より更に好ましくは80質量%以上、そして、抗菌性能の観点から、好ましくは98質量%以下、より好ましくは96質量%以下、更に好ましくは94質量%以下である。洗浄剤組成物に含まれる界面活性剤の合計は、(A)成分、(D)成分及び下記(F)成分の合計含有量であってよい。 In the cleaning composition of the present invention, the ratio of the content of component (A) to the total content of surfactants contained in the cleaning composition, (A)/(total content of surfactants), is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, and even more preferably 80 mass% or more, from the viewpoint of cleaning performance, and is preferably 98 mass% or less, more preferably 96 mass% or less, and even more preferably 94 mass% or less, from the viewpoint of antibacterial performance. The total surfactants contained in the cleaning composition may be the total content of component (A), component (D), and the following component (F).

<(F)成分>
 本発明の洗浄剤組成物は、洗浄や泡立ち抑制の観点から、(F)成分として、(A)成分及び(D)成分以外の界面活性剤を任意に含有することができる。
 (A)成分及び(D)成分以外の界面活性剤としては、両性界面活性剤から選ばれる1種以上が挙げられる。
<Component (F)>
From the viewpoint of cleaning ability and foaming inhibition, the cleaning composition of the present invention may contain, as component (F), any surfactant other than components (A) and (D).
The surfactant other than the components (A) and (D) may be one or more selected from amphoteric surfactants.

 両性界面活性剤としては、N-アルカノイルアミノプロピル-N,N-ジメチルアミンオキシド、N-アルキル-N,N-ジメチルアミンオキシド、N-アルカノイルアミノプロピル-N,N-ジメチル-N-カルボキシメチルアンモニウムベタイン、N-アルキル-N,N-ジメチル-N-カルボキシメチルアンモニウムベタイン、N-アルキル-N,N-ジメチル-N-スルホプロピルアンモニウムスルホベタイン、N-アルキル-N,N-ジメチル-N-(2-ヒドロキシスルホプロピル)アンモニウムスルホベタイン、N-アルカノイルアミノプロピル-N,N-ジメチル-N-スルホプロピルアンモニウムスルホベタイン、及びN-アルカノイルアミノプロピル-N,N-ジメチル-N-(2-ヒドロキシスルホプロピル)アンモニウムスルホベタインから選ばれる1種以上を挙げることができる。これらにおいて、アルカノイル基は、例えばラウロイル又はミリスチロイルである。また、これらにおいて、アルキル基は、例えばラウリル基又はミリスチル基である。 The amphoteric surfactant may be one or more selected from N-alkanoylaminopropyl-N,N-dimethylamine oxide, N-alkyl-N,N-dimethylamine oxide, N-alkanoylaminopropyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine, N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine. In these, the alkanoyl group is, for example, lauroyl or myristyl. In these, the alkyl group is, for example, a lauryl group or a myristyl group.

 本発明の洗浄剤組成物が(F)成分を含有する場合、本発明の洗浄剤組成物は、(F)成分を、洗浄性能及び泡立ちの観点から、前記洗浄剤組成物中、好ましくは0.1質量%以上、より好ましくは0.2質量%以上、更に好ましくは0.3質量%以上、そして、好ましくは2質量%以下、より好ましくは1.5質量%以下、更に好ましくは1.2質量%以下含有する。 When the cleaning composition of the present invention contains component (F), the cleaning composition of the present invention contains component (F) in an amount of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 2% by mass or less, more preferably 1.5% by mass or less, even more preferably 1.2% by mass or less, in terms of cleaning performance and foaming.

<(G)成分>
 本発明の洗浄剤組成物は、(G)成分として、重量平均分子量が100以上100,000以下のポリアルキレングリコールを任意に含有することができる。
 (G)成分としては、ポリエチレングリコール及びポリプロピレングリコールから選ばれる1種以上が挙げられる。
 (G)成分の重量平均分子量は、100以上、好ましくは1,000以上、より好ましくは5,000以上、そして、100,000以下、好ましくは30,000以下、より好ましくは20,000以下、更に好ましくは15,000以下である。
 ここで重量平均分子量はゲルパーミエーションクロマトグラフィーでポリスチレンを標準物質として求めた値である。
<Component (G)>
The cleaning composition of the present invention may optionally contain, as the component (G), a polyalkylene glycol having a weight average molecular weight of 100 or more and 100,000 or less.
The component (G) may be one or more selected from polyethylene glycol and polypropylene glycol.
The weight average molecular weight of component (G) is 100 or more, preferably 1,000 or more, more preferably 5,000 or more, and 100,000 or less, preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
The weight average molecular weight herein is a value determined by gel permeation chromatography using polystyrene as a standard substance.

 本発明の洗浄剤組成物は、(G)成分を含有する場合、(G)成分を、安定性の観点から、前記洗浄剤組成物中、好ましくは0.001質量%以上、より好ましくは0.01質量%以上、更に好ましくは0.1質量%以上、より更に好ましくは0.2質量%以上、そして、好ましくは5質量%以下、より好ましくは4質量%以下、更に好ましくは3質量%以下、より更に好ましくは2質量%以下、より更に好ましくは1質量%以下含有する。 When the cleaning composition of the present invention contains component (G), from the viewpoint of stability, the cleaning composition contains component (G) in an amount of preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, still more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, still more preferably 2% by mass or less, and still more preferably 1% by mass or less.

<(H)成分>
 本発明の洗浄剤組成物は、(H)成分として、任意に、プロテアーゼ、リパーゼ及びアミラーゼから選ばれる1種以上の酵素を含むことができる。
 プロテアーゼは、例えば、セリンプロテアーゼ(EC3.4.21)やメタロプロテアーゼ(EC3.4.17又はEC3.4.24)などが挙げられる。好適なプロテアーゼの例としては、サブチリシン(EC3.4.21.62)などの中性又はアルカリ性セリンプロテアーゼがある。
 リパーゼは、例えば、トリアシルグリセロールリパーゼ(EC3.1.1.3)、ホスホリパーゼA2(EC3.1.1.4)、リゾホスホリパーゼ(EC3.1.1.5)、モノグリセリドリパーゼ(EC3.1.1.23)、ガラクトリパーゼ(EC3.1.1.26)、ホスホリパーゼA1(EC3.1.1.32)、リポタンパク質リパーゼ(EC3.1.1.34)などが挙げられる。
 アミラーゼは、例えば、α-アミラーゼ(EC3.2.1.1)、β-アミラーゼ(EC3.2.1.2)及び/又はグルコアミラーゼ(EC3.2.1.3)などが挙げられる。好適なアミラーゼの例としては中性又はアルカリ性α-アミラーゼがあり、細菌や真菌などの微生物起源のものが好ましい。
<Component (H)>
The cleaning composition of the present invention may optionally contain, as component (H), one or more enzymes selected from proteases, lipases and amylases.
Proteases include, for example, serine proteases (EC 3.4.21) and metalloproteases (EC 3.4.17 or EC 3.4.24). Examples of suitable proteases include neutral or alkaline serine proteases such as subtilisin (EC 3.4.21.62).
Examples of lipases include 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), and lipoprotein lipase (EC 3.1.1.34).
Examples of amylases 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 of microbial origin, such as bacteria or fungi.

 本発明の洗浄剤組成物が(H)成分を含有する場合、本発明の洗浄剤組成物は、(H)成分を、洗浄性能の観点から、前記洗浄剤組成物中、酵素タンパク質量として、好ましくは0.002質量%以上、より好ましくは0.004質量%以上、更に好ましくは0.008質量%以上、そして、好ましくは0.12質量%以下、より好ましくは0.1質量%以下、更に好ましくは0.08質量%以下、より更に好ましくは0.04質量%以下含有する。
 本発明において、(H)成分の質量に関する規定は、酵素タンパク質の量として算出するものとする。
  なお、(H)成分について、酵素たんぱく質の定量法は、例えば、ナカライテクス株式会社製のプロテインアッセイキット  Lowryキットを用い、取り扱い説明書に準拠した方法を採用できる。
When the detergent composition of the present invention contains component (H), the detergent composition of the present invention contains component (H) in an amount, in terms of cleaning performance, of preferably 0.002 mass % or more, more preferably 0.004 mass % or more, even more preferably 0.008 mass % or more, and preferably 0.12 mass % or less, more preferably 0.1 mass % or less, even more preferably 0.08 mass % or less, and still more preferably 0.04 mass % or less, in terms of the amount of enzyme protein in the detergent composition.
In the present invention, the mass of the component (H) is calculated as the amount of enzyme protein.
Regarding the component (H), the enzyme protein can be quantified, for example, using a protein assay kit, Lowry kit, manufactured by Nacalai Tesque, Inc., in accordance with the instruction manual.

<(I)キレート剤>
 本発明の洗浄剤組成物は、任意に(I)キレート剤〔以下、(I)成分という〕を含有することができる。
 (I)成分の具体例として、例えば、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、ヒドロキシエチルイミノ二酢酸等のアミノポリ酢酸又はこれらの塩、クエン酸、乳酸、酒石酸、リンゴ酸等の有機酸又はこれらの塩、1-ヒドロキシエチリデン-1,1-ジホスホン酸、ジエチレントリアミンペンタ(メチレンホスホン酸)、これらのアルカリ金属又は低級アミン塩等が挙げられ、これらは1種以上を用いることができる。
 (I)成分の塩は、ナトリウム塩、カリウム塩等のアルカリ金属塩、モノエタールアミン、ジエタノールアミン、トリエタノールアミン等の低級アミン塩等が挙げられる。
<(I) Chelating Agent>
The cleaning composition of the present invention may optionally contain (I) a chelating agent (hereinafter referred to as "component (I)").
Specific examples of the component (I) include aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or salts thereof; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or salts thereof; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof; and these can be used in combination with one or more of them.
Examples of salts of component (I) include alkali metal salts such as sodium salts and potassium salts, and salts with lower amines such as monoethanolamine, diethanolamine and triethanolamine.

 本発明の洗浄剤組成物が(I)成分を含有する場合、本発明の洗浄剤組成物は、(I)成分を、洗浄性能の観点から、前記洗浄剤組成物中、好ましくは0.5質量%以上、より好ましくは1.0質量%以上、更に好ましくは2.0質量%以上、そして、製剤化の観点から、好ましくは10質量%以下、より好ましくは8質量%以下、更に好ましくは6質量%以下含有する。 When the detergent composition of the present invention contains component (I), the detergent composition of the present invention contains component (I) in an amount of preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and even more preferably 2.0% by mass or more in terms of cleaning performance, and preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less in terms of formulation.

 本発明の洗浄剤組成物は、水を含有することができる。水は、イオン交換水、精製水、蒸留水が挙げられる。水は、(A)成分~(I)成分及び任意成分以外の残部として用いられる。水には、洗浄剤組成物の配合成分を投入するために用いられる水も含まれる。 The cleaning composition of the present invention may contain water. Examples of water include ion-exchanged water, purified water, and distilled water. Water is used as the remainder other than components (A) to (I) and any optional components. Water also includes water used to add the components of the cleaning composition.

 本発明の洗浄剤組成物は、その他の成分として、衣料用洗剤の分野で公知の他の成分、例えば漂白剤(漂白活性化剤等)、再汚染防止剤、有機系の還元剤、蛍光増白剤、抑泡剤(シリコーン等)、有機溶剤、香料、着色剤、抗菌剤(例えば、トリクロサン等)等の成分〔但し、(A)成分~(I)成分に該当するものは除く〕を任意に含有することができる。 The cleaning composition of the present invention may optionally contain other components known in the field of laundry detergents, such as bleaching agents (such as bleach activators), anti-redeposition agents, organic reducing agents, fluorescent brightening agents, foam inhibitors (such as silicones), organic solvents, fragrances, colorants, antibacterial agents (such as triclosan), etc. (excluding those that fall under components (A) to (I)).

 本発明の洗浄剤組成物は、固体洗浄剤組成物であってよい。本発明の洗浄剤組成物は、錠剤、粉末状、粒状、顆粒状又はペースト状であってよい。溶解性の観点から、本発明の洗浄剤組成物は、錠剤、粉末状、粒状、顆粒状及びペースト状から選ばれる洗浄剤組成物が好ましく、より好ましくは錠剤、粉末状及びペースト状から選ばれる洗浄剤組成物である。本発明の洗浄剤組成物は、粉末洗浄剤組成物であってよい。 The cleaning composition of the present invention may be a solid cleaning composition. The cleaning composition of the present invention may be in the form of a tablet, powder, granule, granules, or paste. From the viewpoint of solubility, the cleaning composition of the present invention is preferably a cleaning composition selected from a tablet, powder, granule, granule, and paste, and more preferably a cleaning composition selected from a tablet, powder, and paste. The cleaning composition of the present invention may be a powder cleaning composition.

 本発明の洗浄剤組成物は、公知の方法で製造することができる。例えば、噴霧乾燥法、ドライ中和法、乾燥造粒法、ドライブレンド法、流動層乾燥法、薄膜乾燥法、押出し造粒法、転動造粒法、撹拌造粒法、圧密造粒法、界面活性剤担持法又はこれらから選択して組み合わせた方法を適用して、製造することができる。 The cleaning composition of the present invention can be produced by a known method. For example, it can be produced by applying a spray drying method, a dry neutralization method, a dry granulation method, a dry blend method, a fluidized bed drying method, a thin film drying method, an extrusion granulation method, a rolling granulation method, a stirring granulation method, a compaction granulation method, a surfactant carrying method, or a combination of methods selected from these.

 本発明の洗浄剤組成物の嵩密度は、製造方法によっても異なるが、好ましくは0.2g/cm以上、より好ましくは0.3g/cm以上、更に好ましくは0.35g/cm以上、そして、好ましくは1g/cm以下、より好ましくは0.95g/cm以下、更に好ましくは0.9g/cm以下である。 The bulk density of the cleaning composition of the present invention will vary depending on the production method, but is preferably 0.2 g/ cm3 or more, more preferably 0.3 g/ cm3 or more, even more preferably 0.35 g/ cm3 or more, and is preferably 1 g/ cm3 or less, more preferably 0.95 g/ cm3 or less, even more preferably 0.9 g/ cm3 or less.

 本発明の洗浄剤組成物が粉末洗浄剤組成物である場合、本発明の洗浄剤組成物の平均粒子径は、好ましくは100μm以上、より好ましくは150μm以上、更に好ましくは200μm以上、そして、好ましくは800μm以下、より好ましくは750μm以下、更に好ましくは700μm以下である。
 この平均粒子径は、JIS Z 8801の標準篩を用いて5分間振動させた後、篩目のサイズによる質量分率から求める。
When the cleaning composition of the present invention is a powder cleaning composition, the average particle size of the cleaning composition of the present invention is preferably 100 μm or more, more preferably 150 μm or more, even more preferably 200 μm or more, and preferably 800 μm or less, more preferably 750 μm or less, even more preferably 700 μm or less.
This average particle size is determined by vibrating a standard sieve according to JIS Z 8801 for 5 minutes and then calculating the mass fraction based on the size of the sieve openings.

