WO2017061283A1 - Liquid detergent composition for clothing - Google Patents

Liquid detergent composition for clothing Download PDF

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Publication number
WO2017061283A1
WO2017061283A1 PCT/JP2016/077971 JP2016077971W WO2017061283A1 WO 2017061283 A1 WO2017061283 A1 WO 2017061283A1 JP 2016077971 W JP2016077971 W JP 2016077971W WO 2017061283 A1 WO2017061283 A1 WO 2017061283A1
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WO
WIPO (PCT)
Prior art keywords
component
mass
less
content
clothing
Prior art date
Application number
PCT/JP2016/077971
Other languages
French (fr)
Japanese (ja)
Inventor
杉山陽一
開麻衣
Original Assignee
花王株式会社
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to CN201680057439.5A priority Critical patent/CN108138094B/en
Publication of WO2017061283A1 publication Critical patent/WO2017061283A1/en

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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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase

Definitions

  • the present invention relates to a liquid detergent composition for clothing and a method for washing clothing.
  • 2014-62231 contains polyoxyethylene alkyl ether sulfate, two kinds of compounds having a specific hydrocarbon group and polyoxyalkylene group, and a water-soluble inorganic salt for increasing viscosity to increase viscosity. And a liquid detergent having excellent storage stability under low temperature conditions is described. Sodium sulfate and calcium chloride are disclosed as water-soluble inorganic salts.
  • JP 59-22998 discloses a polyoxyalkylene alkyl ether sulfate ester salt having 2 to 7 oxyethylene groups in the molecule, a protease, and an aminocarboxylic acid, and has excellent enzyme storage stability.
  • An enzyme-containing liquid detergent composition is disclosed.
  • JP-A-6-502197 discloses an enzyme-containing detergent containing an alkyl sulfate ester salt, a fatty acid, water, ethanol and glycerol as a solvent and having excellent enzyme stability.
  • the present invention provides a liquid detergent composition for clothing that has excellent detergency against dirt containing protein and that is excellent in protease stability in the liquid detergent composition for clothes.
  • the present inventors have found a technique for further improving the cleaning performance of soil containing proteins by protease during cleaning. Focusing on surfactants and inorganic salts among a wide variety of ingredients that make up liquid detergent compositions for clothing, alkyl sulfate salts and polyoxyalkylene alkyl ether sulfate salts having a specific structure are identified. It was found that when used in a mass ratio and in combination with a specific sulfate, the cleaning effect of soil containing proteins by proteases in the cleaning liquid increases. In addition, a certain amount of a specific sulfate salt can easily dissolve in a washing solution a protein whose molecular weight has been reduced by protease degradation. There was found.
  • Alkyl sulfate ester salt is a component that contributes to the improvement of detergency, but tends to affect the stability of the enzyme.
  • a liquid detergent composition can be prepared by blending a specific amount of polyoxyalkylene alkyl ether sulfate salt, nonionic surfactant and specific sulfate salt. It was found that the stability of proteases in the product can be improved. The present invention has been completed based on these findings.
  • the present invention comprises the following component (a), component (b), component (c), component (d), component (e) and water:
  • the total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less,
  • the content of the component is 2% by mass or more and 8% by mass or less,
  • the mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more and 10 or less in [(a) component content] / [(b) component content].
  • the present invention relates to a liquid cleaning composition for clothing.
  • R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms
  • AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms
  • n is 1 It is an integer of 20 or more and M is a cation.
  • Component Nonionic surfactant
  • Component One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate)
  • the present invention relates to the use of the liquid cleaning composition for clothing of the present invention for pickling washing.
  • the present invention also relates to a method for washing clothing comprising the following steps 1 to 3.
  • Step 1 Step of mixing the above-mentioned liquid cleaning composition for clothes of the present invention and water and clothing
  • Step 2 Step of submerging clothing in the immersion liquid after Step 1:
  • Step 3 Step After 2, the process of stirring and washing clothes in a cleaning liquid containing a cleaning composition for clothes and water
  • the present invention it is possible to obtain a liquid detergent composition for clothing having excellent detergency against dirt containing protein and excellent protease stability in the liquid detergent composition for clothes. Furthermore, the labor for stirring and washing the clothes after the clothes are immersed can be reduced by immersing the clothes in the cleaning liquid containing the liquid cleaning composition for clothes and water.
  • the component (a) is an alkyl sulfate salt having 10 to 18 carbon atoms.
  • the alkyl sulfate ester salt having 10 to 18 carbon atoms means an alkyl sulfate salt having an alkyl group having 10 to 18 carbon atoms.
  • the component has a dirt cleaning action due to its surface activity.
  • the component (a) when used in combination with the component (d) of the present invention, it is possible to enhance the protein soil cleaning action by the protease (e) component.
  • the component (a) enhances the cleaning activity of the soil containing protein by increasing the enzyme activity of the protease.
  • the number of carbon atoms of the alkyl group of the component (a) is preferably 10 or more and 16 or less from the viewpoint of enhancing the enzyme activity of the protease and enhancing the cleanability of soil containing protein. That is, the component (a) is preferably an alkyl sulfate ester salt having an alkyl group having 10 to 16 carbon atoms and a chain alkyl group.
  • Examples of the salt constituting the component (a) include alkali metal salts such as sodium and potassium, and alkanolamine salts having 2 to 6 carbon atoms in total. From the viewpoint of increasing the enzyme activity of the protease, an alkali metal salt is preferable, and a sodium salt is more preferable.
  • the component (b) is an alkyl ether sulfate salt represented by the following general formula (1).
  • R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms
  • AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms
  • n is 1 It is an integer of 20 or more and M is a cation.
  • R is preferably an alkyl group, and more preferably a chain alkyl group. Further, R is preferably from 10 to 16 carbon atoms from the viewpoint of improving detergency. R is preferably an alkyl group having 10 to 16 carbon atoms, and more preferably a chain alkyl group.
  • AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms.
  • examples of AO include one or more groups selected from an ethyleneoxy group and a propyleneoxy group.
  • n is an integer of 2 or more and 20 or less, AO can contain an ethyleneoxy group and a propyleneoxy group.
  • AO contains an ethyleneoxy group and a propyleneoxy group, either of them may be bonded to R—O—.
  • AO contains an ethyleneoxy group and a propyleneoxy group
  • the bonding mode of the ethyleneoxy group and the propyleneoxy group is bonded to either the random type or the block type, or the random type and the block type are mixed and bonded. It may be a thing.
  • AO is preferably an ethyleneoxy group.
  • n is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and even more preferably 1 from the viewpoint of improvement of detergency.
  • the liquid detergent composition for clothing of the present invention preferably contains a compound in which n in the general formula (1) is 1 or more, 3 or less, 1 or more, 2 or less, and 1 as the component (b).
  • the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is preferably 40% by mass or more, more preferably 50% by mass in all the components (b). % Or more, more preferably 55% by weight or more, further preferably 60% by weight or more, more preferably 65% by weight or more, and 100% by weight or less, preferably 90% by weight or less, more preferably 85% by weight. It is as follows.
  • the specific sulfate of the component (d) further improves the cleaning effect of the soil containing protein by the protease which is the component (e) of the present invention.
  • the ratio of the compound having n of 6 to 20 is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, and further 6% by mass or less.
  • 5% by mass or less is more preferable
  • 4% by mass or less is more preferable
  • 3% by mass or less is more preferable.
  • the lower limit of this ratio is 0% by mass or more.
  • the lower limit of this ratio is 0 mass% or more than 0 mass%.
  • the component ratio of the compound having different n in the general formula (1) in the component (b) is the same as that of the compound having different n in the compound in which the SO 3 M group in the general formula (1) is replaced with H.
  • a composition ratio can be adopted.
  • the area ratio obtained by analyzing the distribution of compounds with different n in the compound in which the SO 3 M group in the general formula (1) is replaced with H is regarded as a mass fraction.
  • the component (b) represented by the general formula (1) is available, when it is difficult to measure the composition ratio as it is, the component (b) is acid-decomposed to form a SO 3 M group.
  • a compound in which is replaced with H can be generated, and the constituent ratio of the different compounds in the compound can be used as the constituent ratio of the different compounds in the general formula (1) in the component (b).
  • the component (b) was obtained by acid decomposition to generate a compound in which the SO 3 M group was replaced with H, and then the distribution of n in the compound was analyzed by gas chromatography.
  • the area ratio is regarded as a mass fraction, and this can be used as a constituent ratio of the different compounds of n in the general formula (1) in the component (b).
  • Sample pretreatment 50 mg of a sample is placed in a 2 mL vial, 1 mL of a trimethylsilylating agent (manufactured by GL Sciences) is added and mixed, and reacted at 30 ° C. for 5 minutes.
  • a trimethylsilylating agent manufactured by GL Sciences
  • ⁇ Conditions for acid decomposition of component (b)> Place 4 g of sample into a 300 mL glass Erlenmeyer flask with a slit. 200 mL of 2N hydrochloric acid and zeolite were put into an Erlenmeyer flask, and an air-cooled tube with a thread was set. The Erlenmeyer flask is placed in a 140 ° C. oil bath and refluxed for 3 hours, and then cooled to 30 ° C. One drop of 1% phenolphthalein solution was added to the Erlenmeyer flask using a Pasteur pipette.
  • aqueous sodium hydroxide solution is added until the contents in the Erlenmeyer flask become a light pink color.
  • Transfer the contents to a 1000 mL separatory funnel add 200 mL petroleum ether and extract 3 times.
  • the petroleum ether layer is washed with 50 mL of a 10% aqueous sodium chloride solution three times, and then 20 g of anhydrous sodium sulfate is added for dehydration.
  • a solution obtained by removing anhydrous sodium sulfate by filtration is placed in a 500 mL triangle, and topped with petroleum ether.
  • M is a cation that forms a salt.
  • M include alkali metal ions such as sodium ions and potassium ions, and alkanol ammonium ions. From the viewpoint of enhancing the activity of the protease, M is preferably an alkali metal ion, more preferably a sodium ion.
  • the alkanol ammonium ion is preferably an alkanol ammonium ion having 2 to 6 carbon atoms in total.
  • the component (c) is a nonionic surfactant.
  • (C) It is thought that a component has the effect which improves the storage stability of the protease in the liquid cleaning composition for clothes.
  • a nonionic surfactant having a polyoxyalkylene group and a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 mol to 50 mol are preferable.
  • a nonionic surfactant represented by the following general formula (c1) is more preferable.
  • R 1c —O— (A′O) m —H (c1) [In the formula, R 1c is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. , M is the average added mole number of A′O, and is a number of 3 or more and 50 or less. ]
  • the number of carbon atoms of R 1c in the general formula (c1) is preferably 10 or more, more preferably 12 or more, and preferably 16 or less, from the viewpoint of further improving the cleaning performance of soil including protein soil.
  • the carbon number of R 1c in the general formula (c1) is preferably 10 or more, preferably 16 or less, and more preferably 14 or less in that the viscosity of the liquid cleaning composition for clothing of the present invention can be further reduced.
  • examples of the aliphatic hydrocarbon group represented by R 1c in the general formula (c1) include an aliphatic hydrocarbon group selected from an alkyl group and an alkenyl group, and an alkyl group is preferable.
  • M in the general formula (c1) is the average number of moles added of A′O, and is preferably 4 or more, and more preferably 5 or more in that the storage stability of the protease in the liquid detergent composition for clothing can be further improved. More preferably, 6 or more is still more preferable, and 7 or more is more preferable. M is preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, still more preferably 30 or less, and even more preferably 25 or less, in view of further improving the effect of the component (d) improving the protein stain detergency with protease.
  • A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms.
  • A′O includes, for example, one or more groups selected from an ethyleneoxy group and a propyleneoxy group.
  • A′O is preferably an alkyleneoxy group containing an ethyleneoxy group from the viewpoint that the storage stability of the protease in the liquid detergent composition for clothing can be further improved.
  • A′O is preferably an ethyleneoxy group.
  • the component (d) is one or more sulfates selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate).
  • the amount of the low molecular weight protein decomposed by the protease on the clothing and dispersed in the washing liquid from the clothing can be improved by the component (d).
  • the stability of protease in the liquid detergent composition for clothes can be improved by the component (d).
  • a compound represented by the following general formula (d1) is preferable from the viewpoint of further improving the cleanability of protein stains by protease.
  • n is an integer of 0 or more and 2 or less
  • x and y are each a number of 0 or more and 4 or less
  • x + y is 4, except when n is 0 and x is 4.
  • C n H 2n + 1 groups they may be the same or different.
  • the organic ammonium sulfate having 1 to 8 carbon atoms is monoethanolammonium sulfate, methylmonoethanolammonium sulfate, ethylmonoethanolammonium sulfate, methyldiethanolammonium, in order to further improve the effect of cleaning protein stains by protease.
  • One or more compounds selected from sulfate, ethyl diethanolammonium sulfate, diethanolammonium sulfate and triethanolammonium sulfate are preferred, and one or more compounds selected from monoethanolammonium sulfate and triethanolammonium sulfate are preferred. More preferred.
  • Inorganic sulfate (excluding calcium sulfate) is one selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate in order to further enhance the effect of washing protein stains by protease.
  • the above inorganic sulfates are preferred.
  • Examples of the alkali metal sulfate include lithium sulfate, sodium sulfate, and potassium sulfate.
  • Examples of the alkaline earth metal sulfate excluding calcium sulfate include magnesium sulfate.
  • an alkali metal sulfate is preferred because it has a high effect of dispersing protein stains decomposed on the clothing by the protease in the washing liquid.
  • the component (d) one or more sulfates selected from anhydrides and hydrates can be used. Accordingly, the component (d) is selected from organic ammonium sulfates having 1 to 8 carbon atoms, inorganic sulfates (excluding calcium sulfate), anhydrous sulfates, and sulfate hydrates. It can be one or more sulfates.
  • the component (d) is preferably one or more sulfates selected from inorganic sulfates (excluding calcium sulfate), and one selected from alkali metal sulfates and alkaline earth metal sulfates excluding calcium sulfate.
  • inorganic sulfates are more preferable, and one or more inorganic sulfates selected from alkali metal sulfates are more preferable.
  • the component (e) is a protease.
  • Preferred proteases include proteases that can act in neutral or alkaline aqueous solutions.
  • a preferred protease is an alkaline protease.
  • preferable protease examples include (e1) alkaline protease described in WO 99/018218, preferably 70% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 of the publication is conserved. (E2) Alkaline protease described in JP-A-5-25492, preferably alkaline protease K-16 or alkaline protease K-14.
  • proteases As proteases, (e3) products of Sabinase (registered trademark), Cannase (registered trademark), Everase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark) manufactured by Novozymes (E4) FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark), Duplex (registered trademark), Perfect Prime (produced by DuPont) (Registered Trademark), (e5) Alkaline protease manufactured by Kao Corporation, for example, KAP4.3G (Registered Trademark), KAP11.1G (Registered Trademark), (e6) Proteases or their variants supplied under these trade names Is mentioned.
  • protease examples include alkaline protease in which 80% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 described in International Publication No. 99/018218 is conserved, sabinase, everase, alcalase, dupon from Novozymes. More preferred are Pfect, Practical Prime, and alkaline protease manufactured by Kao Corporation.
  • the protease is more preferably sabinase from the viewpoint that the detergency can be further improved by combination with the component (a) or the component (b).
  • the protease of component (e) has an activity per gram of enzyme protein, that is, a specific activity, preferably 5000 mPU / g or more, more preferably 20000 mPU / g or more.
  • the specific activity of the protease is obtained by converting the activity unit of the protease measured by the following method per 1 g of the amount of the enzyme protein of the protease.
  • the activity unit of protease can be measured according to the method described in Examples.
  • the detergent composition for clothing of the present invention can contain a polyhydric alcohol having a valence of 2 to 6 as the component (f).
  • Component (f) can be further combined with component (c) and component (d) to further enhance the storage stability of protease in the liquid detergent composition for clothing.
  • Preferred compounds of the divalent alcohol include one or more compounds selected from ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol.
  • a preferred compound of a trivalent alcohol is glycerin.
  • a preferred compound of a tetravalent alcohol is pentaerythritol.
  • Preferable compounds of 5 to 6 valent alcohols include 5 to 6 valent sugar alcohols.
  • An example of the pentavalent sugar alcohol is xylitol.
  • Examples of the hexavalent sugar alcohol include sorbitol and mannitol.
  • the component (f) is preferably at least one compound selected from propylene glycol, glycerin, diethylene glycol, triethylene glycol, and sorbitol, and can be selected from propylene glycol, glycerin, and sorbitol, because the storage stability of the protease can be further improved.
  • One or more compounds are preferred.
  • the detergent composition for clothing of the present invention can contain a calcium ion donor as the component (g).
  • the component (g) is a compound having a property of ion dissociation in water, and is used as a protease stabilizer.
  • the component (g) is preferably composed of an inorganic compound, and specific examples include calcium chloride.
  • the liquid detergent composition for clothes of the present invention is excellent in the cleaning power of dirt containing protein adhering to clothes by enhancing the cleaning effect of dirt containing protein due to protease. Furthermore, in the cleaning liquid prepared from the liquid cleaning composition for clothing of the present invention, the storage stability of protease is excellent.
  • the content of the component (a) and the component (b) in the liquid detergent composition for clothing of the present invention is a value obtained by converting a counter ion, that is, a cation forming a salt, into sodium, that is, converted into a sodium salt. Shall be used.
  • the total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less.
  • the total content of the component (a) component and the component (b) content in the liquid detergent composition for clothing of the present invention is preferably from the standpoint of further enhancing the cleanability of soil containing protein. It is 6 mass% or more, More preferably, it is 7 mass% or more, More preferably, it is 8 mass% or more, More preferably, it is 9 mass% or more.
  • the total content of the content of the component (a) and the content of the component (b) in the liquid detergent composition for clothing of the present invention is more stable in storage stability of the liquid detergent composition for clothing. In terms of improvement, it is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.
  • mass ratio of content of (a) component and content of (b) component is content of (a) component / content of (b) component Thus, it is 0.5 or more and 10 or less.
  • the mass ratio between the content of the component (a) and the content of the component (b) is such that the effect of enhancing the specific sulfate salt as the component (d) enhances the cleaning effect of the soil containing proteins by protease.
  • the content of the component (a) / the content of the component (b) is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, still more preferably 0.65 or more, still more preferably 0.
  • the mass ratio of the content of the component (a) to the content of the component (b) is such that the storage stability of the protease in the detergent composition for clothing of the present invention is further increased.
  • a mixture containing the component (a) and the component (b) can be used as a supply source for the component (a) and the component (b) in preparing the liquid detergent composition for clothing.
  • a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 18 carbon atoms and having a known structure and ratio of the compound can be mentioned.
  • the polyoxyalkylene alkyl ether sulfate ester salt is generally obtained by subjecting an alkylene oxide adduct of alcohol to sulfate esterification, and is obtained as a mixture of compounds having different addition mole numbers of alkylene oxide. Therefore, it can be a mixture containing the components (a) and (b) of the present invention.
  • the liquid detergent composition for clothing of the present invention is characterized in that the storage stability of the protease in the liquid detergent composition for clothing is further improved and the washing property of soil containing protein is further improved.
  • the mass ratio of the content and the total content of the component (a) and the component (b) is (c) component content / [(a) component content + (b) Component content] is preferably 0.02 or more and 2 or less.
  • the mass ratio (c) component content / [(a) component content + (b) component content] is preferably 0.04 or more, and 0.06
  • the above is more preferable, 0.08 or more is further preferable, 0.1 or more is further preferable, and 0.12 or more is further preferable.
