WO2014103583A1 - Composition détergente en poudre destinée aux vêtements - Google Patents

Composition détergente en poudre destinée aux vêtements Download PDF

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Publication number
WO2014103583A1
WO2014103583A1 PCT/JP2013/081467 JP2013081467W WO2014103583A1 WO 2014103583 A1 WO2014103583 A1 WO 2014103583A1 JP 2013081467 W JP2013081467 W JP 2013081467W WO 2014103583 A1 WO2014103583 A1 WO 2014103583A1
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Prior art keywords
component
mass
less
washing
water
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PCT/JP2013/081467
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English (en)
Japanese (ja)
Inventor
吉岡佐知子
上野渉
Original Assignee
花王株式会社
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Priority to CN201380067979.8A priority Critical patent/CN104884600B/zh
Publication of WO2014103583A1 publication Critical patent/WO2014103583A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention relates to a powder detergent composition for clothing and a hand-washing laundry method.
  • washing machine washing There are two types of washing methods: hand washing and washing machine washing. In recent years, there has been a tendency for washing machine washing to increase due to the widespread use of washing machines, but there are still many needs for hand-washing washing from the viewpoint of stain removal and economic efficiency. In addition, hand washing is often employed so that washing can be performed with as little water as possible in regions where water resources are small in the world.
  • JP 2011-89107 A discloses a cleaning composition containing a nonionic surfactant, a specific anionic surfactant, and a fatty acid having 8 to 18 carbon atoms or a salt thereof under specific conditions. It is disclosed that the cleaning composition is excellent in detergency and foaming property, and the foam disappears quickly in the rinsing step, and the rinsing is completed quickly.
  • JP-A-62-230900 discloses a detergent composition for controlling foaming and turbidity during a rinsing cycle, comprising a surfactant, a soluble detergency builder, a fatty acid soap, a quaternary ammonium salt, and a silicone fluid foam suppressor. Is disclosed.
  • Japanese Patent Application Laid-Open No. 63-41596 discloses a detergent composition having an improved effect of washing with an enzyme, comprising a surfactant, an enzyme, a sulfite, a polycarboxylic acid polymer, and zeolite.
  • WO 98/20105 includes a surfactant, a mixture of carbonate and sulfate, silicate, polycarboxylate, PEG, and substantially free of aluminosilicate and phosphate.
  • a granular detergent composition is disclosed.
  • European Patent Application Publication No. 0495554 discloses a detergent composition that exhibits high detergency by combining a specific quaternary ammonium salt and cellulase. Summary of invention
  • the present invention (A) Surfactant [hereinafter referred to as component (A)] 5 mass% or more, 40 mass% or less, (B) a compound selected from carbonate and amorphous silicate [hereinafter referred to as component (B)], (C) a compound selected from sulfate and metal chloride (hereinafter referred to as component (C)), and (D) (D-1) one or more inorganic polyvalent metal ion trapping builders selected from aluminosilicates, crystalline silicates and phosphates (hereinafter referred to as component (D-1)) 0% by mass or more, 15% by mass or less, (D-2) one or more organic polyvalent metal ion capture builders selected from carboxylic acid polymer compounds (hereinafter referred to as component (D-1)) 0% by mass to 4% by mass Contains, As component (A), (A-1) a linear alkylbenzene sulfonate (hereinafter referred to as component (A-1))
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A-2) [(A-2-1) component / (A-2) component] is 0.4 or more and 1 or less
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A) [(A-2-1) / (A)] is 0.05 or more and 0.3 or less
  • the ratio of the total mass of the component (A-1) and the component (A-2) to the mass of the component (B) [[(A-1) component + (A-2) component] / (B) component] 25/75 or more and 67/33 or less
  • the total content of the component (D-1) and the component (D-2) is 0% by mass or more and 15% by mass or less in the composition.
  • the present invention also relates to a hand-washing laundry method for hand-washing an object to be washed that has been brought into contact with washing water containing the powder detergent composition for clothing of the present invention.
  • the present invention provides a powder detergent composition for clothing that can maintain the detergency at the time of washing, is excellent in foaming properties, disappears quickly in the rinsing step, and completes rinsing quickly.
  • a powder detergent composition for clothing in which rinsing is completed quickly by rinsing water with a small number of rinses.
  • Component (A) of the present invention is a surfactant and contains at least a linear alkylbenzene sulfonate of component (A-1) and an alkyl sulfate of component (A-2).
  • the component (A-1) of the present invention is a linear alkylbenzene sulfonate. Those having an alkyl group having 10 to 15 carbon atoms are preferred from the viewpoints of cleaning performance and foamability.
  • Examples of the salt constituting the component (A-1) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of safety, an alkali metal salt is preferable, and sodium is more preferable.
  • the component (A-2) of the present invention is an alkyl sulfate, and an alkyl sulfate having an alkyl group having 10 or more carbon atoms, more preferably 12 or more, and 24 or less is preferable.
  • the proportion of linear alkyl groups in all alkyl groups is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. More preferably, 99% by mass or more is even more preferable, and 100% by mass, that is, it is even more preferable that the component (A-2) is a linear alkyl sulfate.
  • the alkyl group has 16 or more carbon atoms, preferably 16 or more and 24 or less, more preferably 16 or more and 20 or less, more preferably 16 or more. , 18 or less, more preferably 16 alkyl sulfates (hereinafter also referred to as component (A-2-1)).