<洗浄剤物品>
 本発明は、本発明の洗浄剤組成物と、前記洗浄剤組成物を包装する水溶性フィルムと、を備える洗浄剤物品を提供する。換言すれば、本発明は、本発明の洗浄剤組成物と水溶性フィルムからなる洗浄剤物品であって、前記洗浄剤組成物が前記水溶性フィルムに包装されている、洗浄剤物品を提供する。
 本発明の洗浄剤物品は、本発明の洗浄剤組成物を水溶性フィルムで包装してなる、洗浄剤物品であってよい。すなわち、本発明の洗浄剤組成物は、水溶性フィルムで包装されてなる洗浄剤組成物であってよい。
<Cleaning Article>
The present invention provides a cleaning agent article comprising the cleaning agent composition of the present invention and a water-soluble film for packaging the cleaning agent composition. In other words, the present invention provides a cleaning agent article comprising the cleaning agent composition of the present invention and a water-soluble film, in which the cleaning agent composition is packaged in the water-soluble film.
The cleaning article of the present invention may be a cleaning article comprising the cleaning composition of the present invention packaged in a water-soluble film. That is, the cleaning composition of the present invention may be a cleaning composition packaged in a water-soluble film.

 本発明において、水溶性フィルムの「水溶性」とは、1リットルのガラスビーカーに500gの30℃のイオン交換水を入れ、直径が8cmのテフロン(登録商標)製の撹拌子を入れ、その中に評価対象のフィルム1gを投入し、100rpmで30分間撹拌した後に、見かけ上、不溶物が見られないものをいう。
 また、水溶性フィルムの厚さは、誤飲防止、溶解性の観点から、好ましくは1μm以上、より好ましくは10μm以上、更に好ましくは50μm以上、そして、好ましくは200μm以下、より好ましくは150μm以下、更に好ましくは100μm以下である。
In the present invention, the term "water-soluble" refers to a water-soluble film in which 500 g of 30° C. ion-exchanged water is placed in a 1-liter glass beaker, a Teflon (registered trademark) stirrer having a diameter of 8 cm is placed in the beaker, 1 g of the film to be evaluated is placed in the beaker, and the film is stirred at 100 rpm for 30 minutes, after which no insoluble matter is apparent.
In addition, from the viewpoints of preventing accidental ingestion and solubility, the thickness of the water-soluble film is preferably 1 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and preferably 200 μm or less, more preferably 150 μm or less, even more preferably 100 μm or less.

 水溶性フィルムは、好ましくはポリマーを含んで構成される。水溶性フィルムは、当該技術分野において既知の方法、例えば、ポリマーの注型成形、吹込み成形、押出成形、射出成形などによって得ることができる。水溶性フィルムを製造するためのポリマーの非限定例として、ポリビニルアルコール(PVA)、ビニルアルコールコポリマー、ポリビニルピロリドン、ポリアルキレンオキシド、(変性)セルロース、(変性)セルロース-エーテル又は-エステル又は-アミド、ポリアクリレートなどのポリカルボン酸及びその塩、マレイン酸/アクリル酸のコポリマー、ポリアミノ酸つまりペプチド、ポリアクリルアミドなどのポリアミド、デンプン及びゼラチンなどの多糖、キサンタン及びカラゴム(carragum)などの天然ゴムが挙げられる。ビニルアルコールコポリマーは、ビニルアルコールと他のモノマー、例えばエチレン、アクリル酸とのコポリマーである。好ましくは、水溶性フィルムは、ポリアクリレート及び水溶性アクリレート、メチルセルロース、カルボキシメチルセルロースナトリウム、デキストリン、エチルセルロース、ヒドロキシエチルセルロース、マルトデキストリン、ポリメタクリレート、ポリビニルアルコール、ビニルアルコールコポリマー、ヒドロキシプロピルメチルセルロース(HPMC)、並びにこれらの組み合わせからなる群から選択されるポリマーを含む。より好ましくは、水溶性フィルムは、ポリビニルアルコール、ビニルアルコールコポリマー及びヒドロキシプロピルメチルセルロースから選ばれるポリマーを含む。更に好ましくは、水溶性フィルムは、ポリビニルアルコール、例えば、株式会社アイセロから入手可能なソルブロンを含む。水溶性フィルムを製造するのに好適なポリマーは、例えば、米国特許第6995126号に記載されている。 The water-soluble film is preferably composed of a polymer. The water-soluble film can be obtained by methods known in the art, such as casting, blow molding, extrusion, injection molding of polymers, etc. Non-limiting examples of polymers for producing water-soluble films include polyvinyl alcohol (PVA), vinyl alcohol copolymers, polyvinylpyrrolidone, polyalkylene oxides, (modified) cellulose, (modified) cellulose-ethers or -esters or -amides, polycarboxylic acids and their salts such as polyacrylates, maleic acid/acrylic acid copolymers, polyamino acids or peptides, polyamides such as polyacrylamides, polysaccharides such as starch and gelatin, natural gums such as xanthan and carragum. Vinyl alcohol copolymers are copolymers of vinyl alcohol with other monomers, such as ethylene, acrylic acid. Preferably, the water-soluble film comprises a polymer selected from the group consisting of polyacrylates and water-soluble acrylates, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, maltodextrin, polymethacrylates, polyvinyl alcohol, vinyl alcohol copolymers, hydroxypropylmethylcellulose (HPMC), and combinations thereof. More preferably, the water-soluble film comprises a polymer selected from polyvinyl alcohol, vinyl alcohol copolymers, and hydroxypropylmethylcellulose. Even more preferably, the water-soluble film comprises polyvinyl alcohol, for example, Solvron available from Aicello Co., Ltd. Suitable polymers for producing water-soluble films are described, for example, in U.S. Pat. No. 6,995,126.

 本発明の洗浄剤物品において、本発明の洗浄剤組成物と接触する水溶性フィルムの総面積は、製品安定性をより高める観点から、好ましくは10cm以上、より好ましくは20cm以上、更に好ましくは30cm以上、より更に好ましくは40cm以上、そして、同じ観点から、好ましくは100cm以下、より好ましくは70cm以下、更に好ましくは60cm以下、より更に好ましくは45cm以下である。 In the detergent article of the present invention, the total area of the water-soluble film in contact with the detergent composition of the present invention is, from the viewpoint of further enhancing product stability, preferably 10 cm2 or more, more preferably 20 cm2 or more, even more preferably 30 cm2 or more, and still more preferably 40 cm2 or more, and from the same viewpoint, preferably 100 cm2 or less, more preferably 70 cm2 or less, even more preferably 60 cm2 or less, and still more preferably 45 cm2 or less.

 本発明の洗浄剤物品は、当該技術分野において既知の任意の好適なプロセス、例えば既知の洗剤パウチの作製プロセスによって作製できる。パウチの作製プロセス例は、米国特許第6,995,126号、同第7,127,874号、同第8,156,713号、同第7,386,971号、同第7,439,215号、及び米国特許出願公開第2009/199877号に記載されている。 The cleaning articles of the present invention can be made by any suitable process known in the art, such as known detergent pouch making processes. Exemplary pouch making processes are described in U.S. Patent Nos. 6,995,126, 7,127,874, 8,156,713, 7,386,971, 7,439,215, and U.S. Patent Application Publication No. 2009/199877.

 本発明の洗浄剤物品は、1個あたりの内容物の量が、好ましくは5g以上、より好ましくは8g以上、更に好ましくは10g以上、そして、好ましくは50g以下、より好ましくは30g以下、更に好ましくは25g以下である。 The amount of contents per cleaning article of the present invention is preferably 5 g or more, more preferably 8 g or more, even more preferably 10 g or more, and preferably 50 g or less, more preferably 30 g or less, even more preferably 25 g or less.

 本発明の洗浄剤物品の1個あたりの好ましい形状、大きさは、例えば四辺形の形状であり、1辺の長さが、好ましくは1cm以上5cm以下、そして、厚みが好ましくは1cm以上5cm以下、より好ましくは1cm以上4cm以下である。また、本発明の洗浄剤物品の1個あたりの質量は、好ましくは5g以上、より好ましくは10g以上、更に好ましくは15g以上、そして、好ましくは50g以下、より好ましくは40g以下、更に好ましくは30g以下である。 The preferred shape and size of each of the cleaning articles of the present invention is, for example, a quadrilateral, with the length of one side preferably being 1 cm or more and 5 cm or less, and the thickness preferably being 1 cm or more and 5 cm or less, more preferably being 1 cm or more and 4 cm or less. The mass of each of the cleaning articles of the present invention is preferably 5 g or more, more preferably 10 g or more, even more preferably 15 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less.

 また、本発明の洗浄剤物品の1個あたりの別の好ましい形状、大きさは、例えば直方体の形状であり、縦の長さが、好ましくは5cm以上20cm以下、横の長さが、好ましくは1cm以上4cm以下、そして、厚みが好ましくは1cm以上5cm以下、より好ましくは1cm以上4cm以下である。また、本発明の洗浄剤物品の1個あたりの質量は、好ましくは5g以上、より好ましくは10g以上、そして、好ましくは50g以下、より好ましくは40g以下、更に好ましくは30g以下、更に好ましくは20g以下である。 Another preferred shape and size of each of the cleaning articles of the present invention is, for example, a rectangular parallelepiped shape, with a vertical length of preferably 5 cm to 20 cm, a horizontal length of preferably 1 cm to 4 cm, and a thickness of preferably 1 cm to 5 cm, more preferably 1 cm to 4 cm. The mass of each of the cleaning articles of the present invention is preferably 5 g or more, more preferably 10 g or more, and preferably 50 g or less, more preferably 40 g or less, even more preferably 30 g or less, even more preferably 20 g or less.

 本発明の洗浄剤物品としては、例えば、本発明の洗浄剤組成物を水溶性フィルムに包装してなる洗浄剤物品であって、前記洗浄剤物品の最大投影面積の長軸径が、30mm以上200mm以下であり、長軸径と、長軸径と直交する短軸径とのアスペクト比(長軸径/短軸径)が、5以上であり、破裂強度が300N以上である、洗浄剤物品が挙げられる。換言すると、本発明の洗浄剤物品は、本発明の洗浄剤組成物と水溶性フィルムからなる洗浄剤物品であって、前記洗浄剤組成物が前記水溶性フィルムに包装されており、前記洗浄剤物品の最大投影面積の長軸径が、30mm以上200mm以下であり、長軸径と、長軸径と直交する短軸径とのアスペクト比(長軸径/短軸径)が、5以上であり、破裂強度が300N以上である、洗浄剤物品であってよい。 The detergent article of the present invention may be, for example, a detergent article in which the detergent composition of the present invention is packaged in a water-soluble film, the major axis diameter of the maximum projected area of the detergent article is 30 mm or more and 200 mm or less, the aspect ratio between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter (major axis diameter/minor axis diameter) is 5 or more, and the burst strength is 300 N or more. In other words, the detergent article of the present invention may be a detergent article consisting of the detergent composition of the present invention and a water-soluble film, the detergent composition is packaged in the water-soluble film, the major axis diameter of the maximum projected area of the detergent article is 30 mm or more and 200 mm or less, the aspect ratio between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter (major axis diameter/minor axis diameter) is 5 or more, and the burst strength is 300 N or more.

 本発明の洗浄剤物品の最大投影面積の長軸径と、長軸径と直交する短軸径とのアスペクト比(長軸径/短軸径)は、洗浄力の低下が抑制できる観点から、好ましくは5以上、より好ましくは6以上、更に好ましくは7以上、より更に好ましくは8以上、そして、使いやすさ及び収納の観点から、好ましくは20以下、より好ましくは16以下、更に好ましくは13以下、より更に好ましくは10以下である。
 本発明の洗浄剤物品の最大投影面積の長軸径は、使いやすさの観点から、好ましくは30mm以上、より好ましくは50mm以上、更に好ましくは80mm以上、そして、好ましくは200mm以下、より好ましくは160mm以下、更に好ましくは120mm以下である。
 本発明の洗浄剤物品の最大投影面積の短軸径は、使いやすさの観点から、好ましくは5mm以上、より好ましくは10mm以上、更に好ましくは12mm以上、より更に好ましくは14mm以上、そして、好ましくは25mm以下、より好ましくは23mm以下、更に好ましくは20mm以下である。
The aspect ratio (major axis diameter/minor axis diameter) of the major axis diameter of the maximum projected area of the detergent article of the present invention to the minor axis diameter perpendicular to the major axis diameter is preferably 5 or more, more preferably 6 or more, even more preferably 7 or more, and still more preferably 8 or more, from the viewpoint of suppressing a decrease in detergency, and is preferably 20 or less, more preferably 16 or less, even more preferably 13 or less, and still more preferably 10 or less, from the viewpoints of ease of use and storage.
From the viewpoint of ease of use, the major axis diameter of the maximum projected area of the cleaning article of the present invention is preferably 30 mm or more, more preferably 50 mm or more, even more preferably 80 mm or more, and preferably 200 mm or less, more preferably 160 mm or less, even more preferably 120 mm or less.
From the viewpoint of ease of use, the minor axis diameter of the maximum projected area of the cleaning article of the present invention is preferably 5 mm or more, more preferably 10 mm or more, even more preferably 12 mm or more, still more preferably 14 mm or more, and is preferably 25 mm or less, more preferably 23 mm or less, and even more preferably 20 mm or less.