  • the mass ratio (c) component content / [(a) component content + (b) component content] is preferably 1.8 or less in view of further improving the cleaning performance of soil containing protein.
  • .6 or less is more preferable, 1.4 or less is further preferable, 1.2 or less is further preferable, 1.0 or less is further preferable, 0.8 or less is further preferable, 0.6 or less is further preferable, 0.4 The following is more preferable.
  • the content of the component (d) is 2% by mass or more and 8% by mass or less.
  • the content of the component (d) in the liquid detergent composition for clothing of the present invention is to increase the washing rate of dirt by increasing the solubility of the protein, which has been reduced in molecular weight by the action of protease, in the washing solution.
  • it is 2.2% by mass or more, more preferably 2.4% by mass or more, further preferably 2.6% by mass or more, further preferably 2.8% by mass or more, and further preferably 3% by mass or more.
  • It is preferably 7% by mass or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less from the viewpoint of further enhancing the storage stability of the protease in the liquid detergent composition for clothing.
  • the content of the component (d) in the liquid detergent composition for clothing of the present invention is preferably 1.4% by mass or more, more preferably 1.5% by mass or more, and still more preferably 1 as sulfate ions. .6% by weight or more, more preferably 1.7% by weight or more, more preferably 1.8% by weight or more, more preferably 1.9% by weight or more, more preferably 2.0% by weight or more, and Preferably it is 7 mass% or less, More preferably, it is 6 mass% or less, More preferably, it is 5.5 mass% or less, More preferably, it is 4.0 mass% or less, More preferably, it is 3.5 mass% or less.
  • the content of the component (e) in the liquid detergent composition for clothing of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1 as the amount of enzyme protein. It is at most mass%, more preferably at most 0.8 mass%, still more preferably at most 0.5 mass%.
  • the amount of enzyme protein of component (e) is determined according to the method of Lowry et al. (Lowry, OH et al., J. Biol. Chem., 193, 265 (1951)). It is expressed in terms of serum albumin (Bovine Serum Albumin, manufactured by SIGMA, product number A-7030).
  • the content of the component (f) is preferably 0.2% by mass or more and 10% by mass or less in the composition.
  • the content of the component (f) is more preferably 0.4% by mass or more, and still more preferably 0.6% by mass, in that the storage stability of the protease in the detergent composition for clothing is further improved.
  • the content of the component (g) is 0.01 mass% or more and 0.15 mass% or less in the composition as calcium ions. preferable.
  • the content of the component (g) is preferably 0.02% by mass or more, more preferably 0.03% by mass or more in the composition as calcium ions.
  • the content of the component (g) is preferably 0.12% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.1% by mass or less in the composition as calcium ions. It is 08 mass% or less.
  • the liquid detergent composition for clothes of the present invention has a pH of 4 or more and 10 or less at 25 ° C.
  • This pH is preferably 4.5 or more, more preferably 5.0 or more, still more preferably 5.5 or more, and still more preferably, in terms of excellent storage stability of protease in the liquid detergent composition for clothing.
  • the pH can be measured using a pH meter using a glass electrode.
  • the following components (i) to (v) can be blended as other components in an amount that does not impair the effects of the present invention.
  • (I) Anti-staining agent and dispersant i) As the component, polyacrylic acid, polymaleic acid, and claim 1-21 of JP-A-59-62614 (page 1, column 3, line 5 to page 3, 4) Column 14 line) and a recontamination preventive agent and a dispersant such as a polymer.
  • the component (i) is preferably polyacrylic acid, polymaleic acid or a salt thereof, more preferably polyacrylic acid or a salt thereof.
  • the content of the component (i) in the garment cleaning composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably Is 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
  • Fluorescent dye examples include fluorescent dyes commercially available as Chino Pearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
  • (Iii) Monovalent to trivalent alcohol having 1 to 6 carbon atoms
  • the component include one or more alcohols selected from ethanol, ethylene glycol, propylene glycol and glycerin.
  • the content of (iii) in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, Preferably it is 5 mass% or less.
  • the surfactant (v) for example, a surfactant selected from fatty acids having 10 to 18 carbon atoms or salts thereof can be contained.
  • the content of the fatty acid having 10 to 18 carbon atoms or a salt thereof is the total content of the component (a), the component (b) and the component (c).
  • it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.
  • a lower limit is 0 mass% or more than 0 mass%.
  • the content of the fatty acid salt is calculated by the mass obtained by replacing the cation as a counter ion with a hydrogen ion, that is, the mass converted to an acid type compound.
  • an amine oxide having one alkyl group having 10 to 16 carbon atoms can be contained. Specifically, an amine oxide having one alkyl group having 10 to 16 carbon atoms and two groups selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms is given. It is done.
  • liquid detergent composition for clothing described above is suitable for use in a liquid detergent for clothing.
  • the liquid detergent composition for clothing of the present invention is suitable for use in pickling laundry.
  • the liquid detergent composition for clothes of the present invention is suitably used for soaking and washing as a washing liquid mixed with water.
  • the soaking and laundering means a washing method in which clothes are soaked in a washing solution for a certain period of time.
  • the clothes and the cleaning liquid are mixed and washed by stirring manually or by mechanical force such as a washing machine.
  • an operation of rubbing clothing using a tool such as a brush is performed.
  • Step 1 A liquid cleaning composition for clothing of the present invention and a dipping solution containing water and a clothing are mixed
  • Step 2 A step after Step 1 in which clothing is immersed in the dipping solution
  • Step 3 Step 2 After, the step of stirring and washing the clothes in a cleaning solution containing a cleaning composition for clothes and water
  • Step 1 is a step of mixing the liquid cleaning composition for clothing of the present invention and an immersion liquid containing water with clothing.
  • the concentration of the liquid detergent composition for clothing in the immersion liquid obtained by mixing the liquid detergent composition for clothing of the present invention and water is preferably 2.5 g from the viewpoint of detergency. / L or more, more preferably 3 g / L or more, still more preferably 3.5 g / L or more.
  • the concentration of the liquid detergent composition for clothing in the immersion liquid is preferably 10 g / L or less, more preferably 8 g / L or less, and still more preferably 6 g / L or less from the viewpoint of rinsing properties.
  • Water used in step 1 can be water having a German hardness of 1 ° DH to 30 ° DH.
  • German hardness is 1 ° DH or higher, 3 ° DH or higher, 5 ° DH or higher, 6 ° DH or higher, 8 ° or higher due to the fact that it can realize the effect of excellent cleaning performance of soil containing protein.
  • Water of DH or higher, further 9 ° DH or higher, and further 10 ° DH or higher can be used.
  • water having a German hardness of 30 ° DH or less, further 25 ° DH or less, and further 20 ° DH or less can be used.
  • Hardness represents the total hardness determined by chelate titration method using ethylenediaminetetraacetic acid disodium salt.
  • the ratio (hereinafter referred to as bath ratio) of the volume (liter) of the immersion liquid obtained by mixing the liquid cleaning composition for clothing of the present invention and water and the mass (kg) of the clothing is as follows. From the viewpoint of ease of washing at the time of hand washing, [capacity of washing liquid (liter)] / [mass of clothing (kg)] is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, 5 or more is more preferable. From the viewpoint of detergency, the bath ratio is preferably 100 or less, preferably 90 or less, preferably 20 or less, and more preferably 10 or less.
  • an immersion liquid obtained by previously mixing water and the liquid cleaning composition for clothing of the present invention may be mixed with clothing. Moreover, you may mix the water containing the clothing which mixed clothing and water, and the liquid cleaning composition for clothing of this invention. At this time, the immersion liquid is formed by mixing water containing clothing and the liquid cleaning composition for clothing of the present invention. Moreover, you may mix clothing, water, and the liquid cleaning composition for clothing of this invention simultaneously. At this time, an immersion liquid is formed by mixing water and the liquid cleaning composition for clothing of the present invention.
  • Step 2 is a step of immersing clothing in the immersion liquid after Step 1 described above.
  • the time for immersing the clothes is preferably 10 minutes or more, more preferably 20 minutes or more, from the viewpoint of the ability to clean the soil containing protein, or from the viewpoint of reducing the labor required for Step 3 described later. . 120 minutes or less are preferable and 60 minutes or less are more preferable in terms of shortening the time required for washing.
  • the time for immersing the clothes is the time when the liquid cleaning composition for clothes of the present invention, water, and clothes are mixed in a mass necessary for one washing, and stirring and washing in step 3 is started. Say time to.
  • Step 3 is a step of stirring and washing the garment after the step 2 in a washing liquid containing a garment cleaning composition and water.
  • the stirring cleaning means that the clothes and the cleaning liquid are stirred manually or mechanically such as a washing machine to wash the clothes. Washing and washing clothes and cleaning solution manually is to wash the clothing in the cleaning solution, wash the clothing by rubbing the clothing containing the cleaning solution together, and rub the clothing containing the cleaning solution with a tool such as a brush. It means washing the clothes by washing the clothes and the clothes by manually rotating and reciprocating the clothes to wash the clothes, and manually compressing the clothes in the washing liquid a plurality of times.
  • the garment cleaning composition used in step 3 may be the garment liquid cleaning composition of the present invention.
  • the cleaning composition for clothing used in Step 3 may be a cleaning composition for clothing that is different from the liquid cleaning composition for clothing of the present invention.
  • the liquid cleaning composition for clothing of the present invention is preferable as the clothing cleaning composition used in Step 3 in that it further enhances the cleaning action of the soil including protein soil caused by protease.
  • ⁇ 1> Contains the following (a) component, (b) component, (c) component, (d) component, (e) component and water,
  • the total content of component (a) and component (b) is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, and still more preferably 8% by mass or more. More preferably, it is 9% by mass or more and 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and further preferably 20% by mass or less.
  • the content of the component (d) is 2% by mass or more, preferably 2.2% by mass or more, more preferably 2.4% by mass or more, still more preferably 2.6% by mass or more, and further preferably 2.8% by mass. Or more, more preferably 3% by mass or more, and 8% by mass or less, preferably 7% by mass or less, more preferably 6% by mass or less, still more preferably 5% by mass or less,
  • the mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more, preferably 0.00 in terms of the content of the component (a) / the content of the component (b).
  • R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms
  • AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms
  • n is 1 It is an integer of 20 or more and M is a cation.
  • Component Nonionic surfactant
  • Component One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate)
  • the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more in all the components (b). More preferably, it is 60% by mass or more, more preferably 65% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, described in ⁇ 1> or ⁇ 2>.
  • Liquid detergent composition for clothing is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more in all the components (b). More preferably, it is 60% by mass or more, more preferably 65% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, described in ⁇ 1> or ⁇ 2>.
  • Liquid detergent composition for clothing is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more in all the components (b
  • the ratio of the compound in which n is 6 or more and 20 or less is 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, and still more preferably in all the components (b). 7% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and 0% by mass or more or more than 0% by mass.
  • the liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 3>, wherein the composition is 0% by mass.
  • the mass ratio of the content of (c) component and the total content of (a) component and (b) component is (c) component content / [(a) component content Amount + content of component (b)] is 0.02 or more, preferably 0.04 or more, more preferably 0.06 or more, still more preferably 0.08 or more, still more preferably 0.1 or more, and still more preferably.
  • liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 4>, preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.4 or less.
  • the component (c) is a nonionic surfactant having a polyoxyalkylene group, and further a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 mol to 50 mol, ⁇ 1> to ⁇ 5 >
  • it is 40 or less, More preferably, it is 35 or less, More preferably, it is 30 or less, More preferably, it is 25 or less, More preferably, it is 20 or less, More preferably, it is 18 or less, More preferably, it is 16 or less.
  • the number is preferably 12 or less.
  • the organic ammonium sulfate having 1 to 8 carbon atoms as a component is a compound represented by the following general formula (d1), for clothing according to any one of ⁇ 1> to ⁇ 9> Liquid detergent composition.
  • d1 Liquid detergent composition.
  • n is an integer of 0 or more and 2 or less
  • x and y are each a number of 0 or more and 4 or less
  • x + y is 4, except when n is 0 and x is 4.
  • there are a plurality of C n H 2n + 1 groups they may be the same or different.
  • the compound represented by the general formula (d1) is monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, diethanol ammonium sulfate, and
  • the liquid detergent composition for clothes according to ⁇ 10> which is one or more compounds selected from triethanolammonium sulfate.
  • the component inorganic sulfate (excluding calcium sulfate) is one or more inorganic sulfates selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate.
  • the liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 11>.
  • the alkali metal sulfate is at least one selected from lithium sulfate, sodium sulfate and potassium sulfate, and the alkaline earth metal sulfate excluding calcium sulfate is at least one inorganic sulfate selected from magnesium sulfate.
  • the content of the component (d) as sulfate ions is 1.4% by mass or more, preferably 1.5% by mass or more, more preferably 1.6% by mass or more, still more preferably 1.7% by mass or more, Preferably 1.8% by mass or more, more preferably 1.9% by mass or more, further preferably 2.0% by mass or more, and 7% by mass or less, preferably 6% by mass or less, more preferably 5.5% by mass. %, More preferably 4.0% by mass or less, and further preferably 3.5% by mass or less, The liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 13>.
  • liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 14>, which further contains a dihydric or higher polyvalent alcohol having 2 to 8 carbon atoms as a component (f). .
  • the component (f) is at least one compound selected from ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, and sugar alcohols having a valence of 5 to 6.
  • a liquid detergent composition for clothes according to ⁇ 15> which is at least one compound selected from sorbitol and sorbitol.
  • the content of the component (f) is 0.2% by mass or more, preferably 0.4% by mass or more, more preferably 0.6% by mass or more, still more preferably 0.8% by mass or more, and 10% by mass.
  • component (g) a calcium ion donor is contained, and the content of component (g) is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% as calcium ions.
  • the pH of the liquid detergent composition for use at 25 ° C. measured with a pH meter using a glass electrode is 4 or more, preferably 4.5 or more, more preferably 5.0 or more, and still more preferably 5 0.5 or more, more preferably 6.0 or more, more preferably 6.5 or more, more preferably 7.0 or more, more preferably 7.5 or more, more preferably 8.0 or more, and 10 or less, preferably
  • the liquid detergent composition for clothing according to any one of ⁇ 1> to ⁇ 19>, wherein is 9.8 or less, more preferably 9.5 or less.
  • Step 1 Mixing the liquid cleaning composition for clothing according to any one of ⁇ 1> to ⁇ 20> and an immersion liquid containing water
  • Step 2 Step 1 after the immersion Step 3 of immersing clothing in liquid
  • Step 3 Step of stirring and washing clothing in a cleaning solution containing a cleaning composition for clothing and water after Step 2
  • Example 1 to 19 A liquid detergent composition for clothing shown in Table 2 was prepared using the following components, and the cleaning power and enzyme activity stability were evaluated by the following methods using the obtained composition. The results are shown in Table 2.
  • the pH of the composition was adjusted with monoethanolamine or citric acid. A pH meter using a glass electrode was used for pH measurement.
  • Component (a) and component (b)-(a-1) Sodium lauryl sulfate ester, corresponding to component (a).
  • (Ab-1) a surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-1) is 50.3% by mass Yes, the content of component (b) is 49.7% by mass
  • (Ab-2) a surfactant mixture containing the components (a) and (b) in the composition of Table 1, and the content of the component (a) in (ab-2) is 30.5% by mass Yes, the content of component (b) is 69.5% by mass
  • (Ab-3) a surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-3) is 19.0% by mass.
  • content of component (b) is 81% by mass
  • Component (d ′) Comparison compound of component (d) (d′-1): sodium chloride (d′-2): sodium carbonate
  • E Component (e-1); Sabinase Ultra 16L (manufactured by Novozyme) (E-2); alkaline protease (KAP, manufactured by Kao Corporation)
  • (G) Component / (g-1) Calcium chloride.
  • the content of calcium ions in 1 mol of calcium chloride is 36% by mass.
  • the detergency was determined by measuring the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after washing with a self-recording colorimeter (Shimadzu Corporation), and obtaining the washing rate (%) by the following formula.
  • the table shows the average value of the washing rate of the four artificially contaminated cloths. A higher cleaning rate is preferred. In this evaluation, it can be recognized more clearly that the average value of the cleaning rate is 55% or more, which is superior to a cleaning composition having a cleaning power at a general level.
  • (a) / (b) is a mass ratio of [content of (a) component] / [content of (b) component], and (c) / [(a) + (b) ] Is a mass ratio of (c) component content / [(a) component content + (b) component content].
  • the content of the component (a) and the content of the component (b) are the sum of the content based on the composition in Table 1 and the content in (a-1) in Table 2, 2 below the decimal point. The value rounded to the first digit is shown.
  • required from the value is shown.
  • the number in parentheses of the component (d) is mass% as sulfate ion.
  • the mass% of the component (e) is mass% as the amount of enzyme protein.
  • the number in parentheses of the component (g) is mass% as calcium ions. These are the same in Table 3.
  • Comparative Example 7 does not contain the component (d), and is represented by a mass ratio between the content of the component (a) and the content of the component (b) in the liquid cleaning composition for clothing.
  • (A) / (b) is a composition outside the scope of the present invention.
  • (a) / (b) is outside the scope of the present invention and (d) the cleaning rate of the composition of Comparative Example 7 not containing the component, and (a) / (b) are outside the scope of the present invention.
  • the difference in the cleaning rate from the cleaning rate of Comparative Example 1 containing the component (d) is 2%, and the improvement in the cleaning rate due to the inclusion of the component (d) is low.

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Abstract

The present invention is a liquid detergent composition for clothing and contains: (a) an alkyl sulfuric acid ester salt having 10-18 carbon atoms; (b) an alkyl ether sulfuric acid ester salt represented by general formula (1); (c) a nonionic surfactant; (d) at least one sulfuric acid salt selected from organic ammonium sulfuric acid salts having 1-8 carbon atoms, and inorganic sulfuric acid salts (excluding calcium sulfate); (e) a protease; and water, wherein the total of the contained amount of (a) and the contained amount of (b) is 5-40 mass%, the contained amount of (d) is 2-8 mass%, and the mass ratio of (contained amount of (a)/contained amount of (b)) is 0.5-10. R-O-(AO)n-SO3M (1) (in the formula, R represents an aliphatic hydrocarbon group having 10-18 carbon atoms, AO represents an alkyleneoxy group selected from alkyleneoxy groups having 2 carbon atoms and alkyleneoxy groups having 3 carbon atoms, n represents an integer of 1-20, and M represents a cation.)

Description

衣料用液体洗浄剤組成物Liquid detergent composition for clothing
　本発明は、衣料用液体洗浄剤組成物、及び衣料の洗浄方法に関する。 The present invention relates to a liquid detergent composition for clothing and a method for washing clothing.