  • a powder detergent composition for clothing containing a surfactant containing a linear alkylbenzene sulfonate and an alkyl sulfate it may be desired to further improve the foamability and rinsability during the rinsing step.
  • alkyl group carbon atoms that are generally used in clothing powder detergent compositions are alkyl group carbon atoms in place of alkyl sulfates having 12 to 14 carbon atoms. Focusing on alkyl sulfates having a number of 16 or more [component (A-2-1)], and the presence of this component (A-2-1) in the composition under predetermined conditions, linear alkylbenzene sulfonate And it discovered that the foamability and the rinse property at the time of the rinse process of the powder detergent composition for garments which used alkyl sulfate together could be improved more. From this viewpoint, in the present invention, the surfactant used as the component (A) and the blending conditions thereof are specified.
  • Examples of the salt constituting the component (A-2) include alkali metal salts such as sodium and potassium, alkanolamine salts, and alkaline earth metal salts such as magnesium and calcium. From the viewpoint of safety, an alkali metal salt is preferable, and sodium is more preferable.
  • nonionic surfactants are preferable, and polyoxyalkylene alkyl ether (carbon number of alkyl group: 10 or more and 15 or less, average added mole number of alkylene oxide, preferably ethylene oxide: 2 or more, further 4 or more, and 10 Hereinafter, 8 or less) is more preferable.
  • polyoxyalkylene alkyl ether carbon number of alkyl group: 10 or more and 15 or less, average added mole number of alkylene oxide, preferably ethylene oxide: 2 or more, further 4 or more, and 10 Hereinafter, 8 or less
  • the content of the nonionic surfactant is in the composition from the viewpoint of improving detergency and foaming properties.
  • 2% by mass or less Preferably 1.5% by mass or less, and from the viewpoint of improving detergency, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, more preferably 0%. 0.5% by mass or more, more preferably 1% by mass or more.
  • the content of the cationic surfactant is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and more preferably 0.1% by mass or less in the composition from the viewpoint of suppressing a reduction in detergency. Is more preferable, 0% by mass, that is, even more preferably not contained.
  • cationic surfactant selected from ammonium salt and di-long chain alkyl quaternary ammonium salt having alkyl group having 8 or more and 18 or less carbon atoms, among which alkyl group has 8 or more and 18 or less carbon atoms.
  • the content of the mono long-chain alkyl quaternary ammonium salt having a carbon number of 8 or more and 18 or less is 0.5% by mass in the composition from the viewpoint of suppressing a reduction in detergency.
  • Component (B) of the present invention is a compound selected from carbonates and amorphous silicates, preferably carbonates.
  • the component (B) is preferably a water-soluble alkali inorganic salt.
  • water-soluble means that 1 g or more is dissolved in 100 g of water at 20 ° C.
  • melt dissolves 5g or more in 100g of water at 20 degreeC, and also 10g or more is preferable.
  • the 1 type (s) or 2 or more types chosen from an alkali metal carbonate, an alkali metal hydrogencarbonate, an alkali metal percarbonate, and an amorphous alkali metal silicate can be mentioned. More specifically, one or more selected from sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium percarbonate and amorphous sodium silicate can be mentioned. From the viewpoint of cleaning performance, foaming properties, and solubility, the carbonate is preferably one or more selected from alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal percarbonates, and alkali metal carbonates and One or more selected from alkali metal hydrogen carbonates are more preferable, and alkali metal carbonates are more preferable.
  • the ratio of percarbonate is 0.1 mass% or more in (B) component, Furthermore, 0.5 mass% or more, Furthermore, 1 mass% or more is preferable. And 30 mass% or less, Furthermore, 20 mass% or less, Furthermore, 10 mass% or less is preferable.
  • the composition preferably contains at least carbonate as the component (B), and contains both carbonate and amorphous silicate. More preferably.
  • the carbonate is selected from alkali metal carbonates and alkali metal hydrogen carbonates or Two or more are preferred, and alkali metal carbonates are more preferred. More specifically, one or more selected from sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate can be mentioned, and sodium carbonate is preferred.
  • the mass ratio of carbonate to amorphous silicate [carbonate / amorphous silicate] is 2 or more, further 2.5 or more, and further 3 More preferably, it is 3.5 or more, more preferably 4 or more, and 20 or less, further 15 or less, and further preferably 10 or less.
  • Component (C) component of this invention is a compound chosen from a sulfate and a metal chloride, Preferably it is a sulfate.
  • the component (C) is preferably a water-soluble neutral inorganic salt.
  • water-soluble means that 1 g or more is dissolved in 100 g of water at 20 ° C.
  • melt dissolves 5g or more in 100g of water at 20 degreeC, and also 10g or more is preferable.
  • the composition of the present invention preferably contains sodium sulfate as the component (C) from the viewpoint of cleaning performance.
  • the component (C) contains sulfate and metal chloride
  • the mass ratio of sulfate to metal chloride (sulfate / metal chloride) is 30 or more, further 40 or more, further 45 or more, and 60 Hereinafter, it is preferably 56 or less and more preferably 52 or less.
  • the composition of the present invention comprises, as component (C), at least one compound selected from sodium sulfate and potassium sulfate (hereinafter referred to as component (C1)), and at least one compound selected from sodium chloride and potassium chloride. (Hereinafter referred to as the component (C2)).