 本発明において、最大投影面積とは、あらゆる面から洗浄剤物品を水平方向に投影したときの投影図において、水平投影面積が最大になる投影図の面積である。「投影」とは数学において用いられる「投影」と同義であり、すなわち物体に水平方向に平行光線をあてて、その影を平面上に写すことである。
 また本発明において、洗浄剤物品の最大投影面積の長軸径と短軸径の測定方法は、洗浄剤物品の最大投影面積の形状が楕円形である場合、そのまま長軸径と短軸径を測定する。また洗浄剤物品の最大投影面積の形状が矩形である場合(縦軸の長さ>横軸の長さ)、縦軸の長さを長軸径、横軸の長さを短軸径として測定する。また洗浄剤物品の最大投影面積の形状が不定形である場合、最長部分を長軸径とし、前記長軸径と直交する線(軸)の最長部分を短軸径として測定する。
 洗浄剤物品の最大投影面積には、洗浄剤組成物を包装する水溶性フィルムを含み、シール部分のような水溶性フィルム同士が重なる部分も含む。
 例えば、2枚の水溶性フィルムを張り合わせて洗浄剤組成物を該水溶性フィルムで包装する場合、水溶性フィルムが洗浄剤組成物と接触する面積は大きいほど好ましい。2枚の水溶性フィルムを張り合わせて洗浄剤組成物を該水溶性フィルムで包装する場合、水溶性フィルム1枚あたり、他の水溶性フィルムと対向する面の総面積に対する該水溶性フィルムの洗浄剤組成物と接触する面積の割合は、好ましくは60%以上、より好ましくは70%以上、更に好ましくは80%以上、更により好ましくは90%以上、そして、100%未満である。本明細書において、水溶性フィルムが洗浄剤組成物と接触する面積は、洗浄剤組成物を収容する空間を形成する水溶性フィルム面の面積であってよい。
 また、洗浄剤物品は、洗浄剤組成物を包装する水溶性フィルムの端部が、他の洗浄剤組成物を包装する水溶性フィルムの端部と切り離し可能な状態で、接続されていてもよい。このような場合、洗浄剤物品の最大投影面積の長軸径と、長軸径と直交する短軸径とのアスペクト比(長軸径/短軸径)は、洗浄剤組成物を包装する水溶性フィルム毎に、洗浄剤物品の最大投影面積を算出して、算出された最大投影面積に基づいて測定される。すなわち、洗浄剤組成物を包装する水溶性フィルムの端部同士が切り離し可能な状態で接続されている洗浄剤物品の場合、前記のアスペクト比は、洗浄剤組成物を包装する水溶性フィルムの接続部分を切り離して測定する。なお、この接続部分が不明の場合は、包装された洗浄剤組成物毎に等分する線を接続部分とみなすことができる。
In the present invention, the maximum projected area is the area of the projection that has the maximum horizontal projected area when the cleaning article is projected horizontally from all sides. "Projection" is the same as "projection" used in mathematics, that is, it means projecting a parallel light beam horizontally onto an object and projecting the shadow onto a flat surface.
In the present invention, the method for measuring the major axis diameter and minor axis diameter of the maximum projected area of the detergent article is as follows: when the shape of the maximum projected area of the detergent article is elliptical, the major axis diameter and minor axis diameter are measured as they are. When the shape of the maximum projected area of the detergent article is rectangular (length of vertical axis > length of horizontal axis), the length of the vertical axis is measured as the major axis diameter and the length of the horizontal axis is measured as the minor axis diameter. When the shape of the maximum projected area of the detergent article is irregular, the longest part is measured as the major axis diameter, and the longest part of the line (axis) perpendicular to the major axis diameter is measured as the minor axis diameter.
The maximum projected area of the cleaning article includes the water-soluble film that packages the cleaning composition, and also includes overlapping portions of the water-soluble films, such as sealed portions.
For example, when two water-soluble films are laminated together to package a detergent composition with the water-soluble film, the larger the contact area of the water-soluble film with the detergent composition, the more preferable. When two water-soluble films are laminated together to package a detergent composition with the water-soluble film, the ratio of the contact area of the water-soluble film with the detergent composition to the total area of the surface facing the other water-soluble film per water-soluble film is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 90% or more, and less than 100%. In this specification, the contact area of the water-soluble film with the detergent composition may be the area of the water-soluble film surface that forms the space for accommodating the detergent composition.
In addition, the detergent article may have an end of a water-soluble film packaging a detergent composition connected in a detachable manner to an end of a water-soluble film packaging another detergent composition. In such a case, the aspect ratio (long axis diameter/short axis diameter) between the major axis diameter of the maximum projected area of the detergent article and the minor axis diameter perpendicular to the major axis diameter is measured based on the calculated maximum projected area by calculating the maximum projected area of the detergent article for each water-soluble film packaging a detergent composition. That is, in the case of a detergent article in which the ends of the water-soluble films packaging a detergent composition are connected in a detachable manner, the aspect ratio is measured by cutting off the connected portion of the water-soluble film packaging the detergent composition. In addition, when the connected portion is unknown, a line dividing each packaged detergent composition into equal parts can be regarded as the connected portion.

 本発明の洗浄剤組成物及び洗浄剤物品は、繊維製品用、食器などの硬質表面用、又は自動食器洗浄機用として好適に用いることができ、繊維製品用として用いるのが好ましい。 The cleaning composition and cleaning article of the present invention can be suitably used for textile products, for hard surfaces such as tableware, or for automatic dishwashers, and is preferably used for textile products.

 本発明の洗浄剤組成物又は洗浄剤物品で繊維製品を洗浄する場合、洗浄する繊維は、疎水性繊維、親水性繊維のいずれでも良い。疎水性繊維としては、例えば、タンパク質系繊維(牛乳タンパクガゼイン繊維、プロミックスなど)、ポリアミド系繊維(ナイロンなど)、ポリエステル系繊維(ポリエステルなど)、ポリアクリロニトリル系繊維(アクリルなど)、ポリビニルアルコール系繊維(ビニロンなど)、ポリ塩化ビニル系繊維(ポリ塩化ビニルなど)、ポリ塩化ビニリデン系繊維(ビニリデンなど)、ポリオレフィン系繊維(ポリエチレン、ポリプロピレンなど)、ポリウレタン系繊維(ポリウレタンなど)、ポリ塩化ビニル/ポリビニルアルコール共重合系繊維(ポリクレラールなど)、ポリアルキレンパラオキシベンゾエート系繊維(ベンゾエートなど)、ポリフルオロエチレン系繊維(ポリテトラフルオロエチレンなど)、ガラス繊維、炭素繊維、アルミナ繊維、シリコーンカーバイト繊維、岩石繊維(ロックファイバー)、鉱滓繊維(スラッグファイバー)、金属繊維(金糸、銀糸、スチール繊維)等が例示される。親水性繊維としては、例えば、種子毛繊維(木綿、カポックなど)、靭皮繊維(麻、亜麻、苧麻、大麻、黄麻など)、葉脈繊維(マニラ麻、サイザル麻など)、やし繊維、いぐさ、わら、獣毛繊維(羊毛、モヘア、カシミヤ、らくだ毛、アルパカ、ビキュナ、アンゴラなど)、絹繊維(家蚕絹、野蚕絹)、羽毛、セルロース系繊維(レーヨン、ポリノジック、キュプラ、アセテートなど)等が例示される。
 繊維は、仕上がり性の観点から、繊維は木綿繊維を含む繊維であることが好ましい。繊維中の木綿繊維の含有量は、繊維の仕上がり性の観点から、好ましくは5質量%以上、より好ましくは10質量%以上、更に好ましくは15質量%以上、より更に好ましくは20質量%以上、より更に好ましくは40質量%以上、より更に好ましくは60質量%以上、より更に好ましくは80質量%以上、そして、好ましくは100質量%以下であり、100質量%であってよい。
When a textile product is cleaned with the cleaning composition or cleaning article of the present invention, the fiber to be cleaned may be either a hydrophobic fiber or a hydrophilic fiber. Examples of hydrophobic fibers include protein fibers (milk protein casein fiber, promix, etc.), polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride/polyvinyl alcohol copolymer fibers (polycral, etc.), polyalkylene paraoxybenzoate fibers (benzoate, etc.), polyfluoroethylene fibers (polytetrafluoroethylene, etc.), glass fibers, carbon fibers, alumina fibers, silicone carbide fibers, rock fibers (rock fibers), slag fibers (slag fibers), and metal fibers (gold thread, silver thread, steel fibers). Examples of hydrophilic fibers include seed hair fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), leaf vein fibers (Manila hemp, sisal, etc.), palm fibers, rush, straw, animal hair fibers (wool, mohair, cashmere, camel hair, alpaca, vicuna, angora, etc.), silk fibers (domestic silk, wild silk), feathers, and cellulosic fibers (rayon, polynosic, cupra, acetate, etc.).
From the viewpoint of finishing quality, the fiber is preferably a fiber containing cotton fiber. From the viewpoint of finishing quality of the fiber, the content of cotton fiber in the fiber is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 40% by mass or more, still more preferably 60% by mass or more, still more preferably 80% by mass or more, and preferably 100% by mass or less, and may be 100% by mass.

 本発明において繊維製品とは、前記の疎水性繊維や親水性繊維を用いた織物、編物、不織布等の布帛及びそれを用いて得られたアンダーシャツ、Tシャツ、Yシャツ、ブラウス、スラックス、帽子、ハンカチ、タオル、ニット、靴下、下着、タイツ等の製品を意味する。 In the present invention, textile products refer to fabrics such as woven fabrics, knitted fabrics, and nonwoven fabrics that use the hydrophobic and hydrophilic fibers described above, and products obtained using them, such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, and tights.

[繊維製品の洗浄方法]
 本発明は、本発明の洗浄剤組成物と水を混合した洗浄液(以下、本発明の洗浄液という)で、繊維製品を洗浄する、繊維製品の洗浄方法を提供する。本発明の繊維製品の洗浄方法において、本発明の洗浄剤組成物は、本発明の洗浄剤組成物を水溶性フィルムで包装してなる洗浄剤物品の形態で使用することができる。すなわち、本発明は、本発明の洗浄剤物品と水を混合した洗浄液(以下、前記と同様に本発明の洗浄液という)で、繊維製品を洗浄する、繊維製品の洗浄方法を提供する。
 本発明の繊維製品の洗浄方法では、本発明の洗浄剤組成物及び本発明の洗浄剤物品で記載した態様を適宜適用することができる。
 本発明の繊維製品の洗浄方法では、予め洗浄槽に本発明の洗浄剤組成物と水とを投入、混合して本発明の洗浄液を調製してから、被洗浄物である繊維製品を投入して、繊維製品を洗浄する方法でもよいが、本発明の効果を享受する観点から、洗浄槽に本発明の洗浄剤組成物、水及び繊維製品を投入し、本発明の洗浄剤組成物を水に溶かしながら本発明の洗浄液を調製するのと同時に繊維製品を洗浄する方法が好ましい。
 なお、本発明の繊維製品の洗浄方法において、本発明の洗浄剤物品を用いることができ、その場合、洗浄液は、上記の方法において、本発明の洗浄剤組成物を本発明の洗浄剤物品と読み替えて調製することができる。
[Method of cleaning textile products]
The present invention provides a method for cleaning textile products, in which textile products are cleaned with a cleaning liquid obtained by mixing the cleaning composition of the present invention with water (hereinafter referred to as the cleaning liquid of the present invention). In the method for cleaning textile products of the present invention, the cleaning composition of the present invention can be used in the form of a cleaning article obtained by packaging the cleaning composition of the present invention in a water-soluble film. That is, the present invention provides a method for cleaning textile products, in which textile products are cleaned with a cleaning liquid obtained by mixing the cleaning article of the present invention with water (hereinafter referred to as the cleaning liquid of the present invention as above).
In the method for cleaning textile products of the present invention, the embodiments described in relation to the detergent composition of the present invention and the detergent article of the present invention can be appropriately applied.
In the method for washing textile products of the present invention, the detergent composition of the present invention and water may be charged into a washing tank in advance and mixed to prepare the cleaning liquid of the present invention, and then the textile product to be washed is charged therein to wash the textile product. However, from the viewpoint of enjoying the effects of the present invention, a method is preferred in which the detergent composition of the present invention, water and the textile product are charged into a washing tank, and the detergent composition of the present invention is dissolved in the water while the cleaning liquid of the present invention is prepared and the textile product is washed at the same time.
The detergent article of the present invention can be used in the method for cleaning textile products of the present invention. In that case, the cleaning liquid can be prepared in the above-mentioned method by substituting the detergent composition of the present invention for the detergent article of the present invention.

 本発明の洗浄液において、本発明の洗浄剤組成物と水とを混合する際の水の量は、水1Lに対して、本発明の洗浄剤組成物の総量が、環境配慮及び洗浄性能の観点から、好ましくは0.01g以上、より好ましくは0.1g以上、更に好ましくは0.3g以上、そして、好ましくは10g以下、より好ましくは1g以下、更に好ましくは0.5g以下の濃度となるように調製する。 In the cleaning solution of the present invention, the amount of water used when mixing the cleaning composition of the present invention with water is adjusted so that the total amount of the cleaning composition of the present invention 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 per 1 L of water, from the viewpoints of environmental consideration and cleaning performance.

 本発明の洗浄液は、(A)成分を、洗浄性能の観点から、前記洗浄液中、好ましくは15ppm以上、より好ましくは30ppm以上、更に好ましくは45ppm以上、そして、すすぎの観点から、好ましくは300ppm以下、より好ましくは250ppm以下、更に好ましくは200ppm以下含有する。 The cleaning solution of the present invention contains component (A) in an amount of preferably 15 ppm or more, more preferably 30 ppm or more, and even more preferably 45 ppm or more in terms of cleaning performance, and preferably 300 ppm or less, more preferably 250 ppm or less, and even more preferably 200 ppm or less in terms of rinsing.

 本発明の洗浄液は、(B)成分を、洗浄性能の観点から、前記洗浄液中、好ましくは50ppm以上、より好ましくは100ppm以上、更に好ましくは150ppm以上、そして、冷水での残りの観点から、好ましくは800ppm以下、より好ましくは700ppm以下、更に好ましくは600ppm以下含有する。 The cleaning solution of the present invention contains component (B) in an amount of preferably 50 ppm or more, more preferably 100 ppm or more, and even more preferably 150 ppm or more in terms of cleaning performance, and preferably 800 ppm or less, more preferably 700 ppm or less, and even more preferably 600 ppm or less in terms of the residue in cold water.

 本発明の洗浄液は、(C)成分を、溶け残りの抑制の観点から、前記洗浄液中、好ましくは30ppm以上、より好ましくは60ppm以上、更に好ましくは100ppm以上、そして、スジ残りの生成抑制の観点から、好ましくは160ppm以下、より好ましくは150ppm以下、更に好ましくは140ppm以下含有する。 The cleaning solution of the present invention contains component (C) in an amount of preferably 30 ppm or more, more preferably 60 ppm or more, and even more preferably 100 ppm or more in terms of preventing residual dissolution, and preferably 160 ppm or less, more preferably 150 ppm or less, and even more preferably 140 ppm or less in terms of preventing streaking.

 本発明の洗浄液は、(D)成分を、抗菌性能の観点から、前記洗浄液中、好ましくは3ppm以上、より好ましくは5ppm以上、更に好ましくは8ppm以上、そして、例えば、50ppm以下含有する。 The cleaning solution of the present invention contains component (D) in an amount of preferably 3 ppm or more, more preferably 5 ppm or more, even more preferably 8 ppm or more, and for example, 50 ppm or less, in terms of antibacterial performance.

 本発明の洗浄液は、(E)成分を、粒子汚れの洗浄性能の観点から、前記洗浄液中、好ましくは5ppm以上、より好ましくは10ppm以上、更に好ましくは15ppm以上、そして、例えば、100ppm以下含有する。 The cleaning solution of the present invention contains component (E) in an amount of preferably 5 ppm or more, more preferably 10 ppm or more, even more preferably 15 ppm or more, and, for example, 100 ppm or less, in terms of cleaning performance against particulate soiling.

 本発明の洗浄液は、(F)成分を含有する場合、(F)成分を、洗浄性能及び泡立ち性能の観点から、前記洗浄液中、好ましくは0.5ppm以上、より好ましくは1.0ppm以上、更に好ましくは1.5ppm以上、そして、すすぎ性能の観点から、好ましくは20ppm以下、より好ましくは18ppm以下、更に好ましくは16ppm以下含有する。 When the cleaning solution of the present invention contains component (F), the cleaning solution contains component (F) in an amount of preferably 0.5 ppm or more, more preferably 1.0 ppm or more, and even more preferably 1.5 ppm or more in terms of cleaning performance and foaming performance, and preferably 20 ppm or less, more preferably 18 ppm or less, and even more preferably 16 ppm or less in terms of rinsing performance.