背景技術
　消費者は洗濯仕上がりの評価として、襟、袖の汚れ落ちを特に強く意識している。襟汚れや袖の汚れには皮脂と共にタンパク質も含まれている事が知られている。襟、袖の汚れ落ちを向上させた液体洗浄剤として、タンパク質を直接分解するプロテアーゼを含有する組成物が知られている。
　例えば、特開２００１－５２４５９１号公報には、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、プロテアーゼ、脂肪酸、及び硫酸ナトリウムによって特徴づけられる構造化剤を含有し、優秀なクリーニング及び望ましいレオロジーを与えるゲル洗濯洗剤組成物が開示されている。
　特開２０１４－６２２３１号公報には、ポリオキシエチレンアルキルエーテル硫酸塩、特定の炭化水素基とポリオキシアルキレン基を有する２種の化合物、粘度増加の為の水溶性無機塩を含有し、粘度増加が図れ、かつ低温条件での保存安定性に優れた液体洗浄剤が記載されている。水溶性無機塩として硫酸ナトリウムや塩化カルシウムが開示されている。
　特開昭５９－２２９９８号公報には、分子内にオキシエチレン基を２～７個有するポリオキシアルキレンアルキルエーテル硫酸エステル塩、プロテアーゼ、アミノカルボン酸を含有し、酵素の保存安定性に優れた、酵素含有液体洗浄剤組成物が開示されている。
　特開平６－５０２１９７号公報には、アルキル硫酸エステル塩、脂肪酸、溶媒として水とエタノールとグリセロールを含有し、酵素の安定性に優れた、酵素を含有する洗剤が開示されている。 BACKGROUND ART Consumers are particularly conscious of removing dirt from their collars and sleeves as an evaluation of their laundry finish. It is known that collar stains and sleeve stains contain protein as well as sebum. A composition containing a protease that directly degrades proteins is known as a liquid cleaning agent that improves the removal of stains on collars and sleeves.
For example, Japanese Patent Application Laid-Open No. 2001-524591 discloses a gel laundry detergent containing a structuring agent characterized by polyoxyalkylene alkyl ether sulfate, protease, fatty acid, and sodium sulfate and providing excellent cleaning and desirable rheology A composition is disclosed.
Japanese Patent Application Laid-Open No. 2014-62231 contains polyoxyethylene alkyl ether sulfate, two kinds of compounds having a specific hydrocarbon group and polyoxyalkylene group, and a water-soluble inorganic salt for increasing viscosity to increase viscosity. And a liquid detergent having excellent storage stability under low temperature conditions is described. Sodium sulfate and calcium chloride are disclosed as water-soluble inorganic salts.
JP 59-22998 discloses a polyoxyalkylene alkyl ether sulfate ester salt having 2 to 7 oxyethylene groups in the molecule, a protease, and an aminocarboxylic acid, and has excellent enzyme storage stability. An enzyme-containing liquid detergent composition is disclosed.
JP-A-6-502197 discloses an enzyme-containing detergent containing an alkyl sulfate ester salt, a fatty acid, water, ethanol and glycerol as a solvent and having excellent enzyme stability.
発明の概要
　特開２００１－５２４５９１号公報、特開２０１４－６２２３１号公報、特開昭５９－２２９９８号公報、特開平６－５０２１９７号公報のいずれにも、液体洗浄剤組成物中でのプロテアーゼの安定性と洗浄時のプロテアーゼによるタンパク汚れの洗浄性とを、より高めて両立する技術に関する記載はない。 SUMMARY OF THE INVENTION In any of JP-A-2001-524591, JP-A-2014-62231, JP-A-59-22998, and JP-A-6-502197, a protease in a liquid detergent composition is used. There is no description on a technique for further improving both stability and cleanability of protein stains by protease during washing.
　本発明は、タンパク質を含む汚れに対する洗浄力に優れ、衣料用液体洗浄剤組成中でのプロテアーゼの安定性に優れた衣料用液体洗浄剤組成物を提供する。 The present invention provides a liquid detergent composition for clothing that has excellent detergency against dirt containing protein and that is excellent in protease stability in the liquid detergent composition for clothes.
　本発明者らは、検討を重ねた結果、洗浄時のプロテアーゼによるタンパク質を含む汚れの洗浄性をより高める技術を見出した。
　衣料用液体洗浄剤組成物を構成する多種多様な成分の中から、界面活性剤と無機塩に着目したところ、アルキル硫酸エステル塩と特定の構造を有するポリオキシアルキレンアルキルエーテル硫酸エステル塩を特定の質量比で使用し、且つ特定の硫酸塩を併用すると、洗浄液中でのプロテアーゼによるタンパク質を含む汚れの洗浄効果が増大する事が判明した。
　また、一定量の特定の硫酸塩が、プロテアーゼによる分解により低分子量化されたタンパク質を、洗浄液中に溶けやすくすることで、タンパク質を含む襟、袖の汚れ落ちに顕著な効果が発揮されることが判明した。
　また、アルキル硫酸エステル塩は、洗浄力の向上に寄与する成分であるが、酵素の安定性に影響を及ぼす傾向がある。しかし、本発明では、そのようなアルキル硫酸エステル塩を含有しても、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、非イオン界面活性剤及び特定の硫酸塩を特定量配合することで、液体洗浄剤組成物中のプロテアーゼの安定性を向上できる事を見出した。
　本発明は、これらの知見に基づき完成されたものである。 As a result of repeated studies, the present inventors have found a technique for further improving the cleaning performance of soil containing proteins by protease during cleaning.
Focusing on surfactants and inorganic salts among a wide variety of ingredients that make up liquid detergent compositions for clothing, alkyl sulfate salts and polyoxyalkylene alkyl ether sulfate salts having a specific structure are identified. It was found that when used in a mass ratio and in combination with a specific sulfate, the cleaning effect of soil containing proteins by proteases in the cleaning liquid increases.
In addition, a certain amount of a specific sulfate salt can easily dissolve in a washing solution a protein whose molecular weight has been reduced by protease degradation. There was found.
Alkyl sulfate ester salt is a component that contributes to the improvement of detergency, but tends to affect the stability of the enzyme. However, in the present invention, even when such an alkyl sulfate salt is contained, a liquid detergent composition can be prepared by blending a specific amount of polyoxyalkylene alkyl ether sulfate salt, nonionic surfactant and specific sulfate salt. It was found that the stability of proteases in the product can be improved.
The present invention has been completed based on these findings.
　本発明は、下記（ａ）成分、（ｂ）成分、（ｃ）成分、（ｄ）成分、（ｅ）成分及び水を含有し、
　（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量が５質量％以上４０質量％以下であり、
　（ｄ）成分の含有量が２質量％以上８質量％以下であり、
　（ａ）成分の含有量と（ｂ）成分の含有量との質量比が、〔（ａ）成分の含有量〕／〔（ｂ）成分の含有量〕で０．５以上１０以下である、
衣料用液体洗浄剤組成物に関する。
（ａ）成分：炭素数１０以上１８以下のアルキル硫酸エステル塩
（ｂ）成分：下記一般式（１）で表されるアルキルエーテル硫酸エステル塩
　　Ｒ－Ｏ－（ＡＯ）ｎ－ＳＯ３Ｍ　　（１）
〔式中、Ｒは炭素数１０以上１８以下の脂肪族炭化水素基であり、ＡＯは炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｎは１以上２０以下の整数であり、Ｍは陽イオンである。〕
（ｃ）成分：ノニオン界面活性剤
（ｄ）成分：炭素数１以上８以下の有機アンモニウム硫酸塩、及び無機硫酸塩（但し、硫酸カルシウムを除く）から選ばれる１種以上の硫酸塩
（ｅ）成分：プロテアーゼ The present invention comprises the following component (a), component (b), component (c), component (d), component (e) and water:
The total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less,
(D) The content of the component is 2% by mass or more and 8% by mass or less,
The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more and 10 or less in [(a) component content] / [(b) component content].
The present invention relates to a liquid cleaning composition for clothing.
Component (a): Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) n —SO 3 M (1 )
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
(C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease
　また、本発明は、上記本発明の衣料用液体洗浄剤組成物の、漬け置き洗濯への使用に関する。 Also, the present invention relates to the use of the liquid cleaning composition for clothing of the present invention for pickling washing.
　また、本発明は、下記工程１～３を含む衣料の洗浄方法に関する。
工程１：上記本発明の衣料用液体洗浄剤組成物及び水を含有する浸漬液と、衣料とを混合する工程
工程２：工程１の後に、前記浸漬液に衣料を漬け置く工程
工程３：工程２の後に、衣料用洗浄剤組成物と水を含む洗浄液中で、衣料を撹拌洗浄する工程 The present invention also relates to a method for washing clothing comprising the following steps 1 to 3.
Step 1: Step of mixing the above-mentioned liquid cleaning composition for clothes of the present invention and water and clothing Step 2: Step of submerging clothing in the immersion liquid after Step 1: Step 3: Step After 2, the process of stirring and washing clothes in a cleaning liquid containing a cleaning composition for clothes and water
　本発明によれば、タンパク質を含む汚れに対する洗浄力に優れ、衣料用液体洗浄剤組成中でのプロテアーゼの安定性に優れた衣料用液体洗浄剤組成物を得ることができる。更には、前記衣料用液体洗浄剤組成物と水を含む洗浄液に衣料を漬け置くことで、衣料を漬け置いた後に衣料を撹拌洗浄する労力を低減することができる。 According to the present invention, it is possible to obtain a liquid detergent composition for clothing having excellent detergency against dirt containing protein and excellent protease stability in the liquid detergent composition for clothes. Furthermore, the labor for stirring and washing the clothes after the clothes are immersed can be reduced by immersing the clothes in the cleaning liquid containing the liquid cleaning composition for clothes and water.
発明を実施するための形態
＜（ａ）成分＞
　（ａ）成分は、炭素数１０以上１８以下のアルキル硫酸エステル塩である。炭素数１０以上１８以下のアルキル硫酸エステル塩とは、炭素数が１０以上１８以下のアルキル基を有するアルキル硫酸エステル塩を意味する。 MODE FOR CARRYING OUT THE INVENTION <Component (a)>
The component (a) is an alkyl sulfate salt having 10 to 18 carbon atoms. The alkyl sulfate ester salt having 10 to 18 carbon atoms means an alkyl sulfate salt having an alkyl group having 10 to 18 carbon atoms.
　（ａ）成分は、界面活性能による汚れの洗浄作用を有する。また、（ａ）成分は、本発明の（ｄ）成分と併用することで、（ｅ）成分であるプロテアーゼによるタンパク汚れの洗浄作用を増強することができる。また、（ａ）成分がプロテアーゼの酵素活性を高めることでタンパク質を含む汚れの洗浄作用を高めていると考えている。 (A) The component has a dirt cleaning action due to its surface activity. In addition, when the component (a) is used in combination with the component (d) of the present invention, it is possible to enhance the protein soil cleaning action by the protease (e) component. In addition, it is considered that the component (a) enhances the cleaning activity of the soil containing protein by increasing the enzyme activity of the protease.
　プロテアーゼの酵素活性を高め、タンパク質を含む汚れの洗浄性を高める点で、（ａ）成分が有するアルキル基の炭素数は１０以上１６以下が好ましい。すなわち、（ａ）成分は、炭素数１０以上１６以下のアルキル基、更に鎖式アルキル基を有するアルキル硫酸エステル塩が好ましい。 The number of carbon atoms of the alkyl group of the component (a) is preferably 10 or more and 16 or less from the viewpoint of enhancing the enzyme activity of the protease and enhancing the cleanability of soil containing protein. That is, the component (a) is preferably an alkyl sulfate ester salt having an alkyl group having 10 to 16 carbon atoms and a chain alkyl group.
　（ａ）成分を構成する塩は、ナトリウム、カリウムなどのアルカリ金属塩、総炭素数２以上６以下のアルカノールアミン塩などが挙られる。プロテアーゼの酵素活性を高める観点から、アルカリ金属塩が好ましく、ナトリウム塩がより好ましい。 Examples of the salt constituting the component (a) include alkali metal salts such as sodium and potassium, and alkanolamine salts having 2 to 6 carbon atoms in total. From the viewpoint of increasing the enzyme activity of the protease, an alkali metal salt is preferable, and a sodium salt is more preferable.
＜（ｂ）成分＞
　（ｂ）成分は、下記一般式（１）で表されるアルキルエーテル硫酸エステル塩である。
　　　　　　　　Ｒ－Ｏ－（ＡＯ）ｎ－ＳＯ３Ｍ　　（１）
〔式中、Ｒは炭素数１０以上１８以下の脂肪族炭化水素基であり、ＡＯは炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｎは１以上２０以下の整数であり、Ｍは陽イオンである。〕 <(B) component>
The component (b) is an alkyl ether sulfate salt represented by the following general formula (1).
R—O— (AO) n —SO 3 M (1)
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
　一般式（１）中、Ｒは、アルキル基、更に鎖式アルキル基が好ましい。また、Ｒは、洗浄性の向上の点から、炭素数１０以上１６以下が好ましい。Ｒは、炭素数１０以上１６以下のアルキル基、更に鎖式アルキル基が好ましい。 In general formula (1), R is preferably an alkyl group, and more preferably a chain alkyl group. Further, R is preferably from 10 to 16 carbon atoms from the viewpoint of improving detergency. R is preferably an alkyl group having 10 to 16 carbon atoms, and more preferably a chain alkyl group.
　一般式（１）中、ＡＯは、炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基である。ＡＯとしては、例えば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種以上の基が挙げられる。ｎが２以上２０以下の整数の場合、ＡＯはエチレンオキシ基及びプロピレンオキシ基を含むことが出来る。ＡＯ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、Ｒ－Ｏ－にはどちらが結合してもよい。ＡＯ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、エチレンオキシ基及びプロピレンオキシ基の結合様式は、ランダム型、ブロック型のいずれかに結合したもの、又はランダム型とブロック型が混合して結合したものであっても良い。（ｂ）成分の入手が容易な点から、ＡＯはエチレンオキシ基が好ましい。 In the general formula (1), AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. Examples of AO include one or more groups selected from an ethyleneoxy group and a propyleneoxy group. When n is an integer of 2 or more and 20 or less, AO can contain an ethyleneoxy group and a propyleneoxy group. When AO contains an ethyleneoxy group and a propyleneoxy group, either of them may be bonded to R—O—. When AO contains an ethyleneoxy group and a propyleneoxy group, the bonding mode of the ethyleneoxy group and the propyleneoxy group is bonded to either the random type or the block type, or the random type and the block type are mixed and bonded. It may be a thing. In view of easy availability of component (b), AO is preferably an ethyleneoxy group.
　一般式（１）中、ｎは、特に限定されるものではないが、洗浄性の向上の点から３以下が好ましく、２以下がより好ましく、１が更に好ましい。本発明の衣料用液体洗浄剤組成物は、（ｂ）成分として、一般式（１）中のｎが１以上３以下、更に１以上２以下、更に１である化合物を含有することが好ましい。 In the general formula (1), n is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and even more preferably 1 from the viewpoint of improvement of detergency. The liquid detergent composition for clothing of the present invention preferably contains a compound in which n in the general formula (1) is 1 or more, 3 or less, 1 or more, 2 or less, and 1 as the component (b).
　洗浄性の向上の点で、一般式（１）中のｎが１の化合物とｎが２の化合物の合計質量は、全（ｂ）成分中の好ましくは４０質量％以上、より好ましくは５０質量％以上、更に好ましくは５５質量％以上、更に好ましくは６０質量％以上、更に好ましくは６５質量％以上であり、そして１００質量％以下であり、好ましくは９０質量％以下、より好ましくは８５質量％以下である。 From the viewpoint of improving detergency, the total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is preferably 40% by mass or more, more preferably 50% by mass in all the components (b). % Or more, more preferably 55% by weight or more, further preferably 60% by weight or more, more preferably 65% by weight or more, and 100% by weight or less, preferably 90% by weight or less, more preferably 85% by weight. It is as follows.
　また、本発明の（ｅ）成分であるプロテアーゼによるタンパク質を含む汚れの洗浄効果を（ｄ）成分である特定の硫酸塩が更に向上する点で、（ｂ）成分中、一般式（１）中のｎが６以上２０以下の化合物の割合は、１０質量％以下が好ましく、９質量％以下がより好ましく、８質量％以下が更に好ましく、７質量％以下が更に好ましく、６質量％以下が更に好ましく、５質量％以下が更に好ましく、４質量％以下が更に好ましく、３質量％以下が更に好ましい。この割合の下限値は、０質量％以上である。更に、この割合の下限値は、０質量％又は０質量％超である。 In addition, in the component (b), in the general formula (1), the specific sulfate of the component (d) further improves the cleaning effect of the soil containing protein by the protease which is the component (e) of the present invention. The ratio of the compound having n of 6 to 20 is preferably 10% by mass or less, more preferably 9% by mass or less, further preferably 8% by mass or less, further preferably 7% by mass or less, and further 6% by mass or less. Preferably, 5% by mass or less is more preferable, 4% by mass or less is more preferable, and 3% by mass or less is more preferable. The lower limit of this ratio is 0% by mass or more. Furthermore, the lower limit of this ratio is 0 mass% or more than 0 mass%.
　本発明では、（ｂ）成分中の、一般式（１）中のｎが異なる化合物の構成比率は、一般式（１）中のＳＯ３Ｍ基をＨに置き換えた化合物におけるｎの異なる化合物の構成比率を採用することができる。例えば、一般式（１）中のＳＯ３Ｍ基をＨに置き換えた化合物であってｎの異なる化合物の分布を、ガスクロマトグラフィーで分析して得られた面積比を質量分率とみなし、これを、（ｂ）成分における一般式（１）中のｎの異なる化合物の構成比率として用いることができる。
　また、一般式（１）で表される（ｂ）成分が入手できる場合であっても、そのままでは構成比率が測定しにくい場合には、該（ｂ）成分を酸分解してＳＯ３Ｍ基をＨに置き換えた化合物を生成させて、該化合物におけるｎの異なる化合物の構成比率を、（ｂ）成分における一般式（１）中のｎの異なる化合物の構成比率として用いることができる。この場合、具体的には、（ｂ）成分を酸分解してＳＯ３Ｍ基をＨに置き換えた化合物を生成させ、次に当該化合物におけるｎの分布をガスクロマトグラフィーで分析し、得られた面積比を質量分率とみなし、これを、（ｂ）成分における一般式（１）中のｎの異なる化合物の構成比率として用いることができる。 In the present invention, the component ratio of the compound having different n in the general formula (1) in the component (b) is the same as that of the compound having different n in the compound in which the SO 3 M group in the general formula (1) is replaced with H. A composition ratio can be adopted. For example, the area ratio obtained by analyzing the distribution of compounds with different n in the compound in which the SO 3 M group in the general formula (1) is replaced with H is regarded as a mass fraction. Can be used as the constituent ratio of the different compounds of n in the general formula (1) in the component (b).
In addition, even when the component (b) represented by the general formula (1) is available, when it is difficult to measure the composition ratio as it is, the component (b) is acid-decomposed to form a SO 3 M group. A compound in which is replaced with H can be generated, and the constituent ratio of the different compounds in the compound can be used as the constituent ratio of the different compounds in the general formula (1) in the component (b). In this case, specifically, the component (b) was obtained by acid decomposition to generate a compound in which the SO 3 M group was replaced with H, and then the distribution of n in the compound was analyzed by gas chromatography. The area ratio is regarded as a mass fraction, and this can be used as a constituent ratio of the different compounds of n in the general formula (1) in the component (b).
　上記の方法を採用する場合、ガスクロマトグラフィーによる分析条件、及び前記の酸分解の条件の一例を下記に示す。
＜ガスクロマトグラフィーの分析条件＞
ＧＣ機器；アジレントテクノロジー社製、７８９０Ａ
カラム；アジレントテクノロジー社製、ＤＢ－５（３０ｍ、内径０．２５mm、膜厚０．２５μｍ）
検出器；ＦＩＤ
キャリア；ヘリウムガス、１ｍＬ／ｍｉｎ
昇温条件；１００℃から３２５℃まで５℃／ｍｉｎで昇温する。その後、３５分間３２５℃を保持する。
試料の前処理：試料５０ｍｇを２ｍＬ容量のバイアル瓶に入れ、トリメチルシリル化剤（ジーエルサイエンス社製）１ｍＬを加えて混合し、３０℃で５分間反応させる。 In the case of employing the above method, an example of analysis conditions by gas chromatography and the above-mentioned acid decomposition conditions are shown below.