  • component (C1) at least one compound selected from sodium sulfate and potassium sulfate
  • component (C2) at least one compound selected from sodium chloride and potassium chloride.
  • the mass ratio (C1) / (C2) between the component (C1) and the component (C2) is preferably 30 or more, more preferably 40 or more, further 45 or more, and 60 or less, further 56 or less, and further 52 or less.
  • the powder detergent composition for clothing of the present invention contains 5% by mass or more and 40% by mass or less of the component (A).
  • the content of the component (A) is preferably 8% by mass or more, more preferably 10% by mass or more, and still more preferably 12% by mass or more in the composition.
  • 35 mass% or less is preferable in a composition, (A) component content is more preferable 30 mass% or less, 25 mass% or less is more preferable, and 20 mass% or less is still more preferable.
  • the content of the component (A-1) is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more in the composition.
  • the content of the component (A-2) is preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more in the composition.
  • the total mass of the component (A-1) and the component (A-2) in the component (A) is 70% by mass or more, 75% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass or more, more preferably 92% by mass or more, still more preferably 95% by mass or more, and 97% by mass or more. Is more preferable, and 99 mass% or more is still more preferable. It may be 100% by mass.
  • the ratio of the mass of the component (A-1) to the mass of the component (A-2) in the composition [component (A-1) / component (A-2)] is 55/45
  • the ratio is 85/15 or less, preferably 60/40 or more, and more preferably 65/35 or more.
  • the mass ratio is preferably 80/20 or less, and more preferably 75/25 or less.
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A-2) in the composition [(A-2-1) component / ( A-2) component] is 0.4 or more and 1 or less.
  • the mass ratio is preferably 1 or less, more preferably 0.9 or less, further 0.90 or less, and further preferably 0.85 or less.
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A) in the composition [(A-2-1) component / (A) component] is It is 0.05 or more and 0.3 or less. From the viewpoint of defoaming property, 0.05 or more, 0.07 or more, further 0.07 or more, further 0.1 or more, further 0.1 or more, and further 0.15 or more are preferable. Further, from the viewpoint of foaming property, this mass ratio is preferably 0.28 or less, and more preferably 0.25 or less.
  • the content of the component (B) in the powder detergent composition for clothing of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoints of cleaning performance, foaming properties and antifoaming properties, and 45 % By mass or less is preferable, 40% by mass or less is more preferable, and 35% by mass or less is more preferable.
  • the ratio of the total mass of the components (A-1) and (A-2) in the composition to the mass of the component (B) [[(A-1 ) Component + (A-2) component] / (B) component] is 25/75 or more, more preferably 26/74 or more, further 28/72 or more, further 29/71 or more, and more preferably 33/67 or more, And it is 67/33 or less, 66/34 or less, further 64/36 or less, further 63/37 or less, further 60/40 or less, further 55/45 or less, further 50/50 or less, further 45/55 or less. preferable.
  • the powder detergent composition for clothing of the present invention preferably contains 10% by mass or more and 80% by mass or less of the component (C).
  • the content is preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, from the viewpoints of cleaning performance, foaming properties, and defoaming properties.
  • the ratio of the total mass of the components (A-1) and (A-2) in the composition to the mass of the component (C) [[(A-1 Component + (A-2) component] / (C) component] is 11/89 or more and 67/33 or less.
  • This mass ratio is 67/33 or less, particularly 60/40 or less, further 50/50 or less, further 45/55 or less, and further 33/67 from the viewpoint of cleaning performance and foaming performance, particularly from the viewpoint of rinsing properties.
  • this mass ratio is 11/89 or more, more preferably 13/87 or more, further 14/86 or more, and further preferably 20/80 or more.
  • the total mass of the components (A-1) and (A-2) in the composition is preferably 1/20 or more and 1/1 or less. is there. This mass ratio is preferably 1/10 or more, more preferably 1/8 or more, and further preferably 1/7 or more, and is preferably 1/2 or less, and more preferably 1/4 or less.
  • the ratio of the mass of the component (B) and the mass of the component (C) in the composition [(B) component / (C ) Component] is preferably 1/99 or more and 99/1 or less.
  • This mass ratio is 3/97 or more, further 5/95 or more, further 10/90 or more, further 15/85 or more, further 20/80 or more, further 25/75 or more, further 30/70 or more, further 35/65.
  • the above is preferable, and 99/1 or less, further 95/5 or less, further 80/20 or less, further 60/40 or less, 55/45 or less, or 50/50 or less is preferable.
  • the powder detergent composition for clothing of the present invention comprises (D-1) one or more inorganic polyvalent metal ion scavengers selected from (D-1) aluminosilicate, crystalline silicate and phosphate Or (D-1) component] and (D-2) one or more organic polyvalent metal ion trapping builders (hereinafter referred to as (D-2) component) selected from carboxylic acid polymer compounds Or contained under predetermined conditions.
  • these compounds are known to be blended as environmentally high load polyvalent metal ion scavengers in powder detergent compositions for clothing.
  • the component (D) can be preferably contained in combination of a plurality of components (D).
  • the content of the component (D) in the composition is limited. Furthermore, even if it does not contain the component (D), it is possible for a person skilled in the art to recognize the advantageous effects of the present invention remarkably by improving the foaming property and the foam disappearance property while maintaining a good detergency. .