 本発明の洗浄液は、(G)成分を含有する場合、(G)成分を、安定性及び疎水性粒子の分散性の観点から、前記洗浄液中、好ましくは0.5ppm以上、より好ましくは1ppm以上、更に好ましくは1.5ppm以上、そして、例えば、50ppm以下含有する。 When the cleaning solution of the present invention contains component (G), from the viewpoints of stability and dispersibility of hydrophobic particles, the cleaning solution contains component (G) preferably at 0.5 ppm or more, more preferably at 1 ppm or more, even more preferably at 1.5 ppm or more, and for example, at 50 ppm or less.

 本発明の洗浄液は、(H)成分を含有する場合、(H)成分を、洗浄性能の観点からの観点から、前記洗浄液中、酵素タンパク質量として、好ましくは0.02ppm以上、より好ましくは0.04ppm以上、更に好ましくは0.06ppm以上、そして、肌への刺激性の観点から、好ましくは1.2ppm以下、より好ましくは1.0ppm以下、更に好ましくは0.80ppm以下含有する。 When the cleaning solution of the present invention contains component (H), the amount of component (H) in the cleaning solution is preferably 0.02 ppm or more, more preferably 0.04 ppm or more, and even more preferably 0.06 ppm or more in terms of the cleaning performance, and is preferably 1.2 ppm or less, more preferably 1.0 ppm or less, and even more preferably 0.80 ppm or less in terms of skin irritation.

 本発明の洗浄液は、(I)成分を含有する場合、(I)成分を洗浄性能の観点から、前記洗浄液中、好ましくは1ppm以上、より好ましくは2.5ppm以上、更に好ましくは5ppm以上、そして、例えば、100ppm以下含有する。 When the cleaning solution of the present invention contains component (I), from the viewpoint of cleaning performance, the cleaning solution contains component (I) preferably at 1 ppm or more, more preferably at 2.5 ppm or more, even more preferably at 5 ppm or more, and for example, at 100 ppm or less.

 近年、洗濯機が大型化し、繊維製品の質量(kg)と洗浄液の水量(リットル)の比で表される浴比の値、すなわち洗浄液の水量(リットル)/繊維製品の質量(kg)(以下、この比を浴比とする場合もある)の値が小さくなる傾向にある。家庭用洗濯機を用いた場合に浴比が小さくなると、洗浄時の撹拌により繊維製品同士の擦れが大きくなり、繊維製品の仕上がり性が損なわれる場合がある。浴比は、洗浄性能の観点から、好ましくは5以上、より好ましくは10以上、更に好ましくは20以上、そして、洗濯効率の観点から好ましくは100以下、より好ましくは50以下、更に好ましくは30以下である。 In recent years, washing machines have become larger, and the value of the bath ratio, which is the ratio of the mass of the textile product (kg) to the amount of water in the cleaning solution (liters), i.e., the amount of water in the cleaning solution (liters) / mass of the textile product (kg) (hereinafter, this ratio may be referred to as the bath ratio), tends to decrease. When using a domestic washing machine, if the bath ratio becomes small, the textile products may rub against each other more strongly due to agitation during washing, which may impair the finish of the textile product. From the viewpoint of washing performance, the bath 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, and even more preferably 30 or less.

 本発明の繊維製品の洗浄方法は、ローラー等で繊維を送りながら、精錬に使用する液に浸漬する方法、回転式洗浄方法に適している。回転式洗浄方法とは、回転機器に固定されていない繊維製品が洗浄液と共に、回転軸の周りに回転する洗浄方法を意味する。回転式洗浄方法は、回転式洗濯機により実施できる。従って、本発明では、繊維製品がよりきれいに仕上げる点で、繊維製品の洗浄を、回転式洗濯機を用いて行うことが好ましい。回転式の洗濯機としては、具体的には、ドラム式洗濯機、パルセータ式洗濯機又はアジテータ式洗濯機が挙げられる。これらの回転式洗濯機は、それぞれ、家庭用として市販されているものを使用することができる。 The method for washing textile products of the present invention is suitable for a rotary washing method, a method in which the textile products are immersed in a liquid used for scouring while being fed with a roller or the like. The rotary washing method refers to a washing method in which a textile product that is not fixed to a rotating device rotates around a rotating shaft together with the washing liquid. The rotary washing method can be carried out by a rotary washing machine. Therefore, in the present invention, in order to give the textile products a neater finish, it is preferable to wash the textile products using a rotary washing machine. Specific examples of rotary washing machines include drum washing machines, pulsator washing machines, and agitator washing machines. For these rotary washing machines, those commercially available for home use can be used.

 上述した実施の形態に加え、本発明は以下の態様を開示する。 In addition to the above-mentioned embodiment, the present invention discloses the following aspects.

<1>
 下記(A)成分を5質量%以上40質量%以下、下記(B)成分を20質量%以上80質量%以下、下記(C)成分を5質量%以上40質量%以下、下記(D)成分を0.1質量%以上5.0質量%以下、下記(E)成分を0.1質量%以上10質量%以下含有し、
 (a2)成分の含有量と、(a1)成分と(a2)成分の合計含有量との質量比(a2)/[(a1)+(a2)]が0以上0.5以下、
 (b2)成分の含有量と、(b1)成分と(b2)成分の合計含有量との質量比(b2)/[(b1)+(b2)]が0.2以上0.8以下、
 (C)成分の含有量と、(B)成分と(C)成分の合計含有量との質量比(C)/[(B)+(C)]が0を超え0.50以下である、
洗浄剤組成物。
(A)成分:下記(a1)成分及び下記(a2)成分から選ばれる1種以上
(a1)成分:ノニオン界面活性剤
(a2)成分:アニオン界面活性剤
(B)成分:下記(b1)成分及び下記(b2)成分から選ばれる1種以上
(b1)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩
(b2)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩
(C)成分:水不溶性無機成分
(D)成分:カチオン界面活性剤
(E)成分:アニオン性ポリマー
<1>
The composition contains the following component (A) in an amount of 5% by mass or more and 40% by mass or less, the following component (B) in an amount of 20% by mass or more and 80% by mass or less, the following component (C) in an amount of 5% by mass or more and 40% by mass or less, the following component (D) in an amount of 0.1% by mass or more and 5.0% by mass or less, and the following component (E) in an amount of 0.1% by mass or more and 10% by mass or less,
a mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more and 0.5 or less;
a mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) component is 0.2 or more and 0.8 or less;
a mass ratio (C)/[(B)+(C)] of the content of the (C) component to the total content of the (B) component and the (C) component is greater than 0 and is not greater than 0.50;
Cleaning composition.
Component (A): one or more selected from the following component (a1) and component (a2): Component (a1): a nonionic surfactant Component (a2): an anionic surfactant Component (B): one or more selected from the following component (b1) and component (b2): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b1): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b2): a water-soluble inorganic salt having a pH of less than 9.0 at 20°C in a 0.1 g/L aqueous solution of the component (C): a water-insoluble inorganic component Component (D): a cationic surfactant Component (E): an anionic polymer

<2>
 (a1)成分が、下記一般式(a1-1)で表されるノニオン界面活性剤である、前記<1>に記載の洗浄剤組成物。
  R1a(CO)O-(A1aO)-R2a (a1-1)
〔式中、R1aは炭素数8以上、好ましくは10以上、より好ましくは12以上、そして、18以下、好ましくは16以下、より好ましくは14以下の脂肪族炭化水素基、好ましくはアルキル基及びアルケニル基から選ばれる基であり、R2aは水素原子又はメチル基、好ましくは水素原子である。COはカルボニル基であり、mは0又は1の数であり、好ましくは0である。A1aO基は炭素数2以上4以下のアルキレンオキシ基から選ばれる1種以上、好ましくは炭素数2以上3以下のアルキレンオキシ基から選ばれる1種以上、より好ましくはエチレンオキシ基である。nはA1aO基の平均付加モル数であって、1以上、好ましくは6以上、より好ましくは8以上、そして、30以下、好ましくは25以下、より好ましくは20以下、更に好ましくは15以下の数である。〕
<2>
The cleaning composition according to <1> above, wherein the component (a1) is a nonionic surfactant represented by the following general formula (a1-1):
R 1a (CO) m O-(A 1a O) n -R 2a (a1-1)
[In the formula, R 1a is an aliphatic hydrocarbon group having 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, preferably a group selected from an alkyl group and an alkenyl group, and R 2a is a hydrogen atom or a methyl group, preferably a hydrogen atom. CO is a carbonyl group, m is a number of 0 or 1, preferably 0. A 1a O group is one or more selected from alkyleneoxy groups having 2 to 4 carbon atoms, preferably one or more selected from alkyleneoxy groups having 2 to 3 carbon atoms, more preferably an ethyleneoxy group. n is the average number of moles added of A 1a O group, and is a number of 1 or more, preferably 6 or more, more preferably 8 or more, and 30 or less, preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.]

<3>
 (a2)成分が、下記一般式(a2-1)で表される化合物〔以下、(a2-1)成分という〕、一般式(a2-2)で表される化合物〔以下、(a2-2)成分という〕、一般式(a2-3)で表される化合物〔以下、(a2-3)成分という〕及び一般式(a2-4)で表される化合物〔以下、(a2-4)成分という〕から選ばれる1種以上の化合物である、好ましくは(a2-1)成分、(a2-2)成分、及び(a2-3)成分から選ばれる1種以上である、より好ましくは(a2-1)成分、及び(a2-2)成分から選ばれる1種以上である、前記<1>又は<2>に記載の洗浄剤組成物。
 R3a-B-SOM   (a2-1)
〔式(a2-1)中、R3aは炭素数9以上、好ましくは10以上、そして、好ましくは14以下、より好ましくは13以下のアルキル基を示し、Bはベンゼン環を示し、Bの炭素原子と結合するR3aの炭素原子が第2級炭素原子であり、Mは陽イオン、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオン、より好ましくはナトリウムイオンを示す。Bに結合するR3aに対して、スルホン酸基はオルト、メタ又はパラ位に結合している。〕
 R4a-COOM   (a2-2)
〔式(a2-2)中、R4aは炭素数10以上、好ましくは11以上、そして、18以下、好ましくは16以下、より好ましくは14以下、更に好ましくは13以下のアルキル基又はアルケニル基、好ましくは直鎖のアルキル基、分岐鎖のアルキル基、直鎖のアルケニル基及び分岐鎖のアルケニル基から選ばれる1種以上の基、より好ましくは直鎖のアルキル基を示し、Mは陽イオン、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオン、より好ましくはナトリウムイオンを示す。〕
 R5a-O-(AO)-SOM   (a2-3)
〔式(a2-3)中、R5aは炭素数10以上、好ましくは11以上、より好ましくは12以上、そして、18以下、好ましくは16以下、より好ましくは14以下の脂肪族炭化水素基、好ましくは直鎖又は分岐鎖の脂肪族炭化水素基、より好ましくは直鎖の脂肪族炭化水素基、更に好ましくは直鎖アルキル基であり、AO基はエチレンオキシ基及びプロピレンオキシ基から選ばれる1種以上のアルキレンオキシ基、好ましくはエチレンオキシ基を含むアルキレンオキシ基であり、nはAO基の平均付加モル数であって、0以上、そして、20以下、好ましくは16以下、より好ましくは12以下、更に好ましくは8以下、より更に好ましくは4以下の数であり、Mは陽イオン、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオン、より好ましくはナトリウムイオンを示す。〕
 R6a-CH(SOM)COOR7a   (a2-4)
〔式(a2-4)中、R6aは炭素数8以上、より好ましくは10以上、更に好ましくは12以上、そして、好ましくは18以下、より好ましくは16以下のアルキル基を示し、R7aは、水素原子又は炭素数1以上、そして、好ましくは5以下、より好ましくは4以下、更に好ましくは3以下のアルキル基を示し、Mは陽イオン、好ましくはナトリウムイオン、カリウムイオン等のアルカリ金属イオン、又はモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン等のアルカノールアンモニウムイオン、より好ましくはナトリウムイオンを示す。〕
<3>
The cleaning composition according to <1> or <2> above, wherein the component (a2) is one or more compounds selected from a compound represented by the following general formula (a2-1) (hereinafter referred to as the component (a2-1)), a compound represented by general formula (a2-2) (hereinafter referred to as the component (a2-2)), a compound represented by general formula (a2-3) (hereinafter referred to as the component (a2-3)), and a compound represented by general formula (a2-4) (hereinafter referred to as the component (a2-4)), preferably one or more compounds selected from the component (a2-1), the component (a2-2), and the component (a2-3), and more preferably one or more compounds selected from the component (a2-1) and the component (a2-2).
R 3a -B-SO 3 M (a2-1)
[In formula (a2-1), R 3a represents an alkyl group having 9 or more, preferably 10 or more, and preferably 14 or less, more preferably 13 or less carbon atoms; B represents a benzene ring; the carbon atom of R 3a bonded to the carbon atom of B is a secondary carbon atom; M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, more preferably a sodium ion. The sulfonic acid group is bonded to the ortho, meta or para position of R 3a bonded to B.]
R 4a -COOM (a2-2)
[In formula (a2-2), R 4a represents an alkyl or alkenyl group having 10 or more, preferably 11 or more, and 18 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 13 or less carbon atoms, preferably one or more groups selected from a linear alkyl group, a branched alkyl group, a linear alkenyl group, and a branched alkenyl group, more preferably a linear alkyl group, and M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, more preferably a sodium ion.]
R 5a -O-(AO) n -SO 3 M (a2-3)
[In formula (a2-3), R 5a represents an aliphatic hydrocarbon group having 10 or more, preferably 11 or more, more preferably 12 or more and 18 or less, preferably 16 or less, more preferably 14 or less carbon atoms, preferably a linear or branched aliphatic hydrocarbon group, more preferably a linear aliphatic hydrocarbon group, and even more preferably a linear alkyl group; the AO group represents one or more alkyleneoxy groups selected from an ethyleneoxy group and a propyleneoxy group, preferably an alkyleneoxy group containing an ethyleneoxy group; n represents the average number of moles of AO groups added and is a number of 0 or more and 20 or less, preferably 16 or less, more preferably 12 or less, even more preferably 8 or less, and even more preferably 4 or less; and M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanolammonium ion or a diethanolammonium ion, and more preferably a sodium ion.]
R 6a -CH(SO 3 M) COOR 7a (a2-4)
[In formula (a2-4), R 6a represents an alkyl group having 8 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or less, more preferably 16 or less; R 7a represents a hydrogen atom or an alkyl group having 1 or more carbon atoms, preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less; and M represents a cation, preferably an alkali metal ion such as a sodium ion or a potassium ion, or an alkanol ammonium ion such as a monoethanol ammonium ion or a diethanol ammonium ion, more preferably a sodium ion.]

<4>
 (b1)成分が、好ましくはアルカリ金属炭酸塩から選ばれる1種以上である、より好ましくは炭酸ナトリウム及び炭酸カリウムから選ばれる1種以上である、更に好ましくは炭酸ナトリウムである、前記<1>~<3>の何れかに記載の洗浄剤組成物。
<4>
The cleaning composition according to any one of the above <1> to <3>, wherein the component (b1) is preferably one or more selected from alkali metal carbonates, more preferably one or more selected from sodium carbonate and potassium carbonate, and even more preferably sodium carbonate.