<Analysis conditions for gas chromatography>
GC equipment; Agilent Technologies, 7890A
Column: DB-5 manufactured by Agilent Technologies, Inc. (30 m, inner diameter 0.25 mm, film thickness 0.25 μm)
Detector; FID
Carrier; helium gas, 1 mL / min
Temperature raising condition: The temperature is raised from 100 ° C. to 325 ° C. at 5 ° C./min. Thereafter, hold at 325 ° C. for 35 minutes.
Sample pretreatment: 50 mg of a sample is placed in a 2 mL vial, 1 mL of a trimethylsilylating agent (manufactured by GL Sciences) is added and mixed, and reacted at 30 ° C. for 5 minutes.
＜（ｂ）成分の酸分解の条件＞
　３００ｍＬ容量のガラス製スリつき三角フラスコに試料４ｇを入れる。２Ｎ塩酸２００ｍＬと沸石を三角フラスコ内に投入し、スリ付空冷管をセットした。三角フラスコを１４０℃のオイルバスに入れ３時間還流した後に３０℃まで冷却する。三角フラスコ内に１％フェノールフタレイン溶液を、パスツールピペットで１滴加えた。次に、三角フラスコ内の内容物が淡いピンク色になるまで、３５％水酸化ナトリウム水溶液を添加する。
　内容物を１０００ｍＬ容量の分液ロートに写し、石油エーテル２００ｍＬを加えて３回抽出する。石油エーテル層を１０％塩化ナトリウム水溶液５０ｍＬで３回水洗後に無水硫酸ナトリウム２０ｇを添加し脱水する。５００ｍＬ三角に無水硫酸ナトリウムをろ過で取り除いた溶液を入れ、石油エーテルをトッピングする。 <Conditions for acid decomposition of component (b)>
Place 4 g of sample into a 300 mL glass Erlenmeyer flask with a slit. 200 mL of 2N hydrochloric acid and zeolite were put into an Erlenmeyer flask, and an air-cooled tube with a thread was set. The Erlenmeyer flask is placed in a 140 ° C. oil bath and refluxed for 3 hours, and then cooled to 30 ° C. One drop of 1% phenolphthalein solution was added to the Erlenmeyer flask using a Pasteur pipette. Next, 35% aqueous sodium hydroxide solution is added until the contents in the Erlenmeyer flask become a light pink color.
Transfer the contents to a 1000 mL separatory funnel, add 200 mL petroleum ether and extract 3 times. The petroleum ether layer is washed with 50 mL of a 10% aqueous sodium chloride solution three times, and then 20 g of anhydrous sodium sulfate is added for dehydration. A solution obtained by removing anhydrous sodium sulfate by filtration is placed in a 500 mL triangle, and topped with petroleum ether.
　一般式（１）中、Ｍは、塩を形成する陽イオンである。Ｍは、ナトリウムイオン、カリウムイオンなどのアルカリ金属イオン、及びアルカノールアンモニウムイオンなどが挙げられる。プロテアーゼの活性を高める観点から、Ｍは、アルカリ金属イオンが好ましく、ナトリウムイオンがより好ましい。アルカノールアンモニウムイオンは、総炭素数２以上６以下のアルカノールアンモニウムイオンが好ましい。 In general formula (1), M is a cation that forms a salt. Examples of M include alkali metal ions such as sodium ions and potassium ions, and alkanol ammonium ions. From the viewpoint of enhancing the activity of the protease, M is preferably an alkali metal ion, more preferably a sodium ion. The alkanol ammonium ion is preferably an alkanol ammonium ion having 2 to 6 carbon atoms in total.
＜（ｃ）成分＞
　（ｃ）成分はノニオン界面活性剤である。（ｃ）成分は、衣料用液体洗浄剤組成物中でのプロテアーゼの保存安定性を高める作用効果を有すると考えられる。 <(C) component>
The component (c) is a nonionic surfactant. (C) It is thought that a component has the effect which improves the storage stability of the protease in the liquid cleaning composition for clothes.
　（ｃ）成分としては、ポリオキシアルキレン基を有するノニオン界面活性剤、更に平均付加モル数が３モル以上５０モルのポリオキシアルキレン基を有するノニオン界面活性剤が好ましい。
　（ｃ）成分としては、下記一般式（ｃ１）で表されるノニオン界面活性剤がより好ましい。
　　　　　Ｒ１ｃ－Ｏ－（Ａ’Ｏ）ｍ－Ｈ　　　（ｃ１）
〔式中、Ｒ１ｃは炭素数８以上１８以下の脂肪族炭化水素基であり、Ａ’Ｏは、炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｍは、Ａ’Ｏの平均付加モル数であり、３以上５０以下の数である。〕 As the component (c), a nonionic surfactant having a polyoxyalkylene group and a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 mol to 50 mol are preferable.
As the component (c), a nonionic surfactant represented by the following general formula (c1) is more preferable.
R 1c —O— (A′O) m —H (c1)
[In the formula, R 1c is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. , M is the average added mole number of A′O, and is a number of 3 or more and 50 or less. ]
　一般式（ｃ１）中のＲ１ｃの炭素数は、タンパク汚れを含む汚れの洗浄性をより向上出来る点で、１０以上が好ましく、１２以上がより好ましく、そして１６以下が好ましい。
　また、一般式（ｃ１）中のＲ１ｃの炭素数は、本発明の衣料用液体洗浄剤組成物の粘度をより低く出来る点で、１０以上が好ましく、そして１６以下が好ましく、１４以下がより好ましい。
　また、一般式（ｃ１）中のＲ１ｃの脂肪族炭化水素基としては、アルキル基及びアルケニル基から選ばれる脂肪族炭化水素基が挙げられ、アルキル基が好ましい。 The number of carbon atoms of R 1c in the general formula (c1) is preferably 10 or more, more preferably 12 or more, and preferably 16 or less, from the viewpoint of further improving the cleaning performance of soil including protein soil.
In addition, the carbon number of R 1c in the general formula (c1) is preferably 10 or more, preferably 16 or less, and more preferably 14 or less in that the viscosity of the liquid cleaning composition for clothing of the present invention can be further reduced. preferable.
In addition, examples of the aliphatic hydrocarbon group represented by R 1c in the general formula (c1) include an aliphatic hydrocarbon group selected from an alkyl group and an alkenyl group, and an alkyl group is preferable.
　一般式（ｃ１）中のｍは、Ａ’Ｏの平均付加モル数であり、衣料用液体洗浄剤組成物中のプロテアーゼの保存安定性をより向上できる点で、４以上が好ましく、５以上がより好ましく、６以上が更に好ましく、７以上が更に好ましい。プロテアーゼによるタンパク汚れの洗浄性を（ｄ）成分が高める効果をより向上させる点で、ｍは、４５以下が好ましく、４０以下がより好ましく、３５以下が更に好ましく、３０以下が更に好ましく、２５以下が更に好ましく、２０以下が更に好ましく、１８以下が更に好ましく、１６以下が更に好ましく、１４以下が更に好ましく、１２以下が更に好ましい。
　Ａ’Ｏは、炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基である。Ａ’Ｏは、例えば、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種以上の基が挙げられる。衣料用液体洗浄剤組成物中のプロテアーゼの保存安定性をより向上できる点で、Ａ’Ｏが、エチレンオキシ基を含むアルキレンオキシ基であることが好ましい。Ａ’Ｏはエチレンオキシ基が好ましい。 M in the general formula (c1) is the average number of moles added of A′O, and is preferably 4 or more, and more preferably 5 or more in that the storage stability of the protease in the liquid detergent composition for clothing can be further improved. More preferably, 6 or more is still more preferable, and 7 or more is more preferable. M is preferably 45 or less, more preferably 40 or less, still more preferably 35 or less, still more preferably 30 or less, and even more preferably 25 or less, in view of further improving the effect of the component (d) improving the protein stain detergency with protease. Is more preferable, 20 or less is more preferable, 18 or less is more preferable, 16 or less is more preferable, 14 or less is more preferable, and 12 or less is more preferable.
A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. A′O includes, for example, one or more groups selected from an ethyleneoxy group and a propyleneoxy group. A′O is preferably an alkyleneoxy group containing an ethyleneoxy group from the viewpoint that the storage stability of the protease in the liquid detergent composition for clothing can be further improved. A′O is preferably an ethyleneoxy group.
＜（ｄ）成分＞
　（ｄ）成分は、炭素数１以上８以下の有機アンモニウム硫酸塩、及び無機硫酸塩（但し、硫酸カルシウムを除く）から選ばれる１種以上の硫酸塩である。衣料上でプロテアーゼにより分解された低分子量化されたタンパク質が、衣料上から洗浄液中に分散する量が（ｄ）成分により向上できる。また、（ｄ）成分により、衣料用液体洗浄剤組成物中でのプロテアーゼの安定性を向上できる。 <(D) component>
The component (d) is one or more sulfates selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate). The amount of the low molecular weight protein decomposed by the protease on the clothing and dispersed in the washing liquid from the clothing can be improved by the component (d). Moreover, the stability of protease in the liquid detergent composition for clothes can be improved by the component (d).
　炭素数１以上８以下の有機アンモニウム硫酸塩としては、プロテアーゼによるタンパク汚れの洗浄性をより高める点で、下記一般式（ｄ１）で表される化合物が好ましい。
　〔（ＣｎＨ２ｎ＋１）ｘＮ（Ｃ２Ｈ４ＯＨ）ｙ〕２＋・ＳＯ４ ２－　　　　（ｄ１）
〔式中、ｎは０以上２以下の整数であり、ｘ、ｙはそれぞれ０以上４以下の数であり、ｘ＋ｙは４であるが、ｎが０でｘが４の場合を除く。ＣｎＨ２ｎ＋１基が複数存在する場合は、同一でも異なっていても良い。〕 As the organic ammonium sulfate having 1 to 8 carbon atoms, a compound represented by the following general formula (d1) is preferable from the viewpoint of further improving the cleanability of protein stains by protease.
[(C n H 2n + 1 ) x N (C 2 H 4 OH) y ] 2 + · SO 4 2− (d1)
[In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C n H 2n + 1 groups, they may be the same or different. ]
　炭素数１以上８以下の有機アンモニウム硫酸塩としては、プロテアーゼによるタンパク汚れの洗浄効果をより高める点で、モノエタノールアンモニウム硫酸塩、メチルモノエタノールアンモニウム硫酸塩、エチルモノエタノールアンモニウム硫酸塩、メチルジエタノールアンモニウム硫酸塩、エチルジエタノールアンモニウム硫酸塩、ジエタノールアンモニウム硫酸塩及びトリエタノールアンモニウム硫酸塩から選ばれる１種以上の化合物が好ましく、モノエタノールアンモニウム硫酸塩及びトリエタノールアンモニウム硫酸塩から選ばれる１種以上の化合物がより好ましい。 The organic ammonium sulfate having 1 to 8 carbon atoms is monoethanolammonium sulfate, methylmonoethanolammonium sulfate, ethylmonoethanolammonium sulfate, methyldiethanolammonium, in order to further improve the effect of cleaning protein stains by protease. One or more compounds selected from sulfate, ethyl diethanolammonium sulfate, diethanolammonium sulfate and triethanolammonium sulfate are preferred, and one or more compounds selected from monoethanolammonium sulfate and triethanolammonium sulfate are preferred. More preferred.
　無機硫酸塩（但し、硫酸カルシウムを除く）としては、プロテアーゼによるタンパク汚れの洗浄効果をより高める点で、硫酸アンモニウム、アルカリ金属硫酸塩、及び硫酸カルシウムを除くアルカリ土類金属硫酸塩から選ばれる１種以上の無機硫酸塩が好ましい。アルカリ金属硫酸塩としては、硫酸リチウム、硫酸ナトリウム、硫酸カリウムが挙げられる。硫酸カルシウムを除くアルカリ土類金属硫酸塩としては、硫酸マグネシウムが挙げられる。
　無機硫酸塩（但し、硫酸カルシウムを除く）としては、プロテアーゼが衣料上で分解したタンパク汚れを洗浄液中に分散させる効果が高い点で、アルカリ金属硫酸塩が好ましい。 Inorganic sulfate (excluding calcium sulfate) is one selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate in order to further enhance the effect of washing protein stains by protease. The above inorganic sulfates are preferred. Examples of the alkali metal sulfate include lithium sulfate, sodium sulfate, and potassium sulfate. Examples of the alkaline earth metal sulfate excluding calcium sulfate include magnesium sulfate.
As the inorganic sulfate (excluding calcium sulfate), an alkali metal sulfate is preferred because it has a high effect of dispersing protein stains decomposed on the clothing by the protease in the washing liquid.
　（ｄ）成分は、無水物及び水和物から選ばれる１種以上の硫酸塩を用いることが出来る。従って、（ｄ）成分は、炭素数１以上８以下の有機アンモニウム硫酸塩、無機硫酸塩（但し、硫酸カルシウムを除く）、前記硫酸塩の無水物、及び前記硫酸塩の水和物から選ばれる１種以上の硫酸塩であることができる。 As the component (d), one or more sulfates selected from anhydrides and hydrates can be used. Accordingly, the component (d) is selected from organic ammonium sulfates having 1 to 8 carbon atoms, inorganic sulfates (excluding calcium sulfate), anhydrous sulfates, and sulfate hydrates. It can be one or more sulfates.
　（ｄ）成分は、無機硫酸塩（但し、硫酸カルシウムを除く）から選ばれる１種以上の硫酸塩が好ましく、アルカリ金属硫酸塩、及び硫酸カルシウムを除くアルカリ土類金属硫酸塩から選ばれる１種以上の無機硫酸塩がより好ましく、アルカリ金属硫酸塩から選ばれる１種以上の無機硫酸塩が更に好ましい。 The component (d) is preferably one or more sulfates selected from inorganic sulfates (excluding calcium sulfate), and one selected from alkali metal sulfates and alkaline earth metal sulfates excluding calcium sulfate. The above inorganic sulfates are more preferable, and one or more inorganic sulfates selected from alkali metal sulfates are more preferable.
＜（ｅ）成分＞
　（ｅ）成分はプロテアーゼである。
　好ましいプロテアーゼとしては、中性、あるいはアルカリ性の水溶液中で作用できるプロテアーゼが挙げられる。好ましいプロテアーゼは、アルカリプロテアーゼである。 <(E) component>
The component (e) is a protease.
Preferred proteases include proteases that can act in neutral or alkaline aqueous solutions. A preferred protease is an alkaline protease.
　好ましいプロテアーゼの具体例としては、（ｅ１）国際公開第９９／０１８２１８号に記載されているアルカリプロテアーゼ、好ましくは同公報の配列番号１、または２で示されるアミノ酸配列の７０％以上が保存されているアルカリプロテアーゼ、（ｅ２）特開平５－２５４９２号に記載されているアルカリプロテアーゼ、好ましくはアルカリプロテアーゼＫ－１６又はアルカリプロテアーゼＫ－１４などが挙げられる。
　また、プロテアーゼとしては、（ｅ３）ノボザイムズ社製のサビナーゼ（登録商標）、カンナーゼ（登録商標）、エバラーゼ（登録商標）、アルカラーゼ（登録商標）、ポラーザイム（登録商標）、エスペラーゼ（登録商標）の商品名で販売されているバチルス属ズブチリシン類が生産するプロテアーゼ、（ｅ４）デュポン社製のＦＮ２（登録商標）、ＦＮ３（登録商標）及びＦＮ４（登録商標）、プラフェクト（登録商標）、プラフェクトプライム（登録商標）、（ｅ５）花王株式会社製のアルカリプロテアーゼ、例えばＫＡＰ４．３Ｇ（登録商標）、ＫＡＰ１１．１Ｇ（登録商標）、（ｅ６）これらの商品名で供給されるプロテアーゼ類又はその変異型等が挙げられる。
　プロテアーゼとしては、国際公開第９９／０１８２１８号に記載されている配列番号１、または２で示されるアミノ酸配列の８０％以上が保存されているアルカリプロテアーゼ、ノボザイムズ社製のサビナーゼ、エバラーゼ、アルカラーゼ、デュポン社製のプラフェクト、プラフェクトプライム、花王株式会社製のアルカリプロテアーゼがより好ましい。
　（ａ）成分や（ｂ）成分との組合せにより、洗浄性をより向上できる点から、プロテアーゼは、サビナーゼが更に好ましい。 Specific examples of preferable protease include (e1) alkaline protease described in WO 99/018218, preferably 70% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 of the publication is conserved. (E2) Alkaline protease described in JP-A-5-25492, preferably alkaline protease K-16 or alkaline protease K-14.
As proteases, (e3) products of Sabinase (registered trademark), Cannase (registered trademark), Everase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark) manufactured by Novozymes (E4) FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark), Duplex (registered trademark), Perfect Prime (produced by DuPont) (Registered Trademark), (e5) Alkaline protease manufactured by Kao Corporation, for example, KAP4.3G (Registered Trademark), KAP11.1G (Registered Trademark), (e6) Proteases or their variants supplied under these trade names Is mentioned.
Examples of the protease include alkaline protease in which 80% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 described in International Publication No. 99/018218 is conserved, sabinase, everase, alcalase, dupon from Novozymes. More preferred are Pfect, Practical Prime, and alkaline protease manufactured by Kao Corporation.
The protease is more preferably sabinase from the viewpoint that the detergency can be further improved by combination with the component (a) or the component (b).
　洗浄性の観点から、（ｅ）成分のプロテアーゼは、酵素タンパク量１ｇ当たりの活性、すなわち比活性が、好ましくは５０００ｍＰＵ／ｇ以上、より好ましくは２００００ｍＰＵ／ｇ以上である。ここで、プロテアーゼの比活性は、下記の方法で測定されるプロテアーゼの活性単位を、プロテアーゼの酵素タンパク量１ｇ当たりに換算したものである。プロテアーゼの活性単位は、実施例に記載の方法に従い測定することができる。 From the viewpoint of detergency, the protease of component (e) has an activity per gram of enzyme protein, that is, a specific activity, preferably 5000 mPU / g or more, more preferably 20000 mPU / g or more. Here, the specific activity of the protease is obtained by converting the activity unit of the protease measured by the following method per 1 g of the amount of the enzyme protein of the protease. The activity unit of protease can be measured according to the method described in Examples.
＜（ｆ）成分＞
　本発明の衣料用洗浄剤組成物は、（ｆ）成分として、２価以上６価以下の多価アルコールを含有することができる。
　（ｆ）成分は（ｃ）成分及び（ｄ）成分と併用することで、衣料用液体洗浄剤組成物中のプロテアーゼの保存安定性をより高めることができる。 <Component (f)>
The detergent composition for clothing of the present invention can contain a polyhydric alcohol having a valence of 2 to 6 as the component (f).
Component (f) can be further combined with component (c) and component (d) to further enhance the storage stability of protease in the liquid detergent composition for clothing.