  • Aluminosilicates include crystalline or amorphous aluminosilicates, natural zeolites such as chabazite, varinite, erionite, faujasite, clinoptilolite, A-type zeolite, X-type zeolite, Y-type zeolite, L Synthetic zeolites such as type zeolite, omega type zeolite, P type zeolite, and MAP type zeolite.
  • an alkali metal silicate SiO 2 / M 2 O (wherein M represents an alkali metal atom) has a molar ratio of 0.5 or more and 2.6 or less. Can be mentioned.
  • Examples of the phosphate include orthophosphate, metaphosphate, trimetaphosphate, pyrophosphate, and tripolyphosphate.
  • Examples of the salt include alkali metal salts such as sodium salt and potassium salt.
  • the carboxylic acid-based polymer compound a weight average molecular weight of 1,000 or more including a repeating unit derived from monoethylenically unsaturated mono and / or dicarboxylic acid, and further a repeating unit derived from acrylic acid and / or maleic acid
  • the polymer compound examples include 150,000 or less.
  • Such a polymer compound may be a salt such as an alkali metal salt such as a sodium salt or a potassium salt.
  • Specific examples include polyacrylic acid and its salt, polymaleic acid and its salt, or acrylic acid-maleic acid copolymer and its salt. Of these, polyacrylic acid and salts thereof are preferable.
  • the content and ratio of the component (A-1), the component (A-2), the component (B), and the component (C) are in a specific range, so that a relatively large amount has been conventionally blended.
  • D The compounding quantity of an environment high load polyvalent metal ion capture
  • the content of the component (D-1) in the composition is 0% by mass or more and 15% by mass or less, preferably 12% by mass or less, and preferably 9% by mass or less. More preferably, 7 mass% or less is further more preferable, and 5 mass% or less is still more preferable. Further, it may be 3% by mass or less, further 2% by mass or less, further 1% by mass or less, and further 0% by mass.
  • the content of the phosphate is preferably 7% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less, more preferably 2% by mass or less, and preferably 1% by mass or less in the composition. More preferred is 0% by mass.
  • the content of the component (D-2) in the composition is 0% by mass or more and 4% by mass or less, preferably 3% by mass or less, and preferably 2% by mass.
  • the following is more preferable, 1.5% by mass or less is more preferable, 1% by mass or less is more preferable, and 0% by mass is still more preferable.
  • the total content of the component (D-1) and the component (D-2) is 0% by mass to 15% by mass in the composition, preferably 12% by mass or less, preferably 9% by mass.
  • % Is more preferably 5% by mass or less, still more preferably 4% by mass or less, still more preferably 3% by mass or less, still more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • 0% by mass is even more preferable.
  • the composition of the present invention includes a bleaching agent (perborate, bleach activator, etc.) known in the detergent field, a recontamination inhibitor, a softening agent (bentonite, etc.), a reducing agent (sulfite, etc.), An optical brightener, an antifoaming agent (silicone, etc.), a fragrance, an enzyme (cellulase, protease, peptinase, lipase, dextranase, amylase, etc.), a colorant and the like can be contained.
  • a bleaching agent perborate, bleach activator, etc.
  • a recontamination inhibitor e.g., a recontamination inhibitor, a softening agent (bentonite, etc.), a reducing agent (sulfite, etc.), An optical brightener, an antifoaming agent (silicone, etc.), a fragrance, an enzyme (cellulase, protease, pep
  • the content of silicone is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and 0% by mass, ie, not contained, in the composition from the viewpoint of foaming properties during washing. Is even more preferred.
  • the water content by the heat loss method described in JIS K 3362: 2008 is preferably 0.5% by mass or more, more preferably 1% by mass or more. And 10 mass% or less, Furthermore 8 mass% or less, Furthermore 6 mass% or less are preferable.
  • the composition of the present invention preferably has an apparent density of 1,600 g / L or less, more preferably 1,300 g / L or less, as measured by a method defined by JIS K 3362: 2008, More preferably, it is 100 g / L or less. Further, in terms of convenience and reduction of wastes (such as boxes used for product storage and packaging), the apparent density is preferably 300 g / L or more, more preferably 350 g / L or more, and still more preferably 400 g / L or more.
  • the composition of the present invention preferably has an average particle size of 150 ⁇ m or more and 180 ⁇ m or more obtained from a mass fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve of JIS Z 8801. And, it is preferably 1,000 ⁇ m or less, more preferably 800 ⁇ m or less, and further preferably 600 ⁇ m or less.
  • the pH of a 0.1% by mass aqueous solution measured at 20 ° C. described in JIS K 3362: 2008 is preferably 8 or more, more preferably 9 or more, in terms of cleaning performance.
  • the above is more preferable, 10 or more is more preferable, and 12 or less, further 11.5 or less, and further 11 or less are preferable.
  • composition of the present invention is preferably subjected to surface modification with a surface coating agent in terms of fluidity and non-caking property.
  • composition of the present invention can be produced by a known method.
  • spray drying method dry neutralization method, dry granulation method, dry blend method, fluidized bed drying method, thin film drying method, extrusion granulation method, rolling granulation method, stirring granulation method, compaction granulation method
  • the surfactant can be produced by applying a method for supporting a surfactant or a method selected and combined from these.