<5>
 (b2)成分が、無機硫酸塩、無機ハロゲン化合物、及びアルカリ金属炭酸水素塩から選ばれる1種以上の化合物である、好ましくは無機硫酸塩及びアルカリ金属炭酸水素塩から選ばれる1種以上を含む水溶性無機塩である、前記<1>~<4>の何れかに記載の洗浄剤組成物。
<5>
The cleaning composition according to any of the above <1> to <4>, wherein the component (b2) is one or more compounds selected from inorganic sulfates, inorganic halogen compounds, and alkali metal bicarbonates, and is preferably a water-soluble inorganic salt containing one or more compounds selected from inorganic sulfates and alkali metal bicarbonates.

<6>
 (b2)成分が、硫酸ナトリウム、硫酸マグネシウム、硫酸アルミニウム、硫酸カリウム、塩化ナトリウム、塩化カリウム、塩化カルシウム、塩化マグネシウム、炭酸水素ナトリウム、及び炭酸水素カリウムから選ばれる1種以上の化合物である、前記<1>~<4>の何れかに記載の洗浄剤組成物。
<6>
The cleaning composition according to any one of <1> to <4> above, wherein the component (b2) is one or more compounds selected from sodium sulfate, magnesium sulfate, aluminum sulfate, potassium sulfate, sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium hydrogen carbonate, and potassium hydrogen carbonate.

<7>
 (C)成分が、非晶質シリカ、ケイ酸カルシウム、粘土鉱物、結晶性アルミノケイ酸塩及び非晶質アルミノケイ酸塩から選ばれる1種以上である、好ましくは粘土鉱物、及び結晶性アルミノケイ酸塩から選ばれる1種以上である、前記<1>~<6>の何れかに記載の洗浄剤組成物。
<7>
The cleaning composition according to any one of the above <1> to <6>, wherein the component (C) is one or more selected from amorphous silica, calcium silicate, clay minerals, crystalline aluminosilicates, and amorphous aluminosilicates, preferably one or more selected from clay minerals, and crystalline aluminosilicates.

<8>
 (D)成分が、下記一般式(d1)で表される化合物、及び下記一般式(d2)で表される化合物から選ばれる1種以上である、前記<1>~<7>の何れかに記載の洗浄剤組成物。
<8>
The cleaning composition according to any one of <1> to <7> above, wherein the component (D) is at least one selected from the group consisting of a compound represented by the following general formula (d1) and a compound represented by the following general formula (d2):

Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003

〔式中、R1dは、炭素数8以上、好ましくは9以上、より好ましくは10以上、更に好ましくは12以上、そして、18以下、好ましくは16以下の脂肪族炭化水素基、好ましくはアルキル基又はアルケニル基、より好ましくはアルキル基であり、R2dは、炭素数8以上18以下の脂肪族炭化水素基、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基であり、R3d及びR4dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基、好ましくは炭素数1以上3以下のアルキル基から選ばれる基であり、Xは陰イオン、好ましくはハロゲンイオン、及び炭素数1以上3以下のアルキル硫酸イオンから選ばれる1種以上の陰イオンである。〕 [In the formula, R 1d is an aliphatic hydrocarbon group having 8 or more, preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and 18 or less, preferably 16 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group; R 2d is a group selected from an aliphatic hydrocarbon group having 8 to 18 carbon atoms, an alkyl group having 1 to 3 carbon atoms, and a hydroxyalkyl group having 1 to 3 carbon atoms; R 3d and R 4d 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, preferably a group selected from an alkyl group having 1 to 3 carbon atoms; and X is an anion, preferably one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.]

Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004

〔式中、R5dは、炭素数8以上、好ましくは10以上、より好ましくは12以上、そして、18以下、好ましくは16以下の脂肪族炭化水素基、好ましくはアルキル基又はアルケニル基、より好ましくはアルキル基であり、R6d及びR7dは、それぞれ独立に、炭素数1以上3以下のアルキル基及び炭素数1以上3以下のヒドロキシアルキル基から選ばれる基、好ましくは炭素数1以上3以下のアルキル基から選ばれる基であり、Xは陰イオン、好ましくはハロゲンイオン、及び炭素数1以上3以下のアルキル硫酸イオンから選ばれる1種以上の陰イオンである。〕 [In the formula, R 5d is an aliphatic hydrocarbon group having 8 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, preferably an alkyl or alkenyl group, more preferably an alkyl group, R 6d and R 7d 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, preferably a group selected from an alkyl group having 1 to 3 carbon atoms, and X is an anion, preferably one or more anions selected from a halogen ion and an alkyl sulfate ion having 1 to 3 carbon atoms.]

<9>
 (D)成分が、塩化ベンザルコニウム及びアルキルトリメチルアンモニウムクロライドから選ばれる1種以上である、前記<1>~<8>の何れかに記載の洗浄剤組成物。
<9>
The cleaning composition according to any one of <1> to <8> above, wherein the component (D) is at least one selected from the group consisting of benzalkonium chloride and alkyltrimethylammonium chloride.

<10>
 (E)成分が、カルボン酸基又はその塩を有し、重量平均分子量が3,000以上のポリマーである、好ましくはポリアクリル酸及びその塩、アクリル酸とマレイン酸のコポリマー及びその塩、並びにポリマレイン酸及びその塩から選ばれる1種以上のポリマーであって、重量平均分子量が、好ましくは3,000以上、より好ましくは3,500以上、更に好ましくは4,000以上、より更に好ましくは5,000以上、より更に好ましくは6,000以上、より更に好ましくは7,000以上、より更に好ましくは8,000以上、より更に好ましくは9,000以上、より更に好ましくは10,000以上、そして、好ましくは100,000以下、より好ましくは50,000以下、更に好ましくは25,000以下、より更に好ましくは15,000以下のポリマーである、前記<1>~<9>の何れかに記載の洗浄剤組成物。
<10>
The cleaning composition according to any of the above <1> to <9>, wherein the component (E) is a polymer having a carboxylic acid group or a salt thereof and having a weight-average molecular weight of 3,000 or more, preferably one or more polymers selected from polyacrylic acid and salts thereof, copolymers of acrylic acid and maleic acid and salts thereof, and polymaleic acid and salts thereof, and has a weight-average molecular weight of preferably 3,000 or more, more preferably 3,500 or more, even more preferably 4,000 or more, still more preferably 5,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, still more preferably 8,000 or more, still more preferably 9,000 or more, still more preferably 10,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, still more preferably 25,000 or less, and still more preferably 15,000 or less.

<11>
 (A)成分を、前記洗浄剤組成物中、5質量%以上、好ましくは7質量%以上、より好ましくは9質量%以上、更に好ましくは11質量%以上、そして、40質量%以下、好ましくは30質量%以下、より好ましくは25質量%以下、更に好ましくは20質量%以下含有する、前記<1>~<10>の何れかに記載の洗浄剤組成物。
<11>
The cleaning composition according to any one of <1> to <10> above, wherein the cleaning composition contains the component (A) in an amount of 5 mass% or more, preferably 7 mass% or more, more preferably 9 mass% or more, even more preferably 11 mass% or more, and 40 mass% or less, preferably 30 mass% or less, more preferably 25 mass% or less, even more preferably 20 mass% or less.

<12>
 前記洗浄剤組成物中、(a2)成分の含有量と、(a1)成分と(a2)成分の合計含有量との質量比(a2)/[(a1)+(a2)]が、0以上、好ましくは0.05以上、より好ましくは0.10以上、更に好ましくは0.15以上、そして、0.5以下、好ましくは0.45以下、より好ましくは0.40以下、更に好ましくは0.35以下である、前記<1>~<11>の何れかに記載の洗浄剤組成物。
<12>
The cleaning composition according to any of the above <1> to <11>, wherein a mass ratio (a2)/[(a1)+(a2)] of the content of the component (a2) to the total content of the components (a1) and (a2) in the cleaning composition is 0 or more, preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.15 or more, and is 0.5 or less, preferably 0.45 or less, more preferably 0.40 or less, even more preferably 0.35 or less.

<13>
 (B)成分を、前記洗浄剤組成物中、20質量%以上、好ましくは25質量%以上、より好ましくは30質量%以上、更に好ましくは40質量%以上、そして、80質量%以下、好ましくは70質量%以下、より好ましくは65質量%以下、更に好ましくは60質量%以下、より更に好ましくは55質量%以下含有する、前記<1>~<12>の何れかに記載の洗浄剤組成物。
<13>
The cleaning agent composition according to any one of <1> to <12> above, wherein the cleaning agent composition contains the component (B) in an amount of 20 mass% or more, preferably 25 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, and 80 mass% or less, preferably 70 mass% or less, more preferably 65 mass% or less, even more preferably 60 mass% or less, and still more preferably 55 mass% or less.

<14>
 前記洗浄剤組成物中、(b2)成分の含有量と、(b1)成分と(b2)成分の合計含有量との質量比(b2)/[(b1)+(b2)]が、0.2以上、好ましくは0.30以上、より好ましくは0.35以上、更に好ましくは0.40以上、そして、0.8以下、好ましくは0.7以下、より好ましくは0.65以下、更に好ましくは0.60以下、より更に好ましくは0.55以下、より更に好ましくは0.50以下である、前記<1>~<13>の何れかに記載の洗浄剤組成物。
<14>
The cleaning composition according to any of the above <1> to <13>, wherein a mass ratio (b2)/[(b1)+(b2)] of the content of the component (b2) to the total content of the component (b1) and the component (b2) in the cleaning composition is 0.2 or more, preferably 0.30 or more, more preferably 0.35 or more, even more preferably 0.40 or more, and is 0.8 or less, preferably 0.7 or less, more preferably 0.65 or less, even more preferably 0.60 or less, still more preferably 0.55 or less, and still more preferably 0.50 or less.

<15>
 (C)成分を、前記洗浄剤組成物中、5質量%以上、好ましくは10質量%以上、より好ましくは15質量%以上、更に好ましくは20質量%以上、より更に好ましくは25質量%以上、そして、40質量%以下、好ましくは35質量%以下、より好ましくは32.5質量%以下、更に好ましくは30質量%以下含有する、前記<1>~<14>の何れかに記載の洗浄剤組成物。
<15>
The cleaning agent composition according to any one of <1> to <14> above, wherein the cleaning agent composition contains the component (C) in an amount of 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, even more preferably 20 mass% or more, still more preferably 25 mass% or more, and 40 mass% or less, preferably 35 mass% or less, more preferably 32.5 mass% or less, and even more preferably 30 mass% or less.

<16>
 前記洗浄剤組成物中、(C)成分の含有量と、(B)成分と(C)成分の合計含有量との質量比(C)/[(B)+(C)]は、0を超え、好ましくは0.05以上、より好ましくは0.1以上、更に好ましくは0.15以上、より更に好ましくは0.20以上、より更に好ましくは0.25以上、より更に好ましくは0.30以上、そして、0.50以下、好ましくは0.45以下、より好ましくは0.40以下、更に好ましくは0.38以下である、前記<1>~<15>の何れかに記載の洗浄剤組成物。
<16>
The cleaning composition according to any of the above <1> to <15>, wherein a mass ratio (C)/[(B)+(C)] of the content of the component (C) to the total content of the component (B) and the component (C) in the cleaning composition exceeds 0, and is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.15 or more, still more preferably 0.20 or more, still more preferably 0.25 or more, still more preferably 0.30 or more, and is 0.50 or less, preferably 0.45 or less, more preferably 0.40 or less, and even more preferably 0.38 or less.

<17>
 (D)成分を、前記洗浄剤組成物中、0.1質量%以上、好ましくは0.5質量%以上、より好ましくは0.7質量%以上、更に好ましくは1.0質量%以上、より更に好ましくは2.0質量%以上、そして、5.0質量%以下、更には4.0質量%以下、更には3.5質量%以下、更には3.0質量%以下含有する、前記<1>~<16>の何れかに記載の洗浄剤組成物。
<17>
The cleaning agent composition according to any one of <1> to <16>, wherein the cleaning agent composition contains the component (D) in an amount of 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 0.7 mass% or more, even more preferably 1.0 mass% or more, still more preferably 2.0 mass% or more, and 5.0 mass% or less, further 4.0 mass% or less, further 3.5 mass% or less, and further 3.0 mass% or less.

<18>
 (E)成分を、前記洗浄剤組成物中、0.1質量%以上、好ましくは1.0質量%以上、より好ましくは2.0質量%以上、更に好ましくは3.0質量%以上、より更に好ましくは4.0質量%以上、そして、10質量%以下、好ましくは8.0質量%以下、より好ましくは6.0質量%以下、更に好ましくは5.0質量%以下含有する、前記<1>~<17>の何れかに記載の洗浄剤組成物。
<18>
The cleaning agent composition according to any one of <1> to <17> above, wherein the cleaning agent composition contains the component (E) in an amount of 0.1 mass% or more, preferably 1.0 mass% or more, more preferably 2.0 mass% or more, even more preferably 3.0 mass% or more, still more preferably 4.0 mass% or more, and 10 mass% or less, preferably 8.0 mass% or less, more preferably 6.0 mass% or less, and even more preferably 5.0 mass% or less.

<19>
 前記洗浄剤組成物中に含まれる界面活性剤の合計含有量に対する、(A)成分の含有量の割合(A)/(界面活性剤の合計含有量)が、好ましくは50質量%以上、より好ましくは60質量%以上、更に好ましくは70質量%以上、より更に好ましくは80質量%以上、そして、好ましくは98質量%以下、より好ましくは96質量%以下、更に好ましくは94質量%以下である、前記<1>~<18>の何れかに記載の洗浄剤組成物。
<19>
The cleaning agent composition according to any of the above <1> to <18>, wherein a ratio of the content of the component (A) to the total content of surfactants contained in the cleaning agent composition, (A)/(total content of surfactants), is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, still more preferably 80 mass% or more, and is preferably 98 mass% or less, more preferably 96 mass% or less, and even more preferably 94 mass% or less.

<20>
 前記洗浄剤組成物が、固体洗浄剤組成物である、好ましくは錠剤、粉末状、粒状、顆粒状及びペースト状から選ばれる洗浄剤組成物である、より好ましくは錠剤、粉末状及びペースト状から選ばれる洗浄剤組成物である、前記<1>~<19>の何れかに記載の洗浄剤組成物。
<20>
The detergent composition according to any of <1> to <19>, wherein the detergent composition is a solid detergent composition, preferably a detergent composition in the form of a tablet, a powder, a granule, or a paste, more preferably a detergent composition in the form of a tablet, a powder, or a paste.

<21>
 繊維製品用、硬質表面用、又は自動食器洗浄機用である、好ましくは繊維製品用である、前記<1>~<20>の何れかに記載の洗浄剤組成物。
<21>
The cleaning agent composition according to any one of <1> to <20> above, which is for textile products, for hard surfaces, or for automatic dishwashing machines, preferably for textile products.

<22>
 前記<1>~<21>の何れかに記載の洗浄剤組成物と水溶性フィルムからなる洗浄剤物品であって、前記洗浄剤組成物が前記水溶性フィルムに包装されている、洗浄剤物品。
<22>
A cleaning agent article comprising the cleaning agent composition according to any one of <1> to <21> above and a water-soluble film, wherein the cleaning agent composition is packaged in the water-soluble film.