　２価のアルコールの好ましい化合物としては、エチレングリコール、プロピレングリコール、ジエチレングリコール及びトリエチレングリコールから選ばれる１種以上の化合物が挙げられる。３価のアルコールの好ましい化合物としては、グリセリンが挙げられる。４価のアルコールの好ましい化合物は、ペンタエリスリトールが挙げられる。５価以上６価以下のアルコールの好ましい化合物は、５価以上６価以下の糖アルコールが挙げられる。５価の糖アルコールとしてはキシリトールが挙げられる。６価の糖アルコールとしては、ソルビトール、マニトールが挙げられる。プロテアーゼの保存安定性をより向上できる点で、（ｆ）成分は、プロピレングリコール、グリセリン、ジエチレングリコール、トリエチレングリコール及びソルビトールから選ばれる１種以上の化合物が好ましく、プロピレングリコール、グリセリン及びソルビトールから選ばれる１以上の化合物が好ましい。 Preferred compounds of the divalent alcohol include one or more compounds selected from ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol. A preferred compound of a trivalent alcohol is glycerin. A preferred compound of a tetravalent alcohol is pentaerythritol. Preferable compounds of 5 to 6 valent alcohols include 5 to 6 valent sugar alcohols. An example of the pentavalent sugar alcohol is xylitol. Examples of the hexavalent sugar alcohol include sorbitol and mannitol. The component (f) is preferably at least one compound selected from propylene glycol, glycerin, diethylene glycol, triethylene glycol, and sorbitol, and can be selected from propylene glycol, glycerin, and sorbitol, because the storage stability of the protease can be further improved. One or more compounds are preferred.
＜（ｇ）成分＞
　本発明の衣料用洗浄剤組成物は、（ｇ）成分として、カルシウムイオン供与体を含有することができる。
　（ｇ）成分は、水中でイオン解離する性質を有する化合物であり、プロテアーゼの安定化剤として使用される。（ｇ）成分は無機化合物からなるものが好ましく、具体的には、塩化カルシウムが挙げられる。 <(G) component>
The detergent composition for clothing of the present invention can contain a calcium ion donor as the component (g).
The component (g) is a compound having a property of ion dissociation in water, and is used as a protease stabilizer. The component (g) is preferably composed of an inorganic compound, and specific examples include calcium chloride.
＜衣料用液体洗浄剤組成物の組成等＞
　本発明の衣料用液体洗浄剤組成物は、プロテアーゼによるタンパク質を含む汚れの洗浄効果を高めることにより、衣料に付着したタンパク質を含む汚れの洗浄力に優れる。また、更に、本発明の衣料用液体洗浄剤組成物から調製した洗浄液中では、プロテアーゼの保存安定性に優れる。 <Composition etc. of liquid detergent composition for clothing>
The liquid detergent composition for clothes of the present invention is excellent in the cleaning power of dirt containing protein adhering to clothes by enhancing the cleaning effect of dirt containing protein due to protease. Furthermore, in the cleaning liquid prepared from the liquid cleaning composition for clothing of the present invention, the storage stability of protease is excellent.
　本発明の衣料用液体洗浄剤組成物中の（ａ）成分及び（ｂ）成分の含有量は、それぞれ、対イオン、すなわち塩を形成する陽イオンをナトリウムに換算した値、すなわちナトリウム塩に換算した値を用いるものとする。 The content of the component (a) and the component (b) in the liquid detergent composition for clothing of the present invention is a value obtained by converting a counter ion, that is, a cation forming a salt, into sodium, that is, converted into a sodium salt. Shall be used.
　本発明の衣料用液体洗浄剤組成物は、（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量が５質量％以上４０質量％以下である。
　本発明の衣料用液体洗浄剤組成物中の（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量は、タンパク質を含む汚れの洗浄性をより高める点で、好ましくは６質量％以上、より好ましくは７質量％以上、更に好ましくは８質量％以上、更に好ましくは９質量％以上である。また、本発明の衣料用液体洗浄剤組成物中の（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量は、衣料用液体洗浄剤組成物の保存安定性がより良好になる点で、好ましくは３５質量％以下、より好ましくは３０質量％以下、更に好ましくは２５質量％以下、更に好ましくは２０質量％以下である。 In the liquid detergent composition for clothing of the present invention, the total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less.
The total content of the component (a) component and the component (b) content in the liquid detergent composition for clothing of the present invention is preferably from the standpoint of further enhancing the cleanability of soil containing protein. It is 6 mass% or more, More preferably, it is 7 mass% or more, More preferably, it is 8 mass% or more, More preferably, it is 9 mass% or more. Moreover, the total content of the content of the component (a) and the content of the component (b) in the liquid detergent composition for clothing of the present invention is more stable in storage stability of the liquid detergent composition for clothing. In terms of improvement, it is preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and still more preferably 20% by mass or less.
　また、本発明の衣料用液体洗浄剤組成物は、（ａ）成分の含有量と（ｂ）成分の含有量との質量比が、（ａ）成分の含有量／（ｂ）成分の含有量で、０．５以上１０以下である。
　プロテアーゼによるタンパク質を含む汚れの洗浄効果を（ｄ）成分である特定の硫酸塩が増強する効果をより高める点で、（ａ）成分の含有量と（ｂ）成分の含有量との質量比は、（ａ）成分の含有量／（ｂ）成分の含有量で、０．５以上、好ましくは０．５５以上、より好ましくは０．６以上、更に好ましくは０．６５以上、更に好ましくは０．７以上、更に好ましくは０．７５以上、更に好ましくは０．８以上、更に好ましくは０．８５以上、更に好ましくは０．９以上である。
　また、本発明の衣料用洗浄剤組成物中でのプロテアーゼの保存安定性をより高める点で、（ａ）成分の含有量と（ｂ）成分の含有量との質量比は、（ａ）成分の含有量／（ｂ）成分の含有量で、１０以下、好ましくは９以下、より好ましくは８以下、更に好ましくは７以下、更に好ましくは６以下、更に好ましくは５以下、更に好ましくは４以下、更に好ましくは３以下、更に好ましくは２以下である。 Moreover, as for the liquid cleaning composition for clothes of this invention, mass ratio of content of (a) component and content of (b) component is content of (a) component / content of (b) component Thus, it is 0.5 or more and 10 or less.
The mass ratio between the content of the component (a) and the content of the component (b) is such that the effect of enhancing the specific sulfate salt as the component (d) enhances the cleaning effect of the soil containing proteins by protease. The content of the component (a) / the content of the component (b) is 0.5 or more, preferably 0.55 or more, more preferably 0.6 or more, still more preferably 0.65 or more, still more preferably 0. 0.7 or more, more preferably 0.75 or more, further preferably 0.8 or more, more preferably 0.85 or more, and further preferably 0.9 or more.
The mass ratio of the content of the component (a) to the content of the component (b) is such that the storage stability of the protease in the detergent composition for clothing of the present invention is further increased. Content / (b) component content of 10 or less, preferably 9 or less, more preferably 8 or less, still more preferably 7 or less, still more preferably 6 or less, still more preferably 5 or less, still more preferably 4 or less. More preferably, it is 3 or less, more preferably 2 or less.
　本発明では、衣料用液体洗浄剤組成物の調製にあたり、（ａ）成分と（ｂ）成分とを含む混合物を（ａ）成分及び（ｂ）成分の供給源として用いることができる。そのような混合物として、例えば、化合物の構造及び割合が既知の、炭素数１０以上１８以下のアルキル基を有するポリオキシアルキレンアルキルエーテル硫酸エステル塩が挙げられる。ポリオキシアルキレンアルキルエーテル硫酸エステル塩は、一般に、アルコールのアルキレンオキシド付加物を硫酸エステル化して得られ、アルキレンオキシドの付加モル数の異なる化合物の混合物として入手される。そのため、本発明の（ａ）成分と（ｂ）成分とを含む混合物となり得る。 In the present invention, a mixture containing the component (a) and the component (b) can be used as a supply source for the component (a) and the component (b) in preparing the liquid detergent composition for clothing. As such a mixture, for example, a polyoxyalkylene alkyl ether sulfate ester salt having an alkyl group having 10 to 18 carbon atoms and having a known structure and ratio of the compound can be mentioned. The polyoxyalkylene alkyl ether sulfate ester salt is generally obtained by subjecting an alkylene oxide adduct of alcohol to sulfate esterification, and is obtained as a mixture of compounds having different addition mole numbers of alkylene oxide. Therefore, it can be a mixture containing the components (a) and (b) of the present invention.
　本発明の衣料用液体洗浄剤組成物は、衣料用液体洗浄剤組成物中のプロテアーゼの保存安定性をより高める点と、タンパク質を含む汚れの洗浄性をより高める点で、（ｃ）成分の含有量と、（ａ）成分の含有量及び（ｂ）成分の含有量の合計の含有量との質量比が、（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕で、０．０２以上２以下であることが好ましい。
　プロテアーゼの保存安定性をより高める点で、質量比（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕は、０．０４以上が好ましく、０．０６以上がより好ましく、０．０８以上が更に好ましく、０．１以上が更に好ましく、０．１２以上が更に好ましい。
　衣料用液体洗浄剤組成物中の（ｃ）成分の含有量が多くなると、プロテアーゼの保存安定性がより高くなる。しかしながら、保存安定性が高くなりすぎると、洗浄液中でのプロテアーゼが汚れに含まれるタンパク質を分解する作用が弱まり、プロテアーゼによるタンパク汚れの洗浄効果が出にくい場合がある。質量比（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕は、タンパク質を含む汚れの洗浄性をより高める点で、１．８以下が好ましく、１．６以下がより好ましく、１．４以下が更に好ましく、１．２以下が更に好ましく、１．０以下が更に好ましく、０．８以下が更に好ましく、０．６以下が更に好ましく、０．４以下が更に好ましい。 The liquid detergent composition for clothing of the present invention is characterized in that the storage stability of the protease in the liquid detergent composition for clothing is further improved and the washing property of soil containing protein is further improved. The mass ratio of the content and the total content of the component (a) and the component (b) is (c) component content / [(a) component content + (b) Component content] is preferably 0.02 or more and 2 or less.
In terms of further improving the storage stability of the protease, the mass ratio (c) component content / [(a) component content + (b) component content] is preferably 0.04 or more, and 0.06 The above is more preferable, 0.08 or more is further preferable, 0.1 or more is further preferable, and 0.12 or more is further preferable.
When the content of the component (c) in the liquid detergent composition for clothing increases, the storage stability of the protease becomes higher. However, if the storage stability becomes too high, the protease in the cleaning solution weakens the action of degrading the protein contained in the soil, and it may be difficult to obtain a protein soil cleaning effect by the protease. The mass ratio (c) component content / [(a) component content + (b) component content] is preferably 1.8 or less in view of further improving the cleaning performance of soil containing protein. .6 or less is more preferable, 1.4 or less is further preferable, 1.2 or less is further preferable, 1.0 or less is further preferable, 0.8 or less is further preferable, 0.6 or less is further preferable, 0.4 The following is more preferable.
　本発明の衣料用液体洗浄剤組成物は、（ｄ）成分の含有量が２質量％以上８質量％以下である。
　本発明の衣料用液体洗浄剤組成物中の（ｄ）成分の含有量は、プロテアーゼの作用により低分子量化したタンパク質の洗浄液中への溶解性を高くすることで、汚れの洗浄率を高める点で、好ましくは２．２質量％以上、より好ましくは２．４質量％以上、更に好ましくは２．６質量％以上、更に好ましくは２．８質量％以上、更に好ましくは３質量％以上である。衣料用液体洗浄剤組成物中のプロテアーゼの保存安定性をより高める点で、好ましくは７質量％以下、より好ましくは６質量％以下、更に好ましくは５質量％以下である。 In the liquid detergent composition for clothing of the present invention, the content of the component (d) is 2% by mass or more and 8% by mass or less.
The content of the component (d) in the liquid detergent composition for clothing of the present invention is to increase the washing rate of dirt by increasing the solubility of the protein, which has been reduced in molecular weight by the action of protease, in the washing solution. Preferably, it is 2.2% by mass or more, more preferably 2.4% by mass or more, further preferably 2.6% by mass or more, further preferably 2.8% by mass or more, and further preferably 3% by mass or more. . It is preferably 7% by mass or less, more preferably 6% by mass or less, and still more preferably 5% by mass or less from the viewpoint of further enhancing the storage stability of the protease in the liquid detergent composition for clothing.
　また、本発明の衣料用液体洗浄剤組成物中の（ｄ）成分の含有量は、硫酸イオンとして、好ましくは１．４質量％以上、より好ましくは１．５質量％以上、更に好ましくは１．６質量％以上、更に好ましくは１．７質量％以上、更に好ましくは１．８質量％以上、更に好ましくは１．９質量％以上、更に好ましくは２．０質量％以上であり、そして、好ましくは７質量％以下、より好ましくは６質量％以下、更に好ましくは５．５質量％以下、更に好ましくは４．０質量％以下、更に好ましくは３．５質量％以下である。 In addition, the content of the component (d) in the liquid detergent composition for clothing of the present invention is preferably 1.4% by mass or more, more preferably 1.5% by mass or more, and still more preferably 1 as sulfate ions. .6% by weight or more, more preferably 1.7% by weight or more, more preferably 1.8% by weight or more, more preferably 1.9% by weight or more, more preferably 2.0% by weight or more, and Preferably it is 7 mass% or less, More preferably, it is 6 mass% or less, More preferably, it is 5.5 mass% or less, More preferably, it is 4.0 mass% or less, More preferably, it is 3.5 mass% or less.
　本発明の衣料用液体洗浄剤組成物中の（ｅ）成分の含有量は、酵素タンパク量として、好ましくは０．１質量％以上、より好ましくは０．２質量％以上、そして、好ましくは１質量％以下、より好ましくは０．８質量％以下、更に好ましくは０．５質量％以下である。
　なお、本発明において、（ｅ）成分の酵素タンパク量は、ローリーらの方法（Ｌｏｗｒｙ，　Ｏ．Ｈ．ｅｔ．　ａｌ．，　Ｊ．　Ｂｉｏｌ．　Ｃｈｅｍ．，　１９３，　２６５　（１９５１））に準じ、牛血清アルブミン（ＢｏｖｉｎｅＳｅｒｕｍ　Ａｌｂｕｍｉｎ、ＳＩＧＭＡ社製、製品番号Ａ－７０３０）に換算して表したものとする。 The content of the component (e) in the liquid detergent composition for clothing of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 1 as the amount of enzyme protein. It is at most mass%, more preferably at most 0.8 mass%, still more preferably at most 0.5 mass%.
In the present invention, the amount of enzyme protein of component (e) is determined according to the method of Lowry et al. (Lowry, OH et al., J. Biol. Chem., 193, 265 (1951)). It is expressed in terms of serum albumin (Bovine Serum Albumin, manufactured by SIGMA, product number A-7030).
　本発明の衣料用液体洗浄剤組成物が（ｆ）成分を含有する場合、（ｆ）成分の含有量は、組成物中、０．２質量％以上１０質量％以下が好ましい。衣料用洗浄剤組成物中のプロテアーゼの保存安定性が更に向上する点で、（ｆ）成分の含有量は、組成物中、より好ましくは０．４質量％以上、更に好ましくは０．６質量％以上、更に好ましくは０．８質量％以上であり、そして、コストの低減の点で、より好ましくは９質量％以下、更に好ましくは８質量％以下、更に好ましくは７質量％以下である。 When the liquid detergent composition for clothing of the present invention contains the component (f), the content of the component (f) is preferably 0.2% by mass or more and 10% by mass or less in the composition. The content of the component (f) is more preferably 0.4% by mass or more, and still more preferably 0.6% by mass, in that the storage stability of the protease in the detergent composition for clothing is further improved. % Or more, more preferably 0.8% by mass or more, and more preferably 9% by mass or less, still more preferably 8% by mass or less, and even more preferably 7% by mass or less from the viewpoint of cost reduction.
　本発明の衣料用液体洗浄剤組成物が（ｇ）成分を含有する場合、（ｇ）成分の含有量は、カルシウムイオンとして、組成物中、０．０１質量％以上０．１５質量％以下が好ましい。プロテアーゼの安定性を向上させる点で、（ｇ）成分の含有量は、カルシウムイオンとして、組成物中、より好ましくは０．０２質量％以上、更に好ましくは０．０３質量％以上である。また、洗浄性の観点で、（ｇ）成分の含有量は、カルシウムイオンとして、組成物中、より好ましくは０．１２質量％以下、更に好ましくは０．１質量％以下、更に好ましくは０．０８質量％以下である。 When the liquid cleaning composition for clothing of the present invention contains the component (g), the content of the component (g) is 0.01 mass% or more and 0.15 mass% or less in the composition as calcium ions. preferable. In terms of improving the stability of the protease, the content of the component (g) is preferably 0.02% by mass or more, more preferably 0.03% by mass or more in the composition as calcium ions. From the viewpoint of detergency, the content of the component (g) is preferably 0.12% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.1% by mass or less in the composition as calcium ions. It is 08 mass% or less.
　本発明の衣料用液体洗浄剤組成物は、２５℃でのｐＨが４以上１０以下である。このｐＨは、衣料用液体洗浄剤組成物中でのプロテアーゼの保存安定性に優れる点で、好ましくは４．５以上、より好ましくは５．０以上、更に好ましくは５．５以上、更に好ましくは６．０以上、更に好ましくは６．５以上、更に好ましくは７．０以上、更に好ましくは７．５以上、更に好ましくは８．０以上であり、そして、好ましくは９．８以下、より好ましくは９．５以下である。ｐＨは、ガラス電極を使用したｐＨメーターを用いて測定することができる。 The liquid detergent composition for clothes of the present invention has a pH of 4 or more and 10 or less at 25 ° C. This pH is preferably 4.5 or more, more preferably 5.0 or more, still more preferably 5.5 or more, and still more preferably, in terms of excellent storage stability of protease in the liquid detergent composition for clothing. 6.0 or more, more preferably 6.5 or more, more preferably 7.0 or more, more preferably 7.5 or more, still more preferably 8.0 or more, and preferably 9.8 or less, more preferably Is 9.5 or less. The pH can be measured using a pH meter using a glass electrode.
　本発明の液体洗浄剤組成物には、その他の成分として、次の（ｉ）～（ｖ）に示す成分を、本発明の効果を損なわない程度の量で配合することができる。
（ｉ）再汚染防止剤及び分散剤
　（ｉ）成分としては、ポリアクリル酸、ポリマレイン酸、及び特開昭５９－６２６１４号公報の請求項１～２１（１頁３欄５行～３頁４欄１４行）記載のポリマーなどの再汚染防止剤及び分散剤が挙げられる。（ｉ）成分は、好ましくはポリアクリル酸、ポリマレイン酸又はそれらの塩であり、より好ましくはポリアクリル酸又はその塩である。
　本発明の衣料用洗浄剤組成物中の（ｉ）成分の含有量は、好ましくは０．１質量％以上、より好ましくは０．５質量％以上、更に好ましくは１質量％以上、そして、好ましくは１０質量％以下、より好ましくは５質量％以下、更に好ましくは３質量％以下である。 In the liquid detergent composition of the present invention, the following components (i) to (v) can be blended as other components in an amount that does not impair the effects of the present invention.
(I) Anti-staining agent and dispersant (i) As the component, polyacrylic acid, polymaleic acid, and claim 1-21 of JP-A-59-62614 (page 1, column 3, line 5 to page 3, 4) Column 14 line) and a recontamination preventive agent and a dispersant such as a polymer. The component (i) is preferably polyacrylic acid, polymaleic acid or a salt thereof, more preferably polyacrylic acid or a salt thereof.