  • the present invention relates to a hand-washing washing method for hand-washing an object to be washed that has been brought into contact with washing water containing the powder detergent composition for clothing of the present invention.
  • a hand-washing washing method using the powder detergent composition for clothes of the present invention washing prepared from the powder detergent composition for clothes of the present invention is applied to clothes (which may include fabrics and other textile products) to be cleaned.
  • clothes which may include fabrics and other textile products
  • the mass of the washing water with respect to the mass of the clothing (object to be washed) is preferably 2 times or more and 100 times or less.
  • the mass of the washing water relative to the mass of the clothing (object to be cleaned) is preferably 2 times or more, more preferably 3 times or more, and further preferably 5 times or more, and is preferably 100 times or less, more preferably 50 times or less, and further preferably 25 times or less. It is visually preferable that the clothes brought into contact with the washing water according to the present invention are thoroughly rubbed by hand, because not only a good detergency is obtained but also rich foaming. After hand-washing such as rubbing, remove clothing (objects to be washed) from the washing water, squeeze out and drain the water using a dehydrator, and immerse it again in fresh water (hereinafter referred to as rinsing water).
  • the rinsing water may be either water stored in a basin or running water.
  • the mass of the rinsing water with respect to the object to be cleaned is preferably 2 times or more, more preferably 5 times or more, and further preferably 10 times or more based on the total amount of rinsing water used for rinsing, and 1,000 times or less, further 500 times or less, Further, it is preferably 100 times or less. Since the surfactant remaining in the clothing at the stage of immersing the rinse water is redissolved in the rinse water, foaming is observed. When this operation is repeated several times, the foaming disappears and the rinsing is completed.
  • washing by hand washing for example, when a normal detergent is used, it is generally required 5 times or more, but in the present invention, rinsing can be completed in 3 times or less, and rinsing with very little rinsing water is completed. Can be made.
  • the hand-washing washing method of the present invention includes a step of washing the article to be washed in contact with washing water containing the powder detergent composition for clothing of the present invention and water, and a step of rinsing the article to be washed with water. It is preferable to have.
  • the hardness of water used for the preparation of cleaning water and / or the hardness of water used for rinsing is preferably 1 ° DH or more and 50 ° DH or less from the viewpoint of cleaning power and rinsing properties.
  • the hardness of water used for the preparation of washing water and / or the hardness of water used for rinsing is 1 ° DH or more, further 2 ° DH or more, further 3 ° DH or more, further 5 ° DH or more, and further 10 ° DH or more. preferable. And it may be 50 ° DH or less, and further 30 ° DH or less.
  • the present invention (A) Surfactant [hereinafter referred to as component (A)] 5 mass% or more, 40 mass% or less, (B) a compound selected from carbonate and amorphous silicate [hereinafter referred to as component (B)], (C) a compound selected from sulfate and metal chloride (hereinafter referred to as component (C)), and (D) (D-1) one or more inorganic polyvalent metal ion trapping builders selected from aluminosilicates, crystalline silicates and phosphates (hereinafter referred to as component (D-1)) 0% by mass or more, 9% by mass or less, (D-2) one or more organic polyvalent metal ion capture builder selected from carboxylic acid polymer compounds (hereinafter referred to as component (D-2)) 0% by mass or more and 4% by mass or less Contains, As component (A), (A-1) a linear alkylbenzene sulfonate (hereinafter referred to as
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A-2) [(A-2-1) component / (A-2) component] is 0.4 or more and 1 or less
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A) [(A-2-1) / (A)] is 0.05 or more and 0.3 or less
  • the ratio of the total mass of the component (A-1) and the component (A-2) to the mass of the component (B) [[(A-1) component + (A-2) component] / (B) component] 25/75 or more and 67/33 or less
  • the total content of the component (D-1) and the component (D-2) is 0% by mass or more and 9% by mass or less in the composition.
  • component (A) Surfactant [hereinafter referred to as component (A)] 5 mass% or more, 40 mass% or less
  • component (B) a compound selected from carbonate and amorphous silicate [hereinafter referred to as component (B)]
  • component (C) a compound selected from sulfate and metal chloride (hereinafter referred to as component (C))
  • component (D) (D-1) one or more inorganic polyvalent metal ion trapping builders selected from aluminosilicates, crystalline silicates and phosphates (hereinafter referred to as component (D-1)) 0% by mass or more, 15% by mass or less
  • component (D-2) one or more organic polyvalent metal ion capture builder selected from carboxylic acid polymer compounds (hereinafter referred to as “component (D-2)”) of 0% by mass to 4% by mass
  • component (A) A-1) a linear alkylbenzene
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A-2) [(A-2-1) component / (A-2) component] is 0.4 or more and 1 or less
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A) [(A-2-1) / (A)] is 0.05 or more and 0.3 or less
  • the ratio of the total mass of the component (A-1) and the component (A-2) to the mass of the component (B) [[(A-1) component + (A-2) component] / (B) component] 25/75 or more and 67/33 or less
  • the total content of the component (D-1) and the component (D-2) is 0% by mass or more and 15% by mass or less in the composition.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 3>, further comprising (hereinafter also referred to as component (A-2-1)).
  • the component (A) other than the component (A-1) and the component (A-2) is a sulfate ester salt, paraffin sulfonate, ⁇ -sulfo fatty acid alkyl ester salt, ⁇ -olefin sulfonate of an ethoxylated higher alcohol.