<23>
 前記<1>~<21>の何れかに記載の洗浄剤組成物と水を混合した洗浄液で、繊維製品を洗浄する、繊維製品の洗浄方法。
<23>
A method for cleaning textile products, comprising washing the textile products with a cleaning liquid obtained by mixing the detergent composition according to any one of <1> to <21> above with water.

<24>
 前記<22>に記載の洗浄剤物品と水を混合した洗浄液で、繊維製品を洗浄する、繊維製品の洗浄方法。
<24>
A method for cleaning textile products, comprising cleaning the textile products with a cleaning liquid obtained by mixing the detergent article according to <22> with water.

実施例
[実施例、比較例]
<配合成分>
 実施例及び比較例では、以下の成分を用いた。
<(A)成分>
〔(a1)成分:ノニオン界面活性剤〕
・AEO(10):ポリオキシエチレンアルキルエーテル(アルキル基の炭素数12、オキシエチレンの平均付加モル数10)、エマルゲン110、花王株式会社製
〔(a2)成分:アニオン界面活性剤〕
・LAS:ラウリルベンゼンスルホン酸、ネオペレックスGS、花王株式会社製
・AS-Na:アルキル硫酸エステルナトリウム(アルキル基の炭素数12~16)、エマール10G、花王株式会社製
・脂肪酸:脂肪酸(炭素数12~18)、ルナックL-55、花王株式会社製
※LAS及び脂肪酸は、炭酸ナトリウムとの乾式中和によりナトリウム塩となるので、表1の(a2)成分は、「LAS-Na」又は「脂肪酸ナトリウム」と記載した。また、本発明の洗浄剤組成物の製造において、LAS又は脂肪酸の乾式中和により消費される炭酸ナトリウムは別途添加した。
<(B)成分>
〔(b1)成分〕
・炭酸ナトリウム:ライト灰、嵩密度600g/L、平均粒子径100μm、セントラル硝子株式会社製
〔(b2)成分〕
・硫酸ナトリウム:無水中性芒硝、四国化成株式会社製
・塩化ナトリウム:ナクル N、南海塩業株式会社製
<(C)成分>
・ゼオライト: ゼオビルダー、4A型、平均粒子径3.5μm、ZEOBUILDER社製
・ベントナイト:スメクタイト型層状粘土鉱物「オドソルブK-400」、メジアン粒子径 10μm、主成分 [MgAl(Si(OH)X-・MeX+、a=1、b=3、X=1、ナトリウム含有量 1.6%、モル比〔(Na+K+Li)/(Ca+Mg)〕=2.1、黒崎白土株式会社製
<(D)成分:カチオン界面活性剤>
・BAC:塩化ベンザルコニウム(アルキルジメチルベンジルアンモニウムクロライド、アルキル基の炭素数:12~16)、サニゾールB-50、花王株式会社製
・C16TMAC:アルキルトリメチルアンモニウムクロライド(アルキル基の炭素数16)、コータミン60W、花王株式会社製
<(E)成分>
・ポリアクリル酸:ポリアクリル酸ナトリウム、重量平均分子量1万、商品名 ポイズ536、花王株式会社製
<(G)成分>
・ポリエチレングリコール:PEG13000 、重量平均分子量 10,000、固形分60%、三井化学株式会社製
<(H)成分>
・酵素:プロテアーゼ、サビナーゼ8.0T、ノボザイムズ社製
Examples [Examples, Comparative Examples]
<Ingredients>
In the examples and comparative examples, the following components were used.
<Component (A)>
[Component (a1): Nonionic surfactant]
AEO (10): polyoxyethylene alkyl ether (alkyl group carbon number: 12, average number of moles of oxyethylene added: 10), Emulgen 110, manufactured by Kao Corporation [(a2) component: anionic surfactant]
LAS: laurylbenzenesulfonic acid, Neoperex GS, manufactured by Kao Corporation AS-Na: sodium alkyl sulfate (alkyl group has 12 to 16 carbon atoms), EMAL 10G, manufactured by Kao Corporation Fatty acid: fatty acid (having 12 to 18 carbon atoms), Lunac L-55, manufactured by Kao Corporation *Since LAS and fatty acids become sodium salts by dry neutralization with sodium carbonate, the component (a2) in Table 1 is described as "LAS-Na" or "sodium fatty acid." In addition, in the production of the detergent composition of the present invention, sodium carbonate consumed by dry neutralization of LAS or fatty acid was added separately.
<Component (B)>
[Component (b1)]
Sodium carbonate: light ash, bulk density 600 g/L, average particle size 100 μm, manufactured by Central Glass Co., Ltd. [component (b2)]
Sodium sulfate: anhydrous neutral Glauber's salt, manufactured by Shikoku Kasei Co., Ltd. Sodium chloride: Nacl N, manufactured by Nankai Salt Industry Co., Ltd. <Component (C)>
Zeolite: Zeobuilder, 4A type, average particle size 3.5 μm, manufactured by ZEOBUILDER Bentonite: smectite-type layered clay mineral "Odosorb K-400", median particle size 10 μm, main component [Mg a Al b (Si 2 O 5 ) 4 (OH) 4 ] X-.Me X+ , a = 1, b = 3, X = 1, sodium content 1.6%, molar ratio [(Na + K + Li) / (Ca + Mg)] = 2.1, manufactured by Kurosaki Hakudo Co., Ltd. <Component (D): cationic surfactant>
BAC: benzalkonium chloride (alkyl dimethyl benzyl ammonium chloride, alkyl group carbon number: 12 to 16), Sanisol B-50, manufactured by Kao Corporation C16TMAC: alkyl trimethyl ammonium chloride (alkyl group carbon number: 16), Kotamin 60W, manufactured by Kao Corporation <Component (E)>
Polyacrylic acid: sodium polyacrylate, weight average molecular weight 10,000, trade name Poise 536, manufactured by Kao Corporation (Component (G))
Polyethylene glycol: PEG 13000, weight average molecular weight 10,000, solid content 60%, manufactured by Mitsui Chemicals, Inc. <Component (H)>
Enzyme: Protease, Savinase 8.0T, Novozymes

<洗浄剤組成物の調製>
 上記の配合成分を用いて下記の方法で表1に示す洗浄剤組成物を調製した。
 混合槽にて硫酸ナトリウム、炭酸ナトリウム110kg、40%ポリアクリル酸ナトリウム、塩化ナトリウム、ゼオライト93kgを混合して、スラリーを調製した。このスラリーをポンプで噴霧乾燥塔(向流式)に供給し、塔頂付近に設置した圧力噴霧ノズルからスラリーを噴霧して、噴霧乾燥粒子を得た。次に得られた噴霧乾燥粒子、表1の配合組成となるように残りの炭酸ナトリウム及び(b2)成分の乾式中和により消費される炭酸ナトリウムを混合し、(a1)成分のノニオン界面活性剤、ポリエチレングリコール及び(D)成分のカチオン界面活性剤を混合した後に、(a2)成分を用いて乾式中和を行った。次いで、ベントナイトを添加し、更に表1の配合組成となるように残りのゼオライトを添加した。最後に酵素及び香料をブレントして粉末状の洗剤組成物とした。
 なお、実施例1-3では、(a2)成分を用いた乾式中和を行わず、アルキル硫酸塩の顆粒を、最後に酵素及び香料と共にブレンドで混合した。
 なお、表中の(H)成分以外の配合成分の質量%は、全て有効分に基づく数値であり、(H)成分は有姿としての配合量(質量%)を示している。また表中の(a2)成分の配合量(質量%)は、乾式中和後、すなわちナトリウム塩としての量を示している。
<Preparation of cleaning composition>
Using the above-mentioned components, the cleaning compositions shown in Table 1 were prepared by the following method.
Sodium sulfate, 110 kg of sodium carbonate, 40% sodium polyacrylate, sodium chloride, and 93 kg of zeolite were mixed in a mixing tank to prepare a slurry. The slurry was pumped into a spray-drying tower (countercurrent type), and the slurry was sprayed from a pressure spray nozzle installed near the top of the tower to obtain spray-dried particles. Next, the obtained spray-dried particles were mixed with the remaining sodium carbonate and sodium carbonate consumed by dry neutralization of component (b2) so as to obtain the composition shown in Table 1, and then the nonionic surfactant of component (a1), polyethylene glycol, and cationic surfactant of component (D) were mixed, followed by dry neutralization using component (a2). Next, bentonite was added, and the remaining zeolite was added so as to obtain the composition shown in Table 1. Finally, enzymes and fragrances were blended to obtain a powder detergent composition.
In Example 1-3, dry neutralization using component (a2) was not carried out, and alkyl sulfate granules were finally mixed with the enzyme and flavor in a blend.
In the table, the mass% of the blended components other than component (H) are all values based on the active ingredient, and the blended amount (mass%) of component (H) is shown as a solid form. The blended amount (mass%) of component (a2) in the table is shown after dry neutralization, i.e., as a sodium salt.

<洗浄性評価>
1.皮脂汚れの人工汚染布の作製
 使用した人工汚染布は6cm×6cmの木綿/ポリエステルブロード混紡染着布(木綿/ポリエステル比=35/65、谷頭商店より購入)に、下記組成からなる人工汚垢を1枚当たり100mgになるようグラビア塗工したものである。
・人工汚垢
 下記A、B、C、D、Eを含有する組成物を人工汚垢とした。それぞれの質量%は最終組成の人工汚垢の割合であり、合計が100質量%となるようにBの量を調節した。
A :モデル皮脂汚れ(人工汚垢中の質量%がラウリン酸0.44質量%、ミリスチン酸3.15質量%、ペンタデカン酸2.35質量%、パルミチン酸6.31質量%、ヘプタデカン酸0.44質量%、ステアリン酸1.60質量%、オレイン酸7.91質量%、パルミチン酸n-ヘキサデシル2.22質量%、スクアレン6.66質量%となる量で用いる)
B:塩化カルシウムの2水塩105mgを秤量し、蒸留水に溶かして1,000mLとして得た硬水
C:卵白レシチン液晶物1.98質量%(蒸留水80mLにアルギニン塩酸塩11.37g、ヒスチジン4.20g、セリン2.44gを溶解し、濃塩酸でpHを5.0に調整した後、この溶液と卵白レシチンをミキサーで十分混ぜ合わせて得た卵白レシチン液晶物)
D:鹿沼赤土8.11質量%
E:カーボンブラック0.025質量%
<Evaluation of cleaning ability>
1. Preparation of Artificially Stained Cloth with Sebum Stain The artificially stained cloth used was a 6 cm x 6 cm cotton/polyester broadcloth (cotton/polyester ratio = 35/65, purchased from Tanigashira Shoten) gravure coated with 100 mg of artificial dirt per sheet, the composition of which is given below.
Artificial soil A composition containing the following A, B, C, D, and E was used as artificial soil. Each mass % is the proportion of artificial soil in the final composition, and the amount of B was adjusted so that the total was 100 mass %.
A: Model sebum soil (used in amounts such that the mass percentages in the artificial soil were 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 mass% palmitic acid, 0.44 mass% heptadecanoic acid, 1.60 mass% stearic acid, 7.91 mass% oleic acid, 2.22 mass% n-hexadecyl palmitate, and 6.66 mass% squalene)
B: Hard water obtained by weighing out 105 mg of calcium chloride dihydrate and dissolving it in distilled water to make 1,000 mL. C: Egg white lecithin liquid crystals 1.98% by mass (egg white lecithin liquid crystals obtained by dissolving 11.37 g of arginine hydrochloride, 4.20 g of histidine, and 2.44 g of serine in 80 mL of distilled water, adjusting the pH to 5.0 with concentrated hydrochloric acid, and then thoroughly mixing this solution with egg white lecithin in a mixer).
D: Kanuma red soil 8.11% by mass
E: 0.025% by mass of carbon black

2.泥汚れの人工汚染布の作製
 泥汚れ汚染布は、10cm×10cmの綿メリヤス(綿100%、谷頭商店より購入)を用いて、特開平10-204769号の段落0030~0038に記載の製法により作製した。
2. Preparation of artificially soiled cloth with muddy soiling A muddy soiled cloth was prepared by the method described in paragraphs 0030 to 0038 of JP-A-10-204769 using 10 cm x 10 cm cotton knit (100% cotton, purchased from Tanigashira Shoten).

3.洗浄性評価
 皮脂汚れの人工汚染布と泥汚れの人工汚染布のそれぞれの人工汚染布について、下記方法で洗浄を行い、洗浄性の評価を行った。
 人工汚染布4枚を、ターゴトメーター(Ueshima製、MS-8212)にて、100rpmで10分間洗浄した。具体的な洗浄条件は、いずれも、人工汚染布4枚と、表1に記載の各洗浄剤組成物を0.30gターゴトメーターに投入し、水を600mL注入し、洗浄剤組成物を水に溶かしながら洗浄液を調製するのと同時に人工汚染布の洗浄を100rpmで10分間行った。また各洗浄液の水温は20℃であった。
 洗浄後、市水(20℃)で1分間すすいだ。その後二層式洗濯機を用いてすすぎ後の汚染布の脱水処理を3分間行った後、20℃、50%RHの条件下で5時間放置し乾燥させた。
 洗浄率(%)を下記の(1)式に基づいて算出し、4枚の平均値を求めた。なお、人工汚染布の原布、及び洗浄前後の人工汚染布の波長550nmにおける反射率は、分光色彩計(日本電色株式会社製、SE2000)にて測定した。結果を表1に示す。洗浄率の値が大きいほど、洗浄力に優れた洗浄剤組成物である。
洗浄率(%)=100×[(洗浄後の人工汚染布の反射率-洗浄前の人工汚染布の反射率)/(原布の反射率-洗浄前の人工汚染布の反射率)]  (1)
3. Evaluation of cleaning ability Each of the artificially soiled cloths, ie, cloths artificially soiled with sebum stains and cloths artificially soiled with mud stains, was cleaned by the following method, and the cleaning ability was evaluated.
Four pieces of artificially soiled cloth were washed in a tergotometer (MS-8212, manufactured by Ueshiba) at 100 rpm for 10 minutes. The specific washing conditions were as follows: four pieces of artificially soiled cloth and 0.30 g of each detergent composition shown in Table 1 were placed in the tergotometer, 600 mL of water was poured in, and a washing solution was prepared while dissolving the detergent composition in water, and at the same time, the artificially soiled cloth was washed at 100 rpm for 10 minutes. The water temperature of each washing solution was 20° C.
After washing, the stained cloth was rinsed with city water (20° C.) for 1 minute, and then dehydrated for 3 minutes using a two-layer washing machine, and then left to dry for 5 hours under conditions of 20° C. and 50% RH.
The cleaning rate (%) was calculated based on the following formula (1) and the average value of the four pieces was calculated. The reflectance at a wavelength of 550 nm of the original artificially soiled cloth and the artificially soiled cloth before and after cleaning was measured using a spectrophotometer (SE2000, manufactured by Nippon Denshoku Co., Ltd.). The results are shown in Table 1. The higher the cleaning rate, the more excellent the cleaning power of the cleaning composition.
Cleaning rate (%) = 100 × [(reflectance of artificially soiled cloth after cleaning - reflectance of artificially soiled cloth before cleaning) / (reflectance of original cloth - reflectance of artificially soiled cloth before cleaning)] (1)