The content of the component (i) in the garment cleaning composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably Is 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
（ii）蛍光染料
　（ii）成分としては、例えばチノパールＣＢＳ（商品名、チバスペシャリティケミカルズ製）やホワイテックスＳＡ（商品名、住友化学株式会社製）として市販されている蛍光染料が挙げられる。 (Ii) Fluorescent dye (ii) Examples of the component (ii) include fluorescent dyes commercially available as Chino Pearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitetex SA (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
（iii）炭素数１以上６以下の１価以上３価以下のアルコール
　（iii）成分としては、例えば、エタノール、エチレングリコール、プロピレングリコ
ール及びグリセリンから選ばれる１種以上のアルコールが挙げられる。
　本発明の衣料用液体洗浄剤組成物を水に分散させ易くする効果、当該組成物が保管中２つ以上の相に分離したり又は外観が濁ったりすることを抑制する効果などの点で、当該組成物中の（iii）の含有量は、好ましくは０．５質量％以上、より好ましくは１質量％以
上であり、そして、好ましくは１５質量％以下、より好ましくは１０質量％以下、更に好ましくは５質量％以下である。 (Iii) Monovalent to trivalent alcohol having 1 to 6 carbon atoms (iii) Examples of the component include one or more alcohols selected from ethanol, ethylene glycol, propylene glycol and glycerin.
In terms of the effect of easily dispersing the liquid detergent composition for clothing of the present invention in water, the effect of suppressing the composition from separating into two or more phases during storage or the appearance becoming cloudy, etc. The content of (iii) in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, Preferably it is 5 mass% or less.
（iv）色素、香料、抗菌防腐剤、シリコーン等の消泡剤、ｐＨ調整剤。 (Iv) Dyes, fragrances, antibacterial preservatives, antifoaming agents such as silicone, and pH adjusters.
（ｖ）（ａ）成分、（ｂ）成分及び（ｃ）成分以外の界面活性剤。
　（ｖ）成分の界面活性剤として、例えば、炭素数１０以上１８以下の脂肪酸又はその塩から選ばれる界面活性剤を含有することが出来る。しかしながら、本発明の高い洗浄力を維持する点で、炭素数１０以上１８以下の脂肪酸又はその塩の含有量は、（ａ）成分、（ｂ）成分及び（ｃ）成分の合計の含有量に対して、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５質量％以下である。下限値は、０質量％又は０質量％超である。
　なお、前記脂肪酸塩の含有量は、それぞれ、対イオンである陽イオンを水素イオンに置き換えた質量、すなわち酸型の化合物に換算した質量で算出する。
　また、（ｖ）の界面活性剤として、炭素数１０以上１６以下のアルキル基を一つ有するアミンオキシドを含有することができる。具体的には、炭素数１０以上１６以下のアルキル基を一つと、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を２つ有するアミンオキシドが挙げられる。 (V) Surfactants other than the components (a), (b) and (c).
As the surfactant (v), for example, a surfactant selected from fatty acids having 10 to 18 carbon atoms or salts thereof can be contained. However, in order to maintain the high detergency of the present invention, the content of the fatty acid having 10 to 18 carbon atoms or a salt thereof is the total content of the component (a), the component (b) and the component (c). On the other hand, it is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. A lower limit is 0 mass% or more than 0 mass%.
The content of the fatty acid salt is calculated by the mass obtained by replacing the cation as a counter ion with a hydrogen ion, that is, the mass converted to an acid type compound.
Further, as the surfactant (v), an amine oxide having one alkyl group having 10 to 16 carbon atoms can be contained. Specifically, an amine oxide having one alkyl group having 10 to 16 carbon atoms and two groups selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms is given. It is done.
　前に述べた衣料用液体洗浄剤組成物は、衣料用液体洗浄剤への使用に好適である。 The liquid detergent composition for clothing described above is suitable for use in a liquid detergent for clothing.
＜衣料の洗浄方法＞
　本発明の衣料用液体洗浄剤組成物は、漬け置き洗濯への使用として好適である。本発明の衣料用液体洗浄剤組成物は、水と混合した洗浄液として、漬け置き洗濯に好適に供せられる。本発明において、漬け置き洗濯とは、衣料を洗浄液に一定時間漬け置く期間がある洗浄方法をいう。好ましくは、漬け置き洗濯では、洗浄液に一定時間漬け置いた後、手動又は洗濯機などの機械力により、衣料と洗浄液とを混ぜ合わせて攪拌洗浄が行われる。また、洗浄液に一定時間漬け置いた後、ブラシ等の道具を用いて衣料を擦る操作が行われる。
　具体的には、下記工程１～３を含む衣料の洗浄方法が挙げられる。
工程１：本発明の衣料用液体洗浄剤組成物及び水を含有する浸漬液と、衣料とを混合する工程
工程２：工程１の後に、前記浸漬液に衣料を漬け置く工程
工程３：工程２の後に、衣料用洗浄剤組成物と水を含む洗浄液中で、衣料を撹拌洗浄する工程 <How to wash clothes>
The liquid detergent composition for clothing of the present invention is suitable for use in pickling laundry. The liquid detergent composition for clothes of the present invention is suitably used for soaking and washing as a washing liquid mixed with water. In the present invention, the soaking and laundering means a washing method in which clothes are soaked in a washing solution for a certain period of time. Preferably, in pickling washing, after being soaked in the cleaning liquid for a certain period of time, the clothes and the cleaning liquid are mixed and washed by stirring manually or by mechanical force such as a washing machine. In addition, after being immersed in a cleaning solution for a certain period of time, an operation of rubbing clothing using a tool such as a brush is performed.
Specifically, a method for washing clothing including the following steps 1 to 3 can be mentioned.
Step 1: A liquid cleaning composition for clothing of the present invention and a dipping solution containing water and a clothing are mixed Step 2: A step after Step 1 in which clothing is immersed in the dipping solution Step 3: Step 2 After, the step of stirring and washing the clothes in a cleaning solution containing a cleaning composition for clothes and water
　工程１は、本発明の衣料用液体洗浄剤組成物及び水を含有する浸漬液と、衣料とを混合する工程である。
　工程１において、本発明の衣料用液体洗浄剤組成物と水とを混合することで得られる浸漬液中の衣料用液体洗浄剤組成物の濃度は、洗浄性の観点から、好ましくは２．５ｇ／Ｌ以上、より好ましくは３ｇ／Ｌ以上、更に好ましくは３．５ｇ／Ｌ以上である。一方、前記浸漬液中の衣料用液体洗浄剤組成物の濃度は、すすぎ性の観点から、好ましくは１０ｇ／Ｌ以下、より好ましくは８ｇ／Ｌ以下、更に好ましくは６ｇ／Ｌ以下である。 Step 1 is a step of mixing the liquid cleaning composition for clothing of the present invention and an immersion liquid containing water with clothing.
In Step 1, the concentration of the liquid detergent composition for clothing in the immersion liquid obtained by mixing the liquid detergent composition for clothing of the present invention and water is preferably 2.5 g from the viewpoint of detergency. / L or more, more preferably 3 g / L or more, still more preferably 3.5 g / L or more. On the other hand, the concentration of the liquid detergent composition for clothing in the immersion liquid is preferably 10 g / L or less, more preferably 8 g / L or less, and still more preferably 6 g / L or less from the viewpoint of rinsing properties.
　工程１に用いられる水は、ドイツ硬度で１°ＤＨ以上３０°ＤＨ以下の硬度の水を使用できる。タンパク質を含む汚れの優れた洗浄性の効果をより実感できる点から、ドイツ硬度が１°ＤＨ以上、更に３°ＤＨ以上、より更に５°ＤＨ以上、より更に６°ＤＨ以上、より更に８°ＤＨ以上、より更に９°ＤＨ以上、より更に１０°ＤＨ以上の水を使用できる。洗浄時の泡立ち性、泡の持続性の観点から、ドイツ硬度が３０°ＤＨ以下、更に２５°ＤＨ以下、より更に２０°ＤＨ以下の硬度の水を使用できる。硬度は、エチレンジアミン四酢酸二ナトリウム塩を使用したキレート滴定法で求められる全硬度を表す。 Water used in step 1 can be water having a German hardness of 1 ° DH to 30 ° DH. German hardness is 1 ° DH or higher, 3 ° DH or higher, 5 ° DH or higher, 6 ° DH or higher, 8 ° or higher due to the fact that it can realize the effect of excellent cleaning performance of soil containing protein. Water of DH or higher, further 9 ° DH or higher, and further 10 ° DH or higher can be used. From the viewpoints of foaming properties during washing and foam persistence, water having a German hardness of 30 ° DH or less, further 25 ° DH or less, and further 20 ° DH or less can be used. Hardness represents the total hardness determined by chelate titration method using ethylenediaminetetraacetic acid disodium salt.
　工程１において、本発明の衣料用液体洗浄剤組成物と水とを混合して得られる浸漬液の容量（リットル）と、衣料の質量（ｋｇ）との比（以後、浴比と称する）は、手洗い洗浄時の洗濯のしやすさという点から、〔洗浄液の容量（リットル）〕／〔衣料の質量（ｋｇ）〕で、１以上が好ましく、２以上がより好ましく、３以上が更に好ましく、５以上が更に好ましい。洗浄性の観点から、浴比は、１００以下が好ましく、９０以下が好ましく、２０以下が好ましく、１０以下がより好ましい。 In step 1, the ratio (hereinafter referred to as bath ratio) of the volume (liter) of the immersion liquid obtained by mixing the liquid cleaning composition for clothing of the present invention and water and the mass (kg) of the clothing is as follows. From the viewpoint of ease of washing at the time of hand washing, [capacity of washing liquid (liter)] / [mass of clothing (kg)] is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more, 5 or more is more preferable. From the viewpoint of detergency, the bath ratio is preferably 100 or less, preferably 90 or less, preferably 20 or less, and more preferably 10 or less.
　工程１では、水と本発明の衣料用液体洗浄剤組成物とを予め混合して得た浸漬液と、衣料とを混合しても良い。また、衣料と水とを混合した衣料を含む水と、本発明の衣料用液体洗浄剤組成物を混合しても良い。この時に、衣料を含む水と、本発明の衣料用液体洗浄剤組成物が混合されることで浸漬液が形成される。また、衣料と水と本発明の衣料用液体洗浄剤組成物を同時に混合しても良い。この時に、水と本発明の衣料用液体洗浄剤組成物が混合されることで浸漬液が形成される。 In step 1, an immersion liquid obtained by previously mixing water and the liquid cleaning composition for clothing of the present invention may be mixed with clothing. Moreover, you may mix the water containing the clothing which mixed clothing and water, and the liquid cleaning composition for clothing of this invention. At this time, the immersion liquid is formed by mixing water containing clothing and the liquid cleaning composition for clothing of the present invention. Moreover, you may mix clothing, water, and the liquid cleaning composition for clothing of this invention simultaneously. At this time, an immersion liquid is formed by mixing water and the liquid cleaning composition for clothing of the present invention.
　工程２は、前記の工程１の後に、前記浸漬液に衣料を漬け置く工程である。
　本発明の洗浄方法において、衣料を漬け置く時間は、タンパク質を含む汚れの洗浄性の観点、又は後に示す工程３に要する労力の低減の観点から、１０分以上が好ましく、２０分以上がより好ましい。洗濯に要する時間を短くする点で、１２０分以下が好ましく、６０分以下がより好ましい。本発明において衣料を漬け置く時間とは、本発明の衣料用液体洗浄剤組成物と水と衣料とが洗濯１回に必要な質量で混合された時点から、工程３における撹拌洗浄が開始されるまでの時間を言う。 Step 2 is a step of immersing clothing in the immersion liquid after Step 1 described above.
In the cleaning method of the present invention, the time for immersing the clothes is preferably 10 minutes or more, more preferably 20 minutes or more, from the viewpoint of the ability to clean the soil containing protein, or from the viewpoint of reducing the labor required for Step 3 described later. . 120 minutes or less are preferable and 60 minutes or less are more preferable in terms of shortening the time required for washing. In the present invention, the time for immersing the clothes is the time when the liquid cleaning composition for clothes of the present invention, water, and clothes are mixed in a mass necessary for one washing, and stirring and washing in step 3 is started. Say time to.
　工程３は、前記工程２の後に、衣料用洗浄剤組成物と水を含む洗浄液中で、衣料を撹拌洗浄する工程である。撹拌洗浄とは、手動又は洗濯機などの機械力により、衣料と洗浄液を撹拌し、衣料を洗浄することを意味する。手動で衣料と洗浄液を撹拌洗浄するとは、洗浄液中で衣料をもみ洗いすること、洗浄液を含む衣料同士を擦り合わせることで衣料を洗浄すること、洗浄液を含む衣料をブラシ等の道具で擦り衣料を洗浄すること、洗浄液中と衣料を手で回転操作や往復操作により撹拌し衣料を洗浄すること、洗浄液中の衣料を手で圧縮する操作を複数回行い、衣料を洗浄することを意味する。
　工程３で使用する衣料用洗浄剤組成物は、本発明の衣料用液体洗浄剤組成物であっても良い。また、工程３で使用する衣料用洗浄剤組成物は、本発明の衣料用液体洗浄剤組成物とは異なる衣料用洗浄剤組成物であっても良い。プロテアーゼによるタンパク汚れを含む汚れの洗浄作用を更に高める点で、工程３で使用する衣料用洗浄剤組成物は、本発明の衣料用液体洗浄剤組成物が好ましい。 Step 3 is a step of stirring and washing the garment after the step 2 in a washing liquid containing a garment cleaning composition and water. The stirring cleaning means that the clothes and the cleaning liquid are stirred manually or mechanically such as a washing machine to wash the clothes. Washing and washing clothes and cleaning solution manually is to wash the clothing in the cleaning solution, wash the clothing by rubbing the clothing containing the cleaning solution together, and rub the clothing containing the cleaning solution with a tool such as a brush. It means washing the clothes by washing the clothes and the clothes by manually rotating and reciprocating the clothes to wash the clothes, and manually compressing the clothes in the washing liquid a plurality of times.
The garment cleaning composition used in step 3 may be the garment liquid cleaning composition of the present invention. Moreover, the cleaning composition for clothing used in Step 3 may be a cleaning composition for clothing that is different from the liquid cleaning composition for clothing of the present invention. The liquid cleaning composition for clothing of the present invention is preferable as the clothing cleaning composition used in Step 3 in that it further enhances the cleaning action of the soil including protein soil caused by protease.
　本発明のより具体的な態様を以下に示す。これらの態様には、これまでに述べた衣料用液体洗浄剤組成物、及び衣料の洗浄方法に関する事項を適宜適用することができる。
＜１＞
　下記（ａ）成分、（ｂ）成分、（ｃ）成分、（ｄ）成分、（ｅ）成分及び水を含有し、
　（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量が５質量％以上、好ましくは６質量％以上、より好ましくは７質量％以上、更に好ましくは８質量％以上、更に好ましくは９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３０質量％以下、更に好ましくは２５質量％以下、更に好ましくは２０質量％以下であり、
　（ｄ）成分の含有量が２質量％以上、好ましくは２．２質量％以上、より好ましくは２．４質量％以上、更に好ましくは２．６質量％以上、更に好ましくは２．８質量％以上、更に好ましくは３質量％以上、そして、８質量％以下、好ましくは７質量％以下、より好ましくは６質量％以下、更に好ましくは５質量％以下であり、
　（ａ）成分の含有量と（ｂ）成分の含有量との質量比が、〔（ａ）成分の含有量〕／〔（ｂ）成分の含有量〕で０．５以上、好ましくは０．５５以上、より好ましくは０．６以上、更に好ましくは０．６５以上、更に好ましくは０．７以上、更に好ましくは０．７５以上、更に好ましくは０．８以上、更に好ましくは０．８５以上、更に好ましくは０．９以上、そして、１０以下、好ましくは９以下、より好ましくは８以下、更に好ましくは７以下、更に好ましくは６以下、更に好ましくは５以下、更に好ましくは４以下、更に好ましくは３以下、更に好ましくは２以下である、
衣料用液体洗浄剤組成物。
（ａ）成分：炭素数１０以上１８以下のアルキル硫酸エステル塩
（ｂ）成分：下記一般式（１）で表されるアルキルエーテル硫酸エステル塩
　　Ｒ－Ｏ－（ＡＯ）ｎ－ＳＯ３Ｍ　　（１）
〔式中、Ｒは炭素数１０以上１８以下の脂肪族炭化水素基であり、ＡＯは炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｎは１以上２０以下の整数であり、Ｍは陽イオンである。〕
（ｃ）成分：ノニオン界面活性剤
（ｄ）成分：炭素数１以上８以下の有機アンモニウム硫酸塩、及び無機硫酸塩（但し、硫酸カルシウムを除く）から選ばれる１種以上の硫酸塩
（ｅ）成分：プロテアーゼ More specific embodiments of the present invention are shown below. The matters regarding the liquid cleaning composition for clothing and the method for washing the clothing described above can be appropriately applied to these embodiments.
<1>
Contains the following (a) component, (b) component, (c) component, (d) component, (e) component and water,
The total content of component (a) and component (b) is 5% by mass or more, preferably 6% by mass or more, more preferably 7% by mass or more, and still more preferably 8% by mass or more. More preferably, it is 9% by mass or more and 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and further preferably 20% by mass or less.
The content of the component (d) is 2% by mass or more, preferably 2.2% by mass or more, more preferably 2.4% by mass or more, still more preferably 2.6% by mass or more, and further preferably 2.8% by mass. Or more, more preferably 3% by mass or more, and 8% by mass or less, preferably 7% by mass or less, more preferably 6% by mass or less, still more preferably 5% by mass or less,
The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more, preferably 0.00 in terms of the content of the component (a) / the content of the component (b). 55 or more, more preferably 0.6 or more, still more preferably 0.65 or more, still more preferably 0.7 or more, still more preferably 0.75 or more, still more preferably 0.8 or more, still more preferably 0.85 or more. More preferably, it is 0.9 or more and 10 or less, preferably 9 or less, more preferably 8 or less, further preferably 7 or less, further preferably 6 or less, further preferably 5 or less, still more preferably 4 or less, further Preferably it is 3 or less, more preferably 2 or less,
Liquid detergent composition for clothing.
Component (a): Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) n —SO 3 M (1 )
[In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
(C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease
＜２＞
　前記一般式（１）で表されるアルキルエーテル硫酸エステル塩において、ＡＯがエチレンオキシ基である、＜１＞に記載の衣料用液体洗浄剤組成物。 <2>
The liquid detergent composition for clothes according to <1>, wherein in the alkyl ether sulfate salt represented by the general formula (1), AO is an ethyleneoxy group.
＜３＞
　前記一般式（１）中のｎが１の化合物とｎが２の化合物の合計質量が、全（ｂ）成分中の４０質量％以上、好ましくは５０質量％以上、より好ましくは５５質量％以上、更に好ましくは６０質量％以上、更に好ましくは６５質量％以上、そして、１００質量％以下、好ましくは９０質量％以下、より好ましくは８５質量％以下である、＜１＞又は＜２＞に記載の衣料用液体洗浄剤組成物。 <3>
The total mass of the compound in which n is 1 and the compound in which n is 2 in the general formula (1) is 40% by mass or more, preferably 50% by mass or more, more preferably 55% by mass or more in all the components (b). More preferably, it is 60% by mass or more, more preferably 65% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less, described in <1> or <2>. Liquid detergent composition for clothing.
＜４＞
　前記一般式（１）中のｎが６以上２０以下の化合物の割合が、全（ｂ）成分中、１０質量％以下、好ましくは９質量％以下、より好ましくは８質量％以下、更に好ましくは７質量％以下、更に好ましくは６質量％以下、更に好ましくは５質量％以下、更に好ましくは４質量％以下、更に好ましくは３質量％以下、そして、０質量％以上又は０質量％超である、或いは０質量％である、＜１＞～＜３＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <4>
In the general formula (1), the ratio of the compound in which n is 6 or more and 20 or less is 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, and still more preferably in all the components (b). 7% by mass or less, more preferably 6% by mass or less, further preferably 5% by mass or less, more preferably 4% by mass or less, still more preferably 3% by mass or less, and 0% by mass or more or more than 0% by mass. Or the liquid detergent composition for clothing according to any one of <1> to <3>, wherein the composition is 0% by mass.