  • anionic surfactants selected from fatty acid salts, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenyl ethers, sucrose fatty acid esters, sorbitan fatty acid esters, fatty acid alkanolamides
  • nonionic surfactants selected from alkyl glycosides, di-long chain alkylamines having 8 to 18 carbon atoms and polyoxyethylene adducts thereof, and alkyl groups having 8 to 18 carbon atoms.
  • a long mono chain A cationic surfactant selected from an alkyl quaternary ammonium salt and a di-long chain alkyl quaternary ammonium salt having an alkyl group having 8 to 18 carbon atoms, carbobetaine, sulfobetaine and hydroxysulfobetaine
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 4>, wherein the composition is one or more surfactants selected from the group consisting of amphoteric surfactants.
  • the polyoxyalkylene alkyl ether is a polyoxyalkylene having an alkyl group having 10 to 15 carbon atoms, an alkylene oxide, preferably an average added mole number of ethylene oxide of 2 or more, further 4 or more, and 10 or less, and further 8 or less.
  • the powder detergent composition for clothing according to ⁇ 5> which is an alkyl ether.
  • the content of the nonionic surfactant is preferably 2% by mass or less, more preferably 1.5% by mass or less, and preferably 0.1% by mass or more, more preferably 0.3% by mass in the composition.
  • the content of the cationic surfactant is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, more preferably 0.1% by mass or less, more preferably 0% by mass.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 7>.
  • the component (B) is one or more selected from alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal percarbonates and amorphous alkali metal silicates.
  • the component (B) is one or more selected from alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal percarbonates and amorphous alkali metal silicates.
  • the component (B) carbonate and amorphous silicate are contained, and the mass ratio of carbonate to amorphous silicate [carbonate / amorphous silicate] is 2 or more, preferably 2.5 or more, more preferably 3 or more, more preferably 3.5 or more, more preferably 4 or more, and 20 or less, preferably 15 or less, more preferably 10 or less, ⁇ 1> to ⁇ 9>
  • the powder detergent composition for clothing according to any one of the above.
  • the powder detergent composition for clothing according to any one of the above ⁇ 1> to ⁇ 11>, comprising as component (C) a sulfate, preferably sodium sulfate, and a metal chloride, preferably sodium chloride.
  • the content of the component (A) in the composition is 8% by mass or more, preferably 10% by mass or more, more preferably 12% by mass or more, and 35% by mass or less, preferably 30% by mass or less.
  • the content of the component (A-1) is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more in the composition, according to any one of the above ⁇ 1> to ⁇ 13> Powder detergent composition for clothing.
  • the content of the component (A-2) in the composition is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, according to any one of the above ⁇ 1> to ⁇ 14> Powder detergent composition for clothing.
  • the total mass of component (A-1) and component (A-2) in component (A) is 75% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, more preferably 90% by mass. Or more, more preferably 92% by mass or more, more preferably 95% by mass or more, more preferably 97% by mass or more, more preferably 99% by mass or more, more preferably 100% by mass, and more preferably 100% by mass.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 15>, wherein the composition is a mass%.
  • the ratio of the mass of the component (A-1) to the mass of the component (A-2) [component (A-1) / component (A-2)] is 60/40 or more, preferably 65/35 or more.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 16>, which is 80/20 or less, preferably 75/25 or less.
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A-2) [(A-2-1) component / (A-2) component] is 0.42 or more, preferably 0.8.
  • the ratio of the mass of the component (A-2-1) to the mass of the component (A) [(A-2-1) component / (A) component] is 0.07 or more, preferably 0.1 or more.
  • the content of the component (B) is 10% by mass or more, preferably 15% by mass or more, and 45% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, ⁇ 1
  • the powder detergent composition for clothing according to any one of> to ⁇ 19>.
  • the content of the component (C) in the composition is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and 80% by mass or less, preferably 70% by mass or less.
  • ⁇ 23> The ratio of the total mass of component (A-1) and component (A-2) to the mass of component (C) [[(A-1) component + (A-2) component] / (C) component] , 60/40 or less, preferably 50/50 or less, more preferably 45/55 or less, more preferably 33/67 or less, and 13/87 or more, preferably 14/86 or more, more preferably 20 /
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 22>, which is 80 or more.
  • Ratio of the total mass of the components (A-1) and (A-2) to the total mass of the components (B) and (C) [[(A-1) component + (A-2) component] / [(B) component + (C) component]] is 1/20 or more, preferably 1/10 or more, more preferably 1/8 or more, more preferably 1/7 or more, and 1/1 or less.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 23>, preferably 1/2 or less, more preferably 1/4 or less.
  • the ratio of the mass of the component (B) to the mass of the component (C) [(B) component / (C) component] is 1/99 or more, preferably 3/97 or more, more preferably 5/95 or more, more Preferably 10/90 or more, more preferably 15/85 or more, more preferably 20/80 or more, more preferably 25/75 or more, more preferably 30/70 or more, more preferably 35/65 or more, and 99/1 or less, preferably 95/5 or less, more preferably 80/20 or less, more preferably 60/40 or less, more preferably 55/45 or less, and more preferably 50/50 or less.
  • the powder detergent composition for clothing according to any one of> to ⁇ 24>.