<すすぎ性の評価>
1.泡残りの評価
 ドラム式洗濯機(NA-VG1000L、Panasonic社製)に、表1の洗浄剤組成物を40gと、ズボン(UNIQLO社製)、トレーナー(UNIQLO社製)、ボクサーパンツ(UNIQLO社製)、靴下(UNIQLO社製)、上長袖(ヒートテック、UNIQLO社製)を各3セットずつと全体重量が7.5kgになるように木綿製のTシャツ(YG、グンゼ社製)を加えて、標準コース、洗い9分、すすぎ1回、脱水6分で洗浄を行った。洗浄工程後のドラム式洗濯機の洗濯槽を該ドラム式洗濯機の正面から目視で確認し、下記評価指標にしたがって、泡残りの評価を行った。結果を表1に示す。泡残りの評価で、「0」と評価された洗浄剤組成物は、すすぎ性に優れた洗浄性組成物である。
泡残りの評価指標
0:泡の残量が洗濯槽の1/4未満である
1:泡の残量が洗濯槽の1/4以上である
<Evaluation of rinsing ability>
1. Evaluation of foam remaining To a drum-type washing machine (NA-VG1000L, Panasonic), 40 g of the detergent composition in Table 1, 3 sets of pants (UNIQLO), sweatshirt (UNIQLO), boxer shorts (UNIQLO), socks (UNIQLO), and long-sleeved top (Heattech, UNIQLO), and a cotton T-shirt (YG, Gunze) were added so that the total weight was 7.5 kg, and washing was performed with a standard course, washing for 9 minutes, rinsing once, and spin-drying for 6 minutes. The washing tub of the drum-type washing machine after the washing process was visually observed from the front of the drum-type washing machine, and foam remaining was evaluated according to the following evaluation index. The results are shown in Table 1. A detergent composition rated as "0" in the evaluation of foam remaining is a cleaning composition with excellent rinsing properties.
Evaluation index of remaining foam 0: The remaining amount of foam is less than 1/4 of the washing tub 1: The remaining amount of foam is 1/4 or more of the washing tub

2.濁りの評価
 上記ドラム式洗濯機での洗浄工程後に行った1回目のすすぎ工程後のすすぎ水の排水の一部を、たらい(直径30cm、高さ13.5cm)に5L貯留した。たらいの底部には、フォントサイズ18の黒色の文字が記載されたシールを予め張り付けた。たらいにすすぎ水が貯留された状態で、たらい底部に張り付けた文字を、すすぎ水の水面から真上に0.7m離れた位置から目視で観察した。5人のパネラーによって、下記の指標に基づき評価し、5人のパネラーの評価の合計値を求めた。結果を表1に示す。
 濁りの評価で、各パネラーの評価の合計値が低い洗浄剤組成物、更には該合計値が「0」の洗浄剤組成物は、すすぎ性に優れた洗浄性組成物である。
濁りの評価指標
0:たらい底部に張り付けた文字が認識できた。
1:たらい底部に張り付けた文字が認識できなかった。
2. Evaluation of turbidity A portion of the drainage of the rinse water after the first rinse step performed after the washing step in the drum washing machine was stored in a basin (diameter 30 cm, height 13.5 cm) at 5 L. A sticker with black letters of font size 18 was attached to the bottom of the basin in advance. With the rinse water stored in the basin, the letters attached to the bottom of the basin were visually observed from a position 0.7 m away directly above the surface of the rinse water. Evaluation was performed by five panelists based on the following indexes, and the total value of the evaluations of the five panelists was calculated. The results are shown in Table 1.
A cleaning composition having a low total score for the evaluation of turbidity by each panelist, or even a total score of "0", is a cleaning composition having excellent rinsing properties.
Turbidity evaluation index 0: The letters attached to the bottom of the tub were recognizable.
1: The letters attached to the bottom of the tub could not be recognized.

<抗菌性能の評価>
1.抗菌性の試験方法
(1)抗菌性試験に用いる布の調製
 ターゴトメーターに、木綿布(木綿#2003、谷頭商店製)30g、及び表1に記載の各洗浄剤組成物を0.3g溶かした洗浄液600mLを投入し、85rpmで洗浄10分、すすぎ3分の操作を5回累積して行ったものを試験布とした。水は全て煮沸滅菌済みの水道水を使用した。
(2)抗菌性試験
 着用済の衣料から分離したモラクセラ・オスロエンシスを用いて、JIS L 1902に則り抗菌性試験を行った。具体的には以下のように行った。
 上記(1)の方法で作製した試験布を2cm四方に裁断した試験片(1片あたりの質量は約0.4g)を検体とした。
(i)着用済みの衣類から分離されたモラクセラ・オスロエンシスをSCD-LP寒天培地を平板としたプレートに画線培養し、37℃、24時間培養したものを白金耳でかきとり、ニュートリエント(NT)培地10mLに入れて、37℃、110rpmの条件で24時間前培養した。前培養した培養液の濃度を吸光光度法によって推定し、菌濃度を約1×10個/mLに調整した。その後、1/20NT培地でさらに希釈し、菌濃度を1×10個/mLに調整し、試験菌液とした。
(ii)試験菌液をピペットで正確に0.2mL採取し、各検体又は未処理布である標準布(JIS L 1902の標準布)のそれぞれについて、1枚につき数ヵ所に接触させ、バイアル瓶に投入し、蓋を閉めた状態で、37℃で18時間培養した。試験菌液の接種、培養は、検体と標準布のそれぞれについて、複数を行った。
(iii)培養後の標準布及び接触直後の標準布を無作為に5つずつ選定し、洗い出し用LP希釈液20mLを加え、蓋を閉め、試験用撹拌器で30秒撹拌し、菌を洗い流し、菌数を計測した。培養後の検体を無作為に5つ選定し、検体ごとに、洗い流し用LP希釈液20mLを加え、蓋を閉め、試験用撹拌器で30秒撹拌し、菌を洗い流し、菌数を計測した。
 静菌活性値を下記の式で求めた。結果を表1に示す。静菌活性値が高い程、抗菌性能が高いことを表す。
   静菌活性値= LogB - LogC
   A:接種直後の標準布から回収した菌数の平均値
   B:18時間培養後の標準布から回収した菌数の平均値
   C:18時間培養後の検体から回収した菌数の平均値
 ただし、試験成立条件である、LogB - LogAが1.5を超えることを満たすものとする。
<Evaluation of antibacterial performance>
1. Antibacterial Test Method (1) Preparation of Fabric for Antibacterial Test 30 g of cotton fabric (cotton #2003, Tanigashira Shoten Co., Ltd.) and 600 mL of cleaning solution containing 0.3 g of each detergent composition listed in Table 1 were placed in a tergotometer, and the fabric was washed at 85 rpm for 10 minutes and rinsed for 3 minutes for a total of five cycles to prepare a test fabric. Boiled and sterilized tap water was used for all water.
(2) Antibacterial Test Using Moraxella osloensis isolated from worn clothing, an antibacterial test was carried out in accordance with JIS L 1902. Specifically, the test was carried out as follows.
The test cloth prepared by the method in (1) above was cut into test pieces of 2 cm square (each piece had a mass of approximately 0.4 g) to be used as specimens.
(i) Moraxella osloensis isolated from worn clothing was streaked on a plate with SCD-LP agar medium, and the resulting cultured specimen was scraped off with a platinum loop and placed in 10 mL of nutrient (NT) medium and pre-cultured for 24 hours at 37°C and 110 rpm. The concentration of the pre-cultured culture solution was estimated by spectrophotometry, and the bacterial concentration was adjusted to about 1 x 10 8 cells/mL. The culture was then further diluted with 1/20 NT medium to adjust the bacterial concentration to 1 x 10 5 cells/mL, and used as a test bacterial solution.
(ii) Exactly 0.2 mL of the test bacteria liquid was taken with a pipette, and each specimen or untreated standard cloth (JIS L 1902 standard cloth) was contacted with the liquid at several points, placed in a vial, and cultured at 37° C. for 18 hours with the lid closed. Inoculation with the test bacteria liquid and culture were performed multiple times for each of the specimens and standard cloth.
(iii) Five standard cloths after culture and five standard cloths immediately after contact were randomly selected, 20 mL of LP dilution for washing was added, the lid was closed, and the test was stirred for 30 seconds to wash away the bacteria, and the number of bacteria was counted. Five specimens after culture were randomly selected, 20 mL of LP dilution for washing was added to each specimen, the lid was closed, and the test was stirred for 30 seconds to wash away the bacteria, and the number of bacteria was counted.
The bacteriostatic activity value was calculated by the following formula. The results are shown in Table 1. A higher bacteriostatic activity value indicates higher antibacterial performance.
Bacteriostatic activity value = Log B - Log C
A: The average number of bacteria recovered from the control cloth immediately after inoculation. B: The average number of bacteria recovered from the control cloth after 18 hours of culture. C: The average number of bacteria recovered from the specimen after 18 hours of culture. However, this must satisfy the test validity condition, that is, Log B - Log A must exceed 1.5.

<溶け残り性の評価>
 表1の実施例及び比較例の各洗浄剤組成物の溶け残り性を、被洗浄物におけるスジ残りの有無と、洗浄後に溶け残った洗浄剤組成物の溶け残り残留物の直径と、に基づいて評価した。溶け残り性の評価は、下記の方法で行った。
 15cm×15cmにカットした黒色木綿布(黒染着綿ブロード40、谷頭商店より購入)に表1の各洗浄剤組成物40gを載せ、該洗浄剤組成物を包み込むように織り込む。木綿製のTシャツ(YG、グンゼ社製)を7kg(約70枚)準備し、まずは4kg分を全自動洗濯機(NA-FR80H68kg、Panasonic社製)の中に入れ、その上に洗浄剤組成物を包んだ黒色木綿布を載せ、残りの3kgをその上にかぶせるように入れた。5℃に温調した水道水(和歌山市水)にて、おまかせコース(水量60L)、洗い9分、すすぎ1回、脱水7分にセットして、洗濯を開始した。
<Evaluation of residual dissolution>
The residual dissolution property of each of the cleaning compositions of the Examples and Comparative Examples in Table 1 was evaluated based on the presence or absence of streaks on the cleaned object and the diameter of the residual dissolution property of the cleaning composition that remained after cleaning. The residual dissolution property was evaluated by the following method.
40 g of each detergent composition in Table 1 was placed on a black cotton cloth (black dyed cotton broadcloth 40, purchased from Tanigashira Shoten) cut to 15 cm x 15 cm, and the detergent composition was wrapped around the cloth and woven. 7 kg (about 70 pieces) of cotton T-shirts (YG, manufactured by Gunze Co., Ltd.) were prepared, and 4 kg of the T-shirts were first placed in a fully automatic washing machine (NA-FR80H 68 kg, manufactured by Panasonic Co., Ltd.), the black cotton cloth wrapped with the detergent composition was placed on top of the T-shirts, and the remaining 3 kg was placed on top of the T-shirts. Washing was started using tap water (Wakayama City water) adjusted to 5°C, with the automatic cycle (water volume 60 L), washing for 9 minutes, rinsing once, and spin drying for 7 minutes.

1.スジ残りの有無
 洗濯終了後、黒色木綿布を目視で確認し、黒色木綿布におけるスジ残りの有無を確認した。スジ残りの有無は、1枚の黒色木綿布を5人のパネラーによって、下記の指標に基づき評価し、5人のパネラーの評価の合計値を求めた。結果を表1に示す。5人のパネラーの評価の合計値の値が小さく、スジ残りの少ない洗浄剤組成物は、溶解性に優れ、溶け残り性が改善された洗浄剤組成物である。
スジ残りの有無の評価指標
0:まったくスジ残りなし
1:スジ残りあり
1. Presence or absence of streaks remaining After washing, the black cotton cloth was visually inspected to confirm the presence or absence of streaks remaining on the black cotton cloth. The presence or absence of streaks remaining was evaluated by five panelists on one piece of black cotton cloth based on the following criteria, and the total score of the five panelists was calculated. The results are shown in Table 1. A detergent composition with a small total score of the five panelists' evaluations and little streaks remaining is a detergent composition with excellent solubility and improved insolubility.
Evaluation index for the presence or absence of streaks 0: No streaks at all 1: Streaks present

2.溶け残り残留物の評価
 また、黒色木綿布における洗浄剤組成物の溶け残り残留物を回収し、回収した残留物の最大直径(mm)をノギスで測定した。
 そして、下記の指標に基づいて、洗浄剤組成物の溶け残り残留物の評価を行った。結果を表1に示す。溶け残り残留物の評価が、0又は1であれば、十分な溶解性を有する洗浄剤組成物と評価でき、溶け残り残留物の評価は、0であることが好ましい。
溶け残り残留物の評価指標
0:まったく溶け残りなし
1:1mm以上5mm以下の洗浄剤組成物の塊が確認された。
2:5mm以上の洗浄剤組成物の塊が確認された。
2. Evaluation of Undissolved Residue The undissolved residue of the detergent composition on the black cotton fabric was collected, and the maximum diameter (mm) of the collected residue was measured with a vernier caliper.
The undissolved residue of each cleaning composition was evaluated based on the following indexes. The results are shown in Table 1. If the undissolved residue was evaluated as 0 or 1, the cleaning composition was evaluated as having sufficient solubility, and it is preferable that the undissolved residue was evaluated as 0.
Evaluation index for undissolved residue 0: No undissolved residue at all 1: Clumps of the detergent composition measuring 1 mm or more and 5 mm or less were observed.
2: Clumps of the detergent composition measuring 5 mm or more were observed.

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

[参考例]
 以下に、本発明の洗浄剤組成物と、前記洗浄剤組成物を包装する水溶性フィルムと、を備える洗浄剤物品について例示する。前記洗浄剤物品は、以下に示す破裂強度の測定で破裂強度が300N以上とすることができ、以下に示す洗浄性の評価で、洗浄剤組成物を水溶性フィルムで包装した場合でも洗浄力の低下を抑制することができる。
[Reference Example]
The following is an example of a detergent article including the detergent composition of the present invention and a water-soluble film for packaging the detergent composition. The detergent article can have a burst strength of 300 N or more in the burst strength measurement shown below, and can suppress a decrease in detergency even when the detergent composition is packaged in a water-soluble film in the cleaning performance evaluation shown below.