＜５＞
　（ｃ）成分の含有量と、（ａ）成分の含有量及び（ｂ）成分の含有量の合計の含有量との質量比が、（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕で０．０２以上、好ましくは０．０４以上、より好ましくは０．０６以上、更に好ましくは０．０８以上、更に好ましくは０．１以上、更に好ましくは０．１２以上、そして、２以下、好ましくは１．８以下、より好ましくは１．６以下、更に好ましくは１．４以下、更に好ましくは１．２以下、更に好ましくは１．０以下、更に好ましくは０．８以下、更に好ましくは０．６以下、更に好ましくは０．４以下である、＜１＞～＜４＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <5>
The mass ratio of the content of (c) component and the total content of (a) component and (b) component is (c) component content / [(a) component content Amount + content of component (b)] is 0.02 or more, preferably 0.04 or more, more preferably 0.06 or more, still more preferably 0.08 or more, still more preferably 0.1 or more, and still more preferably. 0.12 or more, and 2 or less, preferably 1.8 or less, more preferably 1.6 or less, further preferably 1.4 or less, still more preferably 1.2 or less, still more preferably 1.0 or less, The liquid detergent composition for clothing according to any one of <1> to <4>, preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.4 or less.
＜６＞
　（ｃ）成分が、ポリオキシアルキレン基を有するノニオン界面活性剤である、更に平均付加モル数が３モル以上５０モルのポリオキシアルキレン基を有するノニオン界面活性剤である、＜１＞～＜５＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <6>
The component (c) is a nonionic surfactant having a polyoxyalkylene group, and further a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 mol to 50 mol, <1> to <5 > The liquid cleaning composition for clothes of any one of>.
＜７＞
　（ｃ）成分が、下記一般式（ｃ１）で表されるノニオン界面活性剤である、＜６＞に記載の衣料用液体洗浄剤組成物。
　　　　　Ｒ１ｃ－Ｏ－（Ａ’Ｏ）ｍ－Ｈ　　　（ｃ１）
〔式中、Ｒ１ｃは炭素数８以上１８以下の脂肪族炭化水素基であり、Ａ’Ｏは、炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｍは、Ａ’Ｏの平均付加モル数であり、３以上、好ましくは４以上、より好ましくは５以上、更に好ましくは６以上、更に好ましくは７以上、そして、５０以下、好ましくは４５以下、より好ましくは４０以下、更に好ましくは３５以下、更に好ましくは３０以下、更に好ましくは２５以下、更に好ましくは２０以下、更に好ましくは１８以下、更に好ましくは１６以下、更に好ましくは１４以下、更に好ましくは１２以下の数である。〕 <7>
(C) The liquid cleaning composition for clothes according to <6>, wherein the component is a nonionic surfactant represented by the following general formula (c1).
R 1c —O— (A′O) m —H (c1)
[In the formula, R 1c is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and A′O is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms. , M is the average added mole number of A′O, 3 or more, preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, still more preferably 7 or more, and 50 or less, preferably 45 or less. More preferably, it is 40 or less, More preferably, it is 35 or less, More preferably, it is 30 or less, More preferably, it is 25 or less, More preferably, it is 20 or less, More preferably, it is 18 or less, More preferably, it is 16 or less. The number is preferably 12 or less. ]
＜８＞
　前記一般式（ｃ１）において、Ａ’Ｏが、エチレンオキシ基を含むアルキレンオキシ基である、＜７＞に記載の衣料用液体洗浄剤組成物。 <8>
The liquid detergent composition for clothing according to <7>, wherein in the general formula (c1), A′O is an alkyleneoxy group containing an ethyleneoxy group.
＜９＞
　前記一般式（ｃ１）において、Ａ’Ｏが、エチレンオキシ基を含むエチレンオキシ基である、＜８＞に記載の衣料用液体洗浄剤組成物。 <9>
The liquid detergent composition for clothing according to <8>, wherein in the general formula (c1), A′O is an ethyleneoxy group containing an ethyleneoxy group.
＜１０＞
　（ｄ）成分である炭素数１以上８以下の有機アンモニウム硫酸塩が、下記一般式（ｄ１）で表される化合物である、＜１＞～＜９＞の何れか１項に記載の衣料用液体洗浄剤組成物。
　〔（ＣｎＨ２ｎ＋１）ｘＮ（Ｃ２Ｈ４ＯＨ）ｙ〕２＋・ＳＯ４ ２－　　　　（ｄ１）
〔式中、ｎは０以上２以下の整数であり、ｘ、ｙはそれぞれ０以上４以下の数であり、ｘ＋ｙは４であるが、ｎが０でｘが４の場合を除く。ＣｎＨ２ｎ＋１基が複数存在する場合は、同一でも異なっていても良い。〕 <10>
(D) The organic ammonium sulfate having 1 to 8 carbon atoms as a component is a compound represented by the following general formula (d1), for clothing according to any one of <1> to <9> Liquid detergent composition.
[(C n H 2n + 1 ) x N (C 2 H 4 OH) y ] 2 + · SO 4 2− (d1)
[In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C n H 2n + 1 groups, they may be the same or different. ]
＜１１＞
　前記一般式（ｄ１）で表される化合物が、モノエタノールアンモニウム硫酸塩、メチルモノエタノールアンモニウム硫酸塩、エチルモノエタノールアンモニウム硫酸塩、メチルジエタノールアンモニウム硫酸塩、エチルジエタノールアンモニウム硫酸塩、ジエタノールアンモニウム硫酸塩及びトリエタノールアンモニウム硫酸塩から選ばれる１種以上の化合物である、＜１０＞に記載の衣料用液体洗浄剤組成物。 <11>
The compound represented by the general formula (d1) is monoethanol ammonium sulfate, methyl monoethanol ammonium sulfate, ethyl monoethanol ammonium sulfate, methyl diethanol ammonium sulfate, ethyl diethanol ammonium sulfate, diethanol ammonium sulfate, and The liquid detergent composition for clothes according to <10>, which is one or more compounds selected from triethanolammonium sulfate.
＜１２＞
　（ｄ）成分である無機硫酸塩（但し、硫酸カルシウムを除く）が、硫酸アンモニウム、アルカリ金属硫酸塩、及び硫酸カルシウムを除くアルカリ土類金属硫酸塩から選ばれる１種以上の無機硫酸塩である、＜１＞～＜１１＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <12>
(D) The component inorganic sulfate (excluding calcium sulfate) is one or more inorganic sulfates selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate. The liquid detergent composition for clothing according to any one of <1> to <11>.
＜１３＞
　アルカリ金属硫酸塩が、硫酸リチウム、硫酸ナトリウム及び硫酸カリウムから選ばれる１種以上であり、並びに硫酸カルシウムを除くアルカリ土類金属硫酸塩が、硫酸マグネシウムから選ばれる１種以上の無機硫酸塩である、＜１２＞に記載の衣料用液体洗浄剤組成物。 <13>
The alkali metal sulfate is at least one selected from lithium sulfate, sodium sulfate and potassium sulfate, and the alkaline earth metal sulfate excluding calcium sulfate is at least one inorganic sulfate selected from magnesium sulfate. <12> The liquid cleaning composition for clothes according to <12>.
＜１４＞
　（ｄ）成分の含有量が、硫酸イオンとして、１．４質量％以上、好ましくは１．５質量％以上、より好ましくは１．６質量％以上、更に好ましくは１．７質量％以上、更に好ましくは１．８質量％以上、更に好ましくは１．９質量％以上、更に好ましくは２．０質量％以上、そして、７質量％以下、好ましくは６質量％以下、より好ましくは５．５質量％以下、更に好ましくは４．０質量％以下、更に好ましくは３．５質量％以下である、＜１＞～＜１３＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <14>
The content of the component (d) as sulfate ions is 1.4% by mass or more, preferably 1.5% by mass or more, more preferably 1.6% by mass or more, still more preferably 1.7% by mass or more, Preferably 1.8% by mass or more, more preferably 1.9% by mass or more, further preferably 2.0% by mass or more, and 7% by mass or less, preferably 6% by mass or less, more preferably 5.5% by mass. %, More preferably 4.0% by mass or less, and further preferably 3.5% by mass or less, The liquid detergent composition for clothing according to any one of <1> to <13>.
＜１５＞
　更に（ｆ）成分として、炭素数２以上８以下の２価以上６価以下の多価アルコールを含有する、＜１＞～＜１４＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <15>
The liquid detergent composition for clothing according to any one of <1> to <14>, which further contains a dihydric or higher polyvalent alcohol having 2 to 8 carbon atoms as a component (f). .
＜１６＞
　（ｆ）成分が、エチレングリコール、プロピレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、及び５価以上６価以下の糖アルコールから選ばれる１種以上の化合物、更に、プロピレングリコール、グリセリン、ジエチレングリコール、トリエチレングリコール及びソルビトールから選ばれる１種以上の化合物である、＜１５＞に記載の衣料用液体洗浄剤組成物。 <16>
The component (f) is at least one compound selected from ethylene glycol, propylene glycol, diethylene glycol, glycerin, pentaerythritol, and sugar alcohols having a valence of 5 to 6. In addition, propylene glycol, glycerin, diethylene glycol, triethylene glycol And a liquid detergent composition for clothes according to <15>, which is at least one compound selected from sorbitol and sorbitol.
＜１７＞
　（ｆ）成分の含有量が、０．２質量％以上、好ましくは０．４質量％以上、より好ましくは０．６質量％以上、更に好ましくは０．８質量％以上、そして、１０質量％以下、好ましくは９質量％以下、より好ましくは８質量％以下、更に好ましくは７質量％以下である、＜１５＞又は＜１６＞に記載の衣料用液体洗浄剤組成物。 <17>
The content of the component (f) is 0.2% by mass or more, preferably 0.4% by mass or more, more preferably 0.6% by mass or more, still more preferably 0.8% by mass or more, and 10% by mass. The liquid detergent composition for clothing according to <15> or <16>, preferably 9% by mass or less, more preferably 8% by mass or less, and still more preferably 7% by mass or less.
＜１８＞
　更に（ｇ）成分として、カルシウムイオン供与体を含有し、（ｇ）成分の含有量が、カルシウムイオンとして、０．０１質量％以上、好ましくは０．０２質量％以上、より好ましくは０．０３質量％以上、そして、０．１５質量％以下、好ましくは０．１２質量％以下、より好ましくは０．１質量％以下である、＜１＞～＜１７＞の何れか１項に記載の衣料用液体洗浄剤組成物。 <18>
Further, as component (g), a calcium ion donor is contained, and the content of component (g) is 0.01% by mass or more, preferably 0.02% by mass or more, more preferably 0.03% as calcium ions. The clothing according to any one of <1> to <17>, which is not less than mass% and not more than 0.15 mass%, preferably not more than 0.12 mass%, more preferably not more than 0.1 mass%. Liquid detergent composition.
＜１９＞
　前記（ｇ）成分が、塩化カルシウムである、＜１８＞に記載の衣料用液体洗浄剤組成物。 <19>
The liquid cleaning composition for clothes according to <18>, wherein the component (g) is calcium chloride.
＜２０＞
　料用液体洗浄剤組成物の、ガラス電極を使用したｐＨメーターを用いて測定した２５℃でのｐＨが、４以上、好ましくは４．５以上、より好ましくは５．０以上、更に好ましくは５．５以上、更に好ましくは６．０以上、更に好ましくは６．５以上、更に好ましくは７．０以上、更に好ましくは７．５以上、更に好ましくは８．０以上、そして、１０以下、好ましくは９．８以下、より好ましくは９．５以下である、＜１＞～＜１９＞のの何れか１項に記載の衣料用液体洗浄剤組成物。 <20>
The pH of the liquid detergent composition for use at 25 ° C. measured with a pH meter using a glass electrode is 4 or more, preferably 4.5 or more, more preferably 5.0 or more, and still more preferably 5 0.5 or more, more preferably 6.0 or more, more preferably 6.5 or more, more preferably 7.0 or more, more preferably 7.5 or more, more preferably 8.0 or more, and 10 or less, preferably The liquid detergent composition for clothing according to any one of <1> to <19>, wherein is 9.8 or less, more preferably 9.5 or less.
＜２１＞
　＜１＞～＜２０＞の何れか１項に記載の衣料用液体洗浄剤組成物の、漬け置き洗濯への使用。 <21>
Use of the liquid detergent composition for clothing according to any one of <1> to <20> for pickling washing.
＜２２＞
　下記工程１～３を含む衣料の洗浄方法。
工程１：＜１＞～＜２０＞の何れか１項に記載の衣料用液体洗浄剤組成物及び水を含有する浸漬液と、衣料とを混合する工程
工程２：工程１の後に、前記浸漬液に衣料を漬け置く工程
工程３：工程２の後に、衣料用洗浄剤組成物と水を含む洗浄液中で、衣料を撹拌洗浄する工程 <22>
A method for washing clothing comprising the following steps 1 to 3.
Step 1: Mixing the liquid cleaning composition for clothing according to any one of <1> to <20> and an immersion liquid containing water, and Step 2: Step 1 after the immersion Step 3 of immersing clothing in liquid Step 3: Step of stirring and washing clothing in a cleaning solution containing a cleaning composition for clothing and water after Step 2
実施例
＜実施例１～１９、比較例１～６＞
　下記成分を用い、表２に示す衣料用液体洗浄剤組成物を調製し、得られた組成物を用いて、下記の方法で洗浄力、及び酵素活性安定性の評価を行った。その結果を表２に示す。なお、組成物のｐＨは、モノエタノールアミン又はクエン酸で調整した。ｐＨの測定には、ガラス電極を使用したｐＨメーターを使用した。 Examples <Examples 1 to 19, Comparative Examples 1 to 6>
A liquid detergent composition for clothing shown in Table 2 was prepared using the following components, and the cleaning power and enzyme activity stability were evaluated by the following methods using the obtained composition. The results are shown in Table 2. The pH of the composition was adjusted with monoethanolamine or citric acid. A pH meter using a glass electrode was used for pH measurement.
＜配合成分＞
　（ａ）成分及び（ｂ）成分
・（ａ－１）：ラウリル硫酸エステルナトリウム、（ａ）成分に相当する。
・（ａｂ－１）：（ａ）成分と（ｂ）成分を表１の組成で含有する界面活性剤混合物、（ａｂ－１）中の（ａ）成分の含有量は５０．３質量％であり、（ｂ）成分の含有量は４９．７質量％
・（ａｂ－２）：（ａ）成分と（ｂ）成分を表１の組成で含有する界面活性剤混合物、（ａｂ－２）中の（ａ）成分の含有量は３０．５質量％であり、（ｂ）成分の含有量は６９．５質量％
・（ａｂ－３）：（ａ）成分と（ｂ）成分を表１の組成で含有する界面活性剤混合物、（ａｂ－３）中の（ａ）成分の含有量は１９．０質量％であり、（ｂ）成分の含有量は８１質量％ <Composition ingredients>
Component (a) and component (b)-(a-1): Sodium lauryl sulfate ester, corresponding to component (a).
(Ab-1): a surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-1) is 50.3% by mass Yes, the content of component (b) is 49.7% by mass
(Ab-2): a surfactant mixture containing the components (a) and (b) in the composition of Table 1, and the content of the component (a) in (ab-2) is 30.5% by mass Yes, the content of component (b) is 69.5% by mass
(Ab-3): a surfactant mixture containing the components (a) and (b) in the composition shown in Table 1, and the content of the component (a) in (ab-3) is 19.0% by mass. Yes, content of component (b) is 81% by mass
　（ｃ）成分
・（ｃ－１）：前記一般式（ｃ１）において、Ｒ１ｃがラウリル基／ミリスチル基＝９０／１０（質量比）である混合アルキル基であり、Ａ’Ｏがエチレンオキシ基であり、ｍが平均で１０の数である、ポリオキシエチレンアルキルエーテル
・（ｃ－２）：前記一般式（ｃ１）において、Ｒ１ｃがラウリル基／ミリスチル基＝９０／１０（質量比）である混合アルキル基であり、Ａ’Ｏがエチレンオキシ基であり、ｍが平均で３の数である、ポリオキシエチレンアルキルエーテル
・（ｃ－３）：前記一般式（ｃ１）において、Ｒ１ｃがラウリル基／ミリスチル基＝９０／１０（質量比）である混合アルキル基であり、Ａ’Ｏがエチレンオキシ基であり、ｍが平均で２０の数であるポリオキシエチレンアルキルエーテル Component (c-1): in the general formula (c1), R 1c is a mixed alkyl group of lauryl group / myristyl group = 90/10 (mass ratio), and A′O is an ethyleneoxy group M is an average number of 10, polyoxyethylene alkyl ether (c-2): In the general formula (c1), R 1c is lauryl group / myristyl group = 90/10 (mass ratio) A mixed alkyl group, A′O is an ethyleneoxy group, and m is an average number of 3, polyoxyethylene alkyl ether (c-3): In the general formula (c1), R 1c is Polyoxyethylene alkyl ether in which lauryl group / myristyl group = 90/10 (mass ratio), mixed alkyl group, A′O is ethyleneoxy group, and m is an average of 20
　（ｄ）成分
・（ｄ－１）：硫酸ナトリウム。硫酸ナトリウム１モル中の硫酸イオンの含有量は６８質量％。
・（ｄ－２）：硫酸カリウム。硫酸カリウム１モル中の硫酸イオンの含有量は５５質量％。
・（ｄ－３）：トリエタノールアンモニウム硫酸塩、トリエタノールアンモニウム硫酸塩１モル中の硫酸イオンの含有量は３５質量％ (D) Component / (d-1): Sodium sulfate. The content of sulfate ions in 1 mol of sodium sulfate is 68% by mass.
(D-2): Potassium sulfate. The content of sulfate ions in 1 mol of potassium sulfate is 55% by mass.
(D-3): Triethanolammonium sulfate, the content of sulfate ion in 1 mol of triethanolammonium sulfate is 35% by mass
　（ｄ’）成分：（ｄ）成分の比較化合物
・（ｄ’－１）：塩化ナトリウム
・（ｄ’－２）：炭酸ナトリウム Component (d ′): Comparison compound of component (d) (d′-1): sodium chloride (d′-2): sodium carbonate
　（ｅ）成分
・（ｅ－１）；サビナーゼウルトラ１６Ｌ（ノボザイム社製）
・（ｅ－２）；アルカリプロテアーゼ（ＫＡＰ、花王株式会社製） (E) Component (e-1); Sabinase Ultra 16L (manufactured by Novozyme)
(E-2); alkaline protease (KAP, manufactured by Kao Corporation)
　（ｆ）成分
・（ｆ－１）：プロピレングリコール
・（ｆ－２）：グリセリン
・（ｆ－３）：ジエチレングリコール
・（ｆ－４）：トリエチレングリコール Component (f-1): (f-1): Propylene glycol (f-2): Glycerin (f-3): Diethylene glycol (f-4): Triethylene glycol
　（ｇ）成分
・（ｇ－１）：塩化カルシウム。塩化カルシウム１モル中のカルシウムイオンの含有量は３６質量％。 (G) Component / (g-1): Calcium chloride. The content of calcium ions in 1 mol of calcium chloride is 36% by mass.