  • the content of the component (D-1) in the composition is 12% by mass or less, preferably 9% by mass or less, more preferably 7% by mass or less, more preferably 5% by mass or less, more preferably 3% by mass or less. More preferably 2% by mass or less, more preferably 1% by mass or less, more preferably 0% by mass, more preferably 0% by mass, any one of the above items ⁇ 1> to ⁇ 25> A powder detergent composition for clothing.
  • the content of the component (D-2) is 3% by mass or less, preferably 2% by mass or less, more preferably 1.5% by mass or less, more preferably 1% by mass or less, more preferably 0% by mass in the composition.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 26>, wherein
  • the total content of the component (D-1) and the component (D-2) is 12% by mass or less, preferably 9% by mass or less, more preferably 5% by mass or less, more preferably 4% by mass or less in the composition.
  • Detergent composition is preferably 9% by mass or less, more preferably 5% by mass or less, more preferably 4% by mass or less in the composition.
  • ⁇ 29> For clothing according to any one of ⁇ 1> to ⁇ 28>, wherein the silicone content is 0.1% by mass or less, preferably 0.05% by mass or less, more preferably 0% by mass in the composition. Powder detergent composition.
  • the water content in the composition according to JIS K 3362: 2008 is 0.5% by mass or more, preferably 1% by mass or more, and 10% by mass or less, preferably 8% by mass or less, more preferably
  • the apparent density measured by the method specified by JIS K 3362: 2008 is 1,600 g / L or less, preferably 1,300 g / L or less, more preferably 1,100 g / L or less, and 300 g / L.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 30> above, preferably 350 g / L or more, more preferably 400 g / L or more.
  • the average particle size determined from the mass fraction due to the size of the sieve mesh is 150 ⁇ m or more, preferably 180 ⁇ m or more, and 1,000 ⁇ m or less, preferably
  • the pH of a 0.1% by mass aqueous solution measured at 20 ° C. described in JIS K 3362: 2008 is 8 or more, preferably 9 or more, more preferably 9.5 or more, more preferably 10 or more, and 12 or less.
  • the content of the cationic surfactant in the composition is 0.5% by mass or less, preferably 0.3% by mass or less, more preferably 0.1% by mass or less, more preferably 0% by mass, or ,
  • the content of the mono long-chain alkyl quaternary ammonium salt having 8 to 18 carbon atoms in the alkyl group is 0.5% by mass or less, preferably 0.3% by mass or less, more preferably in the composition.
  • the powder detergent composition for clothing according to any one of ⁇ 1> to ⁇ 33>, which is 0.1% by mass or less, more preferably 0% by mass.
  • a hand-washing laundry method for hand-washing an object to be washed which has been brought into contact with washing water containing the powder detergent composition for clothing according to any one of the above items ⁇ 1> to ⁇ 35>.
  • ⁇ 37> Water for use in preparation of washing water, comprising the steps of washing the article to be washed in contact with the washing water containing the powder detergent composition for clothes of the present invention and water, and rinsing the article to be washed with water.
  • / or the hardness of water used for rinsing is 1 ° DH or higher, preferably 2 ° DH or higher, more preferably 3 ° DH or higher, more preferably 5 ° DH or higher, more preferably 10 ° DH or higher.
  • the hand-washing washing method according to the above ⁇ 36> wherein it is 50 ° DH or less, preferably 30 ° DH or less. Examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.
  • LAS sodium dodecylbenzenesulfonate (manufactured by Kanto Chemical Co., Ltd., linear alkyl (carbon number 12) sodium benzenesulfonate)
  • C16AS linear alkyl sodium sulfate having an alkyl group with 16 carbon atoms (manufactured by Wako Pure Chemical Industries, Ltd.)
  • C12AS linear alkyl sodium sulfate having 12 alkyl groups (manufactured by Wako Pure Chemical Industries, Ltd.)
  • C14AS linear alkyl sodium sulfate having 14 alkyl groups (manufactured by Wako Pure Chemical Industries, Ltd.)
  • AES-Na (EO 2): polyoxyethylene (average number of moles added 2) sodium lauryl ether sulfate, Emar 270J (manufactured by Kao Corporation) ⁇
  • Sodium carbonate Dense ash (manufactured by Central Glass Co., Ltd.) ⁇
  • Sodium hydrogencarbonate ⁇ Amorphous sodium silicate: 43 mass% sodium silicate aqueous solution (manufactured by TOKUYAMA SIAM SILICA CO., LTD) Used to be. ⁇ Sodium sulfate: anhydrous neutral sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.) Sodium chloride: manufactured by Wako Pure Chemical Industries, Ltd. Sodium chlorideZeolite: Type A zeolite: “Zeobuilder” (Zeobuilder, median diameter: 3.0 ⁇ m)
  • the sieved product was a Fitzmill grinder (DKA- 6: manufactured by Hosokawa Micron).
  • the particles of Examples 1 to 10 and Comparative Examples 1 to 5 thus obtained had an apparent density measured by the above method of 700 to 1100 g / L, an average particle size measured by the method of 180 to 600 ⁇ m,
  • the pH (20 ° C.) of the 0.1 mass% aqueous solution measured by the method was 10-11.
  • the preliminarily warmed (60 ° C.) prepared oil (composition is shown below) is added dropwise to the neck using a dropper ( ⁇ : 2 mm) so that the amount becomes 3 g (about 0.33 g per sheet).