<洗浄剤物品の作製>
 参考例ごとに既定の矩形のサイズにカットした76μmの水溶性フィルム(M8685、クラレ(株)製)を2枚重ね、ヒートシーラー(富士インパルス(株)製)を用い、ヒートシーラーのシール条件を8に設定して、水溶性フィルムの三辺をヒートシーラーで各辺の縁から幅2mm融着させ、一辺だけ開口した袋を作製し、この袋に表1の実施例1-4の洗浄剤組成物を各参考例ともに15g入れる。その後、ヒートシーラーで、袋の開口した一辺を融着して閉じて、洗浄剤組成物が水溶性フィルムに内包された円柱状の各洗浄剤物品を得る。得られる各洗浄剤物品の最大投影面積は、矩形であり、最大投影面積の長軸径、及び長軸径と、長軸径と直交する短軸径とのアスペクト比(長軸径/短軸径)は表2に記載の通りである。また洗浄剤組成物と接触している水溶性フィルムの総面積は、48cmである。なお、最大投影面積の測定において、シール部分の面積は、なお、最大投影面積の測定において、水溶性フィルムのシール部分の面積は、最大投影面積に含まれる。
 洗浄剤組成物と接触する水溶性フィルムの総面積は、洗浄剤物品の長軸径からシール部(4mm)を除いた長さと洗浄剤物品の短軸径からシール部(4mm)を除いた長さの積の2倍で求められ、参考例1~5の順に、それぞれ、30.4cm、34.2cm、35.6cm、37.1cm、38.6cmである。
<Preparation of cleaning article>
For each reference example, two sheets of 76 μm water-soluble film (M8685, manufactured by Kuraray Co., Ltd.) cut to a predetermined rectangular size were stacked, and a heat sealer (manufactured by Fuji Impulse Co., Ltd.) was used to set the sealing conditions of the heat sealer to 8, and three sides of the water-soluble film were fused by the heat sealer at a width of 2 mm from the edge of each side to prepare a bag with only one side open. 15 g of the detergent composition of Examples 1-4 in Table 1 was placed in this bag for each reference example. Then, the open side of the bag was fused and closed with a heat sealer to obtain each cylindrical detergent article in which the detergent composition was encapsulated in the water-soluble film. The maximum projected area of each of the obtained detergent articles was rectangular, and the major axis diameter of the maximum projected area and the aspect ratio (major axis diameter/minor axis diameter) between the major axis diameter and the minor axis diameter perpendicular to the major axis diameter were as shown in Table 2. The total area of the water-soluble film in contact with the detergent composition was 48 cm 2 . In addition, in measuring the maximum projected area, the area of the sealed portion of the water-soluble film is included in the maximum projected area.
The total area of the water-soluble film in contact with the detergent composition is calculated as twice the product of the length of the major axis diameter of the detergent article excluding the sealed portion (4 mm) and the length of the minor axis diameter of the detergent article excluding the sealed portion (4 mm), and is 30.4 cm 2 , 34.2 cm 2 , 35.6 cm 2 , 37.1 cm 2 , and 38.6 cm 2 for Reference Examples 1 to 5, respectively.

<破裂強度の測定>
 表2の各洗浄剤物品について破裂強度の測定を行う。測定環境が室温(20℃)/相対湿度約50%の条件下にて、圧縮試験機(AUTOGRAPH AG-X、島津サイエンス(株)製)を用いて、各洗浄剤物品を、最大投影面積となる面が圧縮試験機の固定式圧盤(球座式ではなく、各洗浄剤物品の最大投影面積よりも面積が広い)に接触するように置き、200mm/minの速度にて300Nの圧縮力を加えて評価を行う。この測定により、各参考例の洗浄剤物品はともに300Nの圧縮力で破裂せず、破裂強度が300N以上であることを示すことができる。
<Measurement of burst strength>
Burst strength is measured for each of the detergent articles in Table 2. Under the conditions of room temperature (20°C)/relative humidity of about 50%, a compression tester (AUTOGRAPH AG-X, Shimadzu Science Co., Ltd.) is used to place each detergent article so that the surface with the maximum projected area is in contact with a fixed platen (not a spherical type, and having an area larger than the maximum projected area of each detergent article) of the compression tester, and a compressive force of 300N is applied at a speed of 200mm/min to perform evaluation. This measurement shows that none of the detergent articles of each reference example bursts at a compressive force of 300N, indicating that the burst strength is 300N or more.

<洗浄性評価>
モデル皮脂汚れの調製
 以下の組成を有するモデル皮脂汚れを作製し、モデル皮脂汚れを含む人工汚布及の作製に用いる。
・モデル皮脂汚れ組成:
ラウリン酸0.44質量%、ミリスチン酸3.15質量%、ペンタデカン酸2.35質量%、パルチミチン酸6.31質量%、ヘプタデカン酸0.44質量%、ステアリン酸1.6質量%、オレイン酸7.91質量%、トリオレイン13.33質量%、パルミチン酸n-ヘキサデシル2.22質量%、スクアレン6.66質量%、及び残部の水(合計100質量%)
<Evaluation of cleaning ability>
Preparation of Model Sebum Soil A model sebum soil having the following composition is prepared and used to prepare an artificial soiled cloth containing the model sebum soil.
・Model sebum stain composition:
0.44% by mass of lauric acid, 3.15% by mass of myristic acid, 2.35% by mass of pentadecanoic acid, 6.31% by mass of palmitic acid, 0.44% by mass of heptadecanoic acid, 1.6% by mass of stearic acid, 7.91% by mass of oleic acid, 13.33% by mass of triolein, 2.22% by mass of n-hexadecyl palmitate, 6.66% by mass of squalene, and the balance being water (total 100% by mass)

人工汚染布の作製
 使用した人工汚染布は、6cm×6cmの木綿/ポリエステルブロード混紡布(木綿/ポリエステル比=35/65 谷頭商店より購入)に、上記組成から成るモデル皮脂汚れを1枚当り100mgになるようグラビア塗工して調製する。
Preparation of Artificially Soiled Cloth The artificially soiled cloth used was prepared by gravure coating a 6 cm x 6 cm cotton/polyester broadcloth (cotton/polyester ratio = 35/65, purchased from Tanigashira Shoten) with the model sebum soiling composition described above at 100 mg per sheet.

洗浄方法
 綿Tシャツ(グンゼ(株)製)の胸部に作製した人工汚染布4枚を縫い付けた。洗濯機は、縦型洗濯機(パナソニック(株)製、NA-F70PB1)、を用いた。表2の各参考例の洗浄剤物品を洗濯槽の一番下に置き、その後綿Tシャツ(グンゼ(株)製)を総重量2kgとなるように投入する。
 各参考例はともに、洗濯槽内の洗浄剤物品に含まれる洗浄剤組成物の濃度が0.5g/Lとなるように水を投入して、洗浄時間9分、濯ぎ時間1回、脱水時間7分で洗浄する。また洗浄、及び濯ぎに用いた水の温度は20℃である。
 また各洗浄剤物品に代えて、水溶性フィルムに包装されていない表1の実施例1-4の洗浄剤組成物を洗濯槽に投入し、上記と同様の洗浄方法を行う。これを基準例とする。
Washing method Four artificially soiled cloths were sewn onto the chest of a cotton T-shirt (Gunze Co., Ltd.). A vertical washing machine (NA-F70PB1, Panasonic Co., Ltd.) was used. The detergent article of each Reference Example in Table 2 was placed at the bottom of the washing tub, and then the cotton T-shirt (Gunze Co., Ltd.) was added so that the total weight was 2 kg.
In each of the reference examples, water was added so that the concentration of the detergent composition contained in the detergent article in the washing tub was 0.5 g/L, and the washing was performed for 9 minutes, 1 rinse, and 7 minutes spin-dry time. The temperature of the water used for washing and rinsing was 20° C.
In addition, instead of each detergent article, the detergent composition of Example 1-4 in Table 1 that is not packaged in a water-soluble film is put into the washing tub, and the same washing method as above is carried out. This is used as a reference example.

洗浄性評価
 綿Tシャツに縫い付けた4枚の人工汚染布を外して、洗浄率を下記の方法にて測定し、4枚の平均値を求める。
汚染前の原布、及び人工汚染布の洗浄前後の550nmにおける反射率を分光色彩計(日本電色株式会社製、SE-2000)にて測定し、次式によって洗浄率(%)を求め、4枚の平均値を算出する。
洗浄率(%)=100×[(洗浄後の反射率-洗浄前の反射率)/(原布の反射率-洗浄前の反射率)]
 算出する各参考例の洗浄率について、水溶性フィルムに包装していない洗浄剤組成物を用いた基準例の洗浄率を100%とした場合の基準例との相対洗浄率(%)を算出する。表2の各洗浄剤物品は相対洗浄率が高くすることができ、洗浄剤組成物を水溶性フィルムで包装した場合でも洗浄力の低下を抑制することができる。
Evaluation of cleaning ability The four pieces of artificially soiled cloth sewn onto the cotton T-shirt were removed, and the cleaning rate was measured by the following method, and the average value of the four pieces was calculated.
The reflectance at 550 nm of the unsoiled raw cloth and the artificially soiled cloth before and after washing was measured using a spectrophotometer (SE-2000, manufactured by Nippon Denshoku Co., Ltd.). The cleaning rate (%) was calculated using the following formula, and the average value of the four pieces was calculated.
Cleaning rate (%) = 100 x [(reflectance after cleaning - reflectance before cleaning) / (reflectance of original fabric - reflectance before cleaning)]
The cleaning rate of each Reference Example is calculated by taking the cleaning rate of a Reference Example using a cleaning composition not packaged in a water-soluble film as 100%, and calculating the relative cleaning rate (%) to the Reference Example. Each of the cleaning articles in Table 2 can increase the relative cleaning rate, and can suppress a decrease in cleaning power even when the cleaning composition is packaged in a water-soluble film.

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

Claims (8)

 下記(A)成分を5質量%以上40質量%以下、下記(B)成分を20質量%以上80質量%以下、下記(C)成分を5質量%以上40質量%以下、下記(D)成分を0.1質量%以上5.0質量%以下、下記(E)成分を0.1質量%以上10質量%以下含有し、
 (a2)成分の含有量と、(a1)成分と(a2)成分の合計含有量との質量比(a2)/[(a1)+(a2)]が0以上0.5以下、
 (b2)成分の含有量と、(b1)成分と(b2)成分の合計含有量との質量比(b2)/[(b1)+(b2)]が0.2以上0.8以下、
 (C)成分の含有量と、(B)成分と(C)成分の合計含有量との質量比(C)/[(B)+(C)]が0を超え0.50以下である、
洗浄剤組成物。
(A)成分:下記(a1)成分及び下記(a2)成分から選ばれる1種以上
(a1)成分:ノニオン界面活性剤
(a2)成分:アニオン界面活性剤
(B)成分:下記(b1)成分及び下記(b2)成分から選ばれる1種以上
(b1)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0以上である水溶性無機塩
(b2)成分:水溶性無機塩であり、その0.1g/L水溶液の20℃におけるpHが9.0未満である水溶性無機塩
(C)成分:水不溶性無機成分
(D)成分:カチオン界面活性剤
(E)成分:アニオン性ポリマー
The composition contains the following component (A) in an amount of 5% by mass or more and 40% by mass or less, the following component (B) in an amount of 20% by mass or more and 80% by mass or less, the following component (C) in an amount of 5% by mass or more and 40% by mass or less, the following component (D) in an amount of 0.1% by mass or more and 5.0% by mass or less, and the following component (E) in an amount of 0.1% by mass or more and 10% by mass or less,
a mass ratio (a2)/[(a1)+(a2)] of the content of the (a2) component to the total content of the (a1) component and the (a2) component is 0 or more and 0.5 or less;
a mass ratio (b2)/[(b1)+(b2)] of the content of the (b2) component to the total content of the (b1) component and the (b2) component is 0.2 or more and 0.8 or less;
a mass ratio (C)/[(B)+(C)] of the content of the (C) component to the total content of the (B) component and the (C) component is greater than 0 and is not greater than 0.50;
Cleaning composition.
Component (A): one or more selected from the following component (a1) and component (a2): Component (a1): a nonionic surfactant Component (a2): an anionic surfactant Component (B): one or more selected from the following component (b1) and component (b2): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b1): a water-soluble inorganic salt having a pH of 9.0 or more at 20°C in a 0.1 g/L aqueous solution of the component (b2): a water-soluble inorganic salt having a pH of less than 9.0 at 20°C in a 0.1 g/L aqueous solution of the component (C): a water-insoluble inorganic component Component (D): a cationic surfactant Component (E): an anionic polymer
 (b1)成分は、アルカリ金属炭酸塩から選ばれる1種以上のアルカリ剤である、請求項1に記載の洗浄剤組成物。 The cleaning composition according to claim 1, wherein component (b1) is one or more alkaline agents selected from alkali metal carbonates.  (b2)成分は、無機硫酸塩及びアルカリ金属炭酸水素塩から選ばれる1種以上の水溶性無機塩を含む、請求項1又は2に記載の洗浄剤組成物。 The cleaning composition according to claim 1 or 2, wherein component (b2) contains one or more water-soluble inorganic salts selected from inorganic sulfates and alkali metal hydrogen carbonates.  (D)成分は、塩化ベンザルコニウム及びアルキルトリメチルアンモニウムクロライドから選ばれる1種以上である、請求項1~3の何れか1項に記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 3, wherein component (D) is at least one selected from benzalkonium chloride and alkyltrimethylammonium chloride.  固体洗浄剤組成物である、請求項1~4の何れか1項に記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 4, which is a solid cleaning composition.  錠剤、粉末状又はペースト状である、請求項1~5の何れか1項に記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 5, which is in the form of a tablet, powder or paste.  繊維製品用である、請求項1~6の何れか1項に記載の洗浄剤組成物。 The cleaning composition according to any one of claims 1 to 6, which is for use on textile products.  請求項1~6の何れか1項に記載の洗浄剤組成物と、前記洗浄剤組成物を包装する水溶性フィルムと、を備える洗浄剤物品。 A cleaning agent article comprising the cleaning agent composition according to any one of claims 1 to 6 and a water-soluble film for packaging the cleaning agent composition.
PCT/JP2024/003614 2023-02-06 2024-02-05 Cleaning agent composition Ceased WO2024166840A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0987691A (en) * 1995-09-27 1997-03-31 Lion Corp Granular nonionic detergent composition and method for producing the same
JP2002241799A (en) * 2001-02-20 2002-08-28 Kao Corp Laundry goods
WO2006016700A1 (en) * 2004-08-13 2006-02-16 Lion Corporation Nonionic surfactant-containing particle and method for producing same
JP2008156565A (en) * 2006-12-26 2008-07-10 Lion Corp Laundry additive particles, method for producing the same, and detergent for clothing containing the same
JP2008163253A (en) * 2006-12-28 2008-07-17 Kao Corp Detergent composition
JP2010065116A (en) * 2008-09-10 2010-03-25 Kao Corp Detergent composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0987691A (en) * 1995-09-27 1997-03-31 Lion Corp Granular nonionic detergent composition and method for producing the same
JP2002241799A (en) * 2001-02-20 2002-08-28 Kao Corp Laundry goods
WO2006016700A1 (en) * 2004-08-13 2006-02-16 Lion Corporation Nonionic surfactant-containing particle and method for producing same
JP2008156565A (en) * 2006-12-26 2008-07-10 Lion Corp Laundry additive particles, method for producing the same, and detergent for clothing containing the same
JP2008163253A (en) * 2006-12-28 2008-07-17 Kao Corp Detergent composition
JP2010065116A (en) * 2008-09-10 2010-03-25 Kao Corp Detergent composition

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