＜洗浄力の評価＞
　衣料用液体洗浄剤組成物と水を混合した洗浄液１Ｌに、ＡＳ－１０人工汚染布（Testfabrics社製、１０ｃｍ×１０ｃｍに裁断したもの）を４枚（合計１２ｇ）入れ、３０分浸
漬した後、ターゴトメーター（Ueshima社製MS-8212、内径１２ｃｍ、高さ１７．５ｃｍ）にて、１００ｒ／ｍｉｎで３分間洗浄した。洗浄液中の液体洗浄剤組成物の濃度は０．４質量％であった。また、洗浄液の調製に使用した水は、イオン交換水に塩化カルシウムを加え、ドイツ硬度を１０°ＤＨ（１７８ｍｇＣａＣＯ３／Ｌ）に調整した水であった。洗浄液の水温は３０℃であり人工汚染布の浸漬中もこの温度を維持した。洗浄後、同１０°ＤＨに調整した水にて３０秒間すすぎを行った。 <Evaluation of cleaning power>
After placing 4 sheets of AS-10 artificially contaminated cloth (made by Testfabrics, cut into 10 cm × 10 cm) (total 12 g) in 1 L of a cleaning liquid obtained by mixing a liquid cleaning composition for clothing and water, Washing was performed at 100 r / min for 3 minutes with a targotometer (MS-8212 manufactured by Ueshima Co., Ltd., inner diameter 12 cm, height 17.5 cm). The concentration of the liquid detergent composition in the cleaning liquid was 0.4% by mass. The water used for the preparation of the cleaning liquid was water in which calcium chloride was added to ion-exchanged water and the German hardness was adjusted to 10 ° DH (178 mg CaCO 3 / L). The water temperature of the cleaning liquid was 30 ° C., and this temperature was maintained during the immersion of the artificially contaminated cloth. After washing, rinsing was performed for 30 seconds with water adjusted to 10 ° DH.
　洗浄力は、汚染前の原布及び洗浄前後の汚染布の５５０ｎｍにおける反射率を自記色彩計（株式会社島津製作所）にて測定し、次式によって洗浄率（％）を求めた。表には、４枚の人工汚染布の洗浄率の平均値を示した。
　洗浄率は値が高い方が好ましい。この評価では、洗浄率の平均値が５５％以上であると、一般的な水準で洗浄力を有する洗浄剤組成物に対して優位であることを、より明確に認識できる。 The detergency was determined by measuring the reflectance at 550 nm of the raw cloth before contamination and the contaminated cloth before and after washing with a self-recording colorimeter (Shimadzu Corporation), and obtaining the washing rate (%) by the following formula. The table shows the average value of the washing rate of the four artificially contaminated cloths.
A higher cleaning rate is preferred. In this evaluation, it can be recognized more clearly that the average value of the cleaning rate is 55% or more, which is superior to a cleaning composition having a cleaning power at a general level.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
＜酵素活性安定性の評価＞
　１％（ｗ／ｖ）のカゼイン（ハマーステイン；メルク社製）を含む５０ｍＭホウ酸緩衝液（ｐＨ１０．５）の１．０ｍＬを３０℃で５分間保持した後、０．１ｍＬの酵素溶液を添加し、３０℃で１５分間反応させた。次に反応停止液であるＴＣＡ溶液（０．１１Ｍトリクロロ酢酸、０．２２Ｍ酢酸ナトリウム、０．３３Ｍ酢酸）の２．０ｍＬを添加し、室温で１０分間放置した後に、ろ過により酸変性タンパク質を除去し、ろ液に含まれる酸可溶性タンパク質分解物をローリー法により定量した。すなわち、ろ液０．５ｍＬに、２．５ｍＬのアルカリ性銅溶液〔１％（ｗ／ｖ）酒石酸カリウムナトリウム水溶液、１％（ｗ／ｖ）硫酸銅水溶液、炭酸ナトリウムの０．１Ｍ水酸化ナトリウム水溶液溶解物（炭酸ナトリウム濃度２％（ｗ／ｖ）を１：１：１００（ｖ／ｖ）で混合したもの〕を添加し、３０℃、１０分間保温した後に、０．２５ｍＬの希釈フェノール試薬（フェノール試薬（関東化学株式会社）をイオン交換水で２倍に希釈したもの）を更に加え、３０℃、３０分間保温した後に、６６０ｎｍにおける吸光度を測定し、その吸光度の値から酵素活性を求めた。尚、ＴＣＡ溶液を加え室温１０分間放置した後に酵素溶液を加えた結果をブランクとした。
　表１の液体洗浄剤組成物について、保存前の酵素活性と４０℃で１４日保存した後の酵素活性とをそれぞれ上記の方法で測定し、酵素活性安定性を以下の式により求めた。酵素活性安定性は、値が高い方が好ましく、この評価では７０％以上が実用上好ましい水準である。
　酵素活性安定性（％）＝（保存後の酵素活性）／（保存前の酵素活性）×１００ <Evaluation of enzyme activity stability>
After holding 1.0 mL of 50 mM borate buffer (pH 10.5) containing 1% (w / v) casein (Hammerstein; manufactured by Merck) for 5 minutes at 30 ° C., 0.1 mL of the enzyme solution was added. The mixture was added and reacted at 30 ° C. for 15 minutes. Next, 2.0 mL of a TCA solution (0.11 M trichloroacetic acid, 0.22 M sodium acetate, 0.33 M acetic acid), which is a reaction stop solution, is added and left at room temperature for 10 minutes, and then the acid-denatured protein is removed by filtration. The acid-soluble proteolysate contained in the filtrate was quantified by the Raleigh method. That is, to 0.5 mL of the filtrate, 2.5 mL of an alkaline copper solution [1% (w / v) potassium sodium tartrate aqueous solution, 1% (w / v) copper sulfate aqueous solution, sodium carbonate 0.1 M sodium hydroxide aqueous solution After adding a lysate (sodium carbonate concentration 2% (w / v) mixed at 1: 1: 100 (v / v)) and incubating at 30 ° C. for 10 minutes, 0.25 mL of diluted phenol reagent ( Phenol reagent (Kanto Chemical Co., Ltd. diluted twice with ion-exchanged water) was further added, and the mixture was kept at 30 ° C. for 30 minutes. Then, the absorbance at 660 nm was measured, and the enzyme activity was determined from the absorbance value. The result of adding the enzyme solution after adding the TCA solution and allowing to stand at room temperature for 10 minutes was used as a blank.
For the liquid detergent composition of Table 1, the enzyme activity before storage and the enzyme activity after 14 days of storage at 40 ° C. were measured by the above methods, and the enzyme activity stability was determined by the following equation. The enzyme activity stability is preferably as high as possible. In this evaluation, 70% or more is a practically preferred level.
Enzyme activity stability (%) = (enzyme activity after storage) / (enzyme activity before storage) × 100
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２中、（ａ）／（ｂ）は、〔（ａ）成分の含有量〕／〔（ｂ）成分の含有量〕の質量比であり、（ｃ）／［（ａ）＋（ｂ）］は、（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕の質量比である。
　なお、表２中の（ａ）成分の含有量及び（ｂ）成分の含有量は、表１の組成に基づく含有量及び表２の（ａ－１）の含有量の合計において、小数点以下２桁目を四捨五入した値を記載している。また、表２では、その値から求めた各質量比を示している。
　また、（ｄ）成分のかっこ内の数字は、硫酸イオンとしての質量％である。
　また、（ｅ）成分の質量％は、酵素タンパク量としての質量％である。
　また、（ｇ）成分のかっこ内の数字は、カルシウムイオンとしての質量％である。
　これらは、表３でも同様である。 In Table 2, (a) / (b) is a mass ratio of [content of (a) component] / [content of (b) component], and (c) / [(a) + (b) ] Is a mass ratio of (c) component content / [(a) component content + (b) component content].
In Table 2, the content of the component (a) and the content of the component (b) are the sum of the content based on the composition in Table 1 and the content in (a-1) in Table 2, 2 below the decimal point. The value rounded to the first digit is shown. Moreover, in Table 2, each mass ratio calculated | required from the value is shown.
The number in parentheses of the component (d) is mass% as sulfate ion.
Further, the mass% of the component (e) is mass% as the amount of enzyme protein.
The number in parentheses of the component (g) is mass% as calcium ions.
These are the same in Table 3.
＜試験例１～４＞
　比較例１、及び実施例１、３、５の衣料用液体洗浄剤組成物を基準として、それぞれの組成を表３のように変更した衣料用液体洗浄剤組成物を調製し、実施例１と同様に洗浄力の評価を行った。その結果を表３に示す。なお、組成物のｐＨは、モノエタノールアミン又はクエン酸で調整した。 <Test Examples 1 to 4>
With reference to the liquid detergent composition for clothing of Comparative Example 1 and Examples 1, 3, and 5, a liquid detergent composition for clothing having respective compositions changed as shown in Table 3 was prepared. Similarly, the cleaning power was evaluated. The results are shown in Table 3. The pH of the composition was adjusted with monoethanolamine or citric acid.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　比較例７は、（ｄ）成分を含有しておらず、また、衣料用液体洗浄剤組成物中の（ａ）成分の含有量と（ｂ）成分の含有量との質量比で表される（ａ）／（ｂ）が、本発明の範囲外の組成物である。（ａ）／（ｂ）が本発明の範囲外で、且つ（ｄ）成分を含まない比較例７の組成物の洗浄率と、（ａ）／（ｂ）が本発明の範囲外であるが、（ｄ）成分を含有する比較例１の洗浄率との洗浄率の差は２％であり、（ｄ）成分を含有することによる洗浄率の向上は低い。
　一方、（ａ）／（ｂ）が本発明の範囲内であるが、（ｄ）成分を含まない比較例８、９、１０の組成物に対して、それぞれの比較例に（ｄ）成分を含有する実施例１、３、５の洗浄率は、飛躍的に向上する事が判る。
　また、試験例２～４から、（ａ）／（ｂ）が大きい程、（ｄ）成分を含有する事による洗浄率の向上度合は大きいことが判る。 Comparative Example 7 does not contain the component (d), and is represented by a mass ratio between the content of the component (a) and the content of the component (b) in the liquid cleaning composition for clothing. (A) / (b) is a composition outside the scope of the present invention. Although (a) / (b) is outside the scope of the present invention and (d) the cleaning rate of the composition of Comparative Example 7 not containing the component, and (a) / (b) are outside the scope of the present invention. The difference in the cleaning rate from the cleaning rate of Comparative Example 1 containing the component (d) is 2%, and the improvement in the cleaning rate due to the inclusion of the component (d) is low.
On the other hand, although (a) / (b) is within the scope of the present invention, the composition of Comparative Examples 8, 9, and 10 that does not contain the component (d), the component (d) is added to each comparative example. It turns out that the washing | cleaning rate of Example 1, 3, 5 to contain improves dramatically.
Further, it can be seen from Test Examples 2 to 4 that the greater the ratio (a) / (b), the greater the improvement in the cleaning rate due to the inclusion of the component (d).
＜配合例１～７＞
　実施例１等で用いた配合成分を用いて、表４の配合例１～７の衣料用液体洗浄剤組成物を調製した。組成物のｐＨは、モノエタノールアミン又はクエン酸で調整した。配合例１～７の組成物は、いずれも本発明の効果を有すると考えられる。
　また、配合例５～７において、酵素活性安定性は、配合例７が最も高く、次いで配合例５であり、次いで配合例６と考えられる。また、プロテアーゼによるタンパク汚れの洗浄性を（ｄ）成分が高める効果をより向上させる点については、配合例５と６が最も高く、次いで配合例７であると考えられる。前記の２つの効果のバランスが取れている点で、配合例６が好ましい。 <Formulation examples 1 to 7>
Using the blending components used in Example 1 and the like, liquid cleaning compositions for clothing of Formulation Examples 1 to 7 in Table 4 were prepared. The pH of the composition was adjusted with monoethanolamine or citric acid. All of the compositions of Formulation Examples 1 to 7 are considered to have the effects of the present invention.
In Formulation Examples 5 to 7, the enzyme activity stability is highest in Formulation Example 7, then Formulation Example 5, and then Formulation Example 6. In terms of further improving the effect of the component (d) to improve the protein stain detergency with protease, Formulation Examples 5 and 6 are the highest, followed by Formulation Example 7. Formulation Example 6 is preferable in that the above two effects are balanced.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (10)

  1. 　下記（ａ）成分、（ｂ）成分、（ｃ）成分、（ｄ）成分、（ｅ）成分及び水を含有し、
    　（ａ）成分の含有量と（ｂ）成分の含有量との合計の含有量が５質量％以上４０質量％以下であり、
    　（ｄ）成分の含有量が２質量％以上８質量％以下であり、
    　（ａ）成分の含有量と（ｂ）成分の含有量との質量比が、〔（ａ）成分の含有量〕／〔（ｂ）成分の含有量〕で０．５以上１０以下である、
    衣料用液体洗浄剤組成物。
    （ａ）成分：炭素数１０以上１８以下のアルキル硫酸エステル塩
    （ｂ）成分：下記一般式（１）で表されるアルキルエーテル硫酸エステル塩
    　　Ｒ－Ｏ－（ＡＯ）ｎ－ＳＯ３Ｍ　　（１）
    〔式中、Ｒは炭素数１０以上１８以下の脂肪族炭化水素基であり、ＡＯは炭素数２のアルキレンオキシ基及び炭素数３のアルキレンオキシ基から選ばれるアルキレンオキシ基であり、ｎは１以上２０以下の整数であり、Ｍは陽イオンである。〕
    （ｃ）成分：ノニオン界面活性剤
    （ｄ）成分：炭素数１以上８以下の有機アンモニウム硫酸塩、及び無機硫酸塩（但し、硫酸カルシウムを除く）から選ばれる１種以上の硫酸塩
    （ｅ）成分：プロテアーゼ     Contains the following (a) component, (b) component, (c) component, (d) component, (e) component and water,
    The total content of the content of the component (a) and the content of the component (b) is 5% by mass or more and 40% by mass or less,
    (D) The content of the component is 2% by mass or more and 8% by mass or less,
    The mass ratio of the content of the component (a) and the content of the component (b) is 0.5 or more and 10 or less in [(a) component content] / [(b) component content].
    Liquid detergent composition for clothing.
    Component (a): Alkyl sulfate ester salt having 10 to 18 carbon atoms (b) Component: Alkyl ether sulfate salt represented by the following general formula (1) R—O— (AO) n —SO 3 M (1 )
    [In the formula, R is an aliphatic hydrocarbon group having 10 to 18 carbon atoms, AO is an alkyleneoxy group selected from an alkyleneoxy group having 2 carbon atoms and an alkyleneoxy group having 3 carbon atoms, and n is 1 It is an integer of 20 or more and M is a cation. ]
    (C) Component: Nonionic surfactant (d) Component: One or more sulfates (e) selected from organic ammonium sulfates having 1 to 8 carbon atoms and inorganic sulfates (excluding calcium sulfate) Ingredient: Protease
  2. 　（ｃ）成分の含有量と、（ａ）成分の含有量及び（ｂ）成分の含有量の合計の含有量との質量比が、（ｃ）成分の含有量／〔（ａ）成分の含有量＋（ｂ）成分の含有量〕で０．０２以上２以下である、請求項１に記載の衣料用液体洗浄剤組成物。 The mass ratio of the content of (c) component and the total content of (a) component and (b) component is (c) component content / [(a) component content The liquid detergent composition for clothing according to claim 1, which is 0.02 or more and 2 or less in terms of “amount + content of component (b)”.
  3. 　（ｄ）成分である炭素数１以上８以下の有機アンモニウム硫酸塩が、下記一般式（ｄ１）で表される化合物である、請求項１又は２に記載の衣料用液体洗浄剤組成物。
    　〔（ＣｎＨ２ｎ＋１）ｘＮ（Ｃ２Ｈ４ＯＨ）ｙ〕２＋・ＳＯ４ ２－　　　　（ｄ１）
    〔式中、ｎは０以上２以下の整数であり、ｘ、ｙはそれぞれ０以上４以下の数であり、ｘ＋ｙは４であるが、ｎが０でｘが４の場合を除く。ＣｎＨ２ｎ＋１基が複数存在する場合は、同一でも異なっていても良い。〕     The liquid detergent composition for clothes according to claim 1 or 2, wherein the organic ammonium sulfate having 1 to 8 carbon atoms as the component (d) is a compound represented by the following general formula (d1).
    [(C n H 2n + 1 ) x N (C 2 H 4 OH) y ] 2 + · SO 4 2− (d1)
    [In the formula, n is an integer of 0 or more and 2 or less, x and y are each a number of 0 or more and 4 or less, and x + y is 4, except when n is 0 and x is 4. When there are a plurality of C n H 2n + 1 groups, they may be the same or different. ]
  4. 　（ｄ）成分である無機硫酸塩（但し、硫酸カルシウムを除く）が、硫酸アンモニウム、アルカリ金属硫酸塩、及び硫酸カルシウムを除くアルカリ土類金属硫酸塩から選ばれる１種以上の無機硫酸塩である、請求項１～３の何れかに記載の衣料用液体洗浄剤組成物。 (D) The component inorganic sulfate (excluding calcium sulfate) is one or more inorganic sulfates selected from ammonium sulfate, alkali metal sulfate, and alkaline earth metal sulfate excluding calcium sulfate. The liquid detergent composition for clothing according to any one of claims 1 to 3.
  5. 　（ｄ）成分の含有量が、硫酸イオンとして、１．４質量％以上７質量％以下である、請求項１～４の何れかに記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothing according to any one of claims 1 to 4, wherein the content of the component (d) is from 1.4% by mass to 7% by mass as sulfate ions.
  6. 　更に（ｆ）成分として、炭素数２以上８以下の２価以上６価以下の多価アルコールを含有する、請求項１～５の何れかに記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothing according to any one of claims 1 to 5, further comprising, as component (f), a polyhydric alcohol having 2 to 8 carbon atoms and having 2 to 8 carbon atoms.
  7. 　更に（ｇ）成分として、カルシウムイオン供与体を含有し、（ｇ）成分の含有量が、カルシウムイオンとして、０．０１質量％以上０．１５質量％以下である、請求項１～６の何れかに記載の衣料用液体洗浄剤組成物。 The component (g) further contains a calcium ion donor, and the content of the component (g) is 0.01% by mass or more and 0.15% by mass or less as calcium ions. A liquid detergent composition for clothing according to claim 1.
  8. 　（ｃ）成分が、平均付加モル数が３モル以上５０モルのポリオキシアルキレン基を有するノニオン界面活性剤である、請求項１～７の何れかに記載の衣料用液体洗浄剤組成物。 The liquid detergent composition for clothing according to any one of claims 1 to 7, wherein the component (c) is a nonionic surfactant having a polyoxyalkylene group having an average addition mole number of 3 to 50 moles.
  9. 　前記請求項１～８の何れかに記載の衣料用液体洗浄剤組成物の、漬け置き洗濯への使用。 Use of the liquid detergent composition for clothing according to any one of claims 1 to 8 for pickling and washing.
  10. 　下記工程１～３を含む衣料の洗浄方法。
    工程１：請求項１～８の何れか１項に記載の衣料用液体洗浄剤組成物及び水を含有する浸漬液と、衣料とを混合する工程
    工程２：工程１の後に、前記浸漬液に衣料を漬け置く工程
    工程３：工程２の後に、衣料用洗浄剤組成物と水を含む洗浄液中で、衣料を撹拌洗浄する工程     A method for washing clothing comprising the following steps 1 to 3.
    Step 1: Mixing the liquid cleaning composition for clothing according to any one of claims 1 to 8 and a dipping solution containing water, and a step Step 2: After step 1, the dipping solution is added to the dipping solution. Step 3 for soaking clothes: Step after step 2, washing and stirring clothes in a cleaning solution containing a cleaning composition for clothes and water
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