  • the underwear is poured into the washing liquid and left for 15 minutes in a completely immersed state. After leaving, the neck is attached to one undergarment and the neck is washed 50 times (converted to 1 time in one reciprocation (about 1 second) while rubbing the necks together). Thereafter, the underwear is taken out and squeezed 10 cm above the basin so that the moisture content of the underwear is about 100 to 140% of the underwear. Measure the bubble height immediately after squeezing 3 sheets. The measurement was performed by the following method.
  • model circular washbasin In each area where the model circular washbasin is divided into four parts (divided into four sectors), measure the foam height from the water surface, using a ruler, one place for each area, a total of four places. Calculate the average height. The same evaluation was performed by three people, and the average value of the three people was adopted.
  • the bubble height during washing is preferably 1.0 cm or more, more preferably 1.3 cm or more, and more preferably 1.6 cm or more.
  • the water content of the undergarment is squeezed 10 cm above the basin so that the moisture content of the undergarment is about 100 to 140% of the undergarment.
  • the condition of the rinse water immediately after rinsing and dehydration was observed, and points were given according to the following criteria to evaluate the rinsing properties and transparency. The same evaluation was performed by three people, and the average value of the three people was adopted.
  • the number of rinses will be repeated many times until the foam breaks or the rinse water is clear. Will increase. As a result, a large amount of water is consumed. From such a viewpoint, it is preferable that there are few bubbles at the time of rinsing or the rinsing water is transparent.
  • the rinsing properties and transparency are both preferably 3 points or less, and more preferably 2 points or less.
  • A Preparation oil used in the evaluation of foaming properties (mass% in artificial dirt is 0.44 mass% lauric acid, 3.15 mass% myristic acid, 2.35 mass% pentadecanoic acid, 6.31 palmitic acid) Wt%, heptadecanoic acid 0.44 wt%, stearic acid 1.6 wt%, oleic acid 7.91 wt%, triolein 13.33 wt%, n-hexadecyl palmitate 2.22 wt%, squalene 6.66 (Use in an amount of mass%)
  • B Hard water obtained by weighing 105 mg of calcium chloride (dihydrate) and dissolving in distilled water to obtain 1,000 ml C: 1.98% by mass of egg white lecithin liquid
  • ⁇ Cleaning conditions Dissolve the powder detergent composition in 1 L of 179 mg / L of hard water (prepared in the same manner as used in the evaluation of foaming properties) so that the total component (A) is 150 ppm.

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Abstract

L'invention concerne une composition détergente en poudre destinée aux vêtements, qui contient, dans des conditions spécifiques, (A) un agent tensioactif qui contient un sulfonate d'alkylbenzène à chaîne linéaire (A-1) et un sulfate d'alkyle (A-2), (B) un composé choisi parmi les carbonates et les silicates non cristallins, (C) un composé choisi parmi les sulfates et les chlorures de métal, et (D) un adjuvant inorganique spécifique séquestrant d'ion métallique polyvalent (D-1) et un adjuvant organique spécifique séquestrant d'ion métallique polyvalent (D-2). La composition contient un sulfate d'alkyle possédant 16 atomes de carbone ou plus dans le groupe alkyle en tant que composant (A-2).
PCT/JP2013/081467 2012-12-26 2013-11-22 Composition détergente en poudre destinée aux vêtements WO2014103583A1 (fr)

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MY194496A (en) * 2017-07-14 2022-11-30 Kao Corp Method for washing hard article

Citations (4)

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JPH1112593A (ja) * 1997-06-25 1999-01-19 Kao Corp 洗浄剤組成物
JP2011089107A (ja) * 2009-09-28 2011-05-06 Kao Corp 洗浄剤組成物
JP2013082889A (ja) * 2011-09-26 2013-05-09 Kao Corp 衣料用粉末洗剤組成物
JP2013100460A (ja) * 2011-10-14 2013-05-23 Kao Corp 衣料用粉末洗剤組成物及びその製造方法

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US4637890A (en) * 1986-01-23 1987-01-20 The Procter & Gamble Company Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone
JP2777129B2 (ja) * 1986-08-08 1998-07-16 花王株式会社 洗浄剤組成物
JPH01112593A (ja) * 1987-10-26 1989-05-01 Hitachi Ltd 半導体記憶装置
EP0495554A1 (fr) * 1991-01-16 1992-07-22 The Procter & Gamble Company Compositions de détergent contenant de la cellulase de haute activité et de composés d'ammonium quaternaire
US5756444A (en) * 1996-11-01 1998-05-26 The Procter & Gamble Company Granular laundry detergent compositions which are substantially free of phosphate and aluminosilicate builders
CN102471733A (zh) * 2009-07-27 2012-05-23 宝洁公司 洗涤剂组合物

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JPH1112593A (ja) * 1997-06-25 1999-01-19 Kao Corp 洗浄剤組成物
JP2011089107A (ja) * 2009-09-28 2011-05-06 Kao Corp 洗浄剤組成物
JP2013082889A (ja) * 2011-09-26 2013-05-09 Kao Corp 衣料用粉末洗剤組成物
JP2013100460A (ja) * 2011-10-14 2013-05-23 Kao Corp 衣料用粉末洗剤組成物及びその製造方法

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