WO2022250123A1 - 酵素反応促進方法 - Google Patents

酵素反応促進方法 Download PDF

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Publication number
WO2022250123A1
WO2022250123A1 PCT/JP2022/021663 JP2022021663W WO2022250123A1 WO 2022250123 A1 WO2022250123 A1 WO 2022250123A1 JP 2022021663 W JP2022021663 W JP 2022021663W WO 2022250123 A1 WO2022250123 A1 WO 2022250123A1
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Prior art keywords
component
less
mass
detergent composition
enzyme
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PCT/JP2022/021663
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English (en)
French (fr)
Japanese (ja)
Inventor
憲介 近藤
恵太 青野
平塚 絵美 多勢
耕造 山田
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Kao Corp
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Kao Corp
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Priority to EP22811391.6A priority Critical patent/EP4365287A4/en
Priority to MX2023012085A priority patent/MX2023012085A/es
Priority to JP2023524236A priority patent/JPWO2022250123A1/ja
Priority to US18/563,449 priority patent/US20240254410A1/en
Priority to CN202280037674.1A priority patent/CN117377758A/zh
Publication of WO2022250123A1 publication Critical patent/WO2022250123A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/123Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618Protease or amylase in liquid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/3869Enzyme enhancers or mediators
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/16Hydrolases (3) acting on ester bonds (3.1)
    • C12N9/18Carboxylic ester hydrolases (3.1.1)
    • C12N9/20Triglyceride splitting, e.g. by means of lipase
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/24Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2405Glucanases
    • C12N9/2408Glucanases acting on alpha -1,4-glucosidic bonds
    • C12N9/2411Amylases
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14Hydrolases (3)
    • C12N9/48Hydrolases (3) acting on peptide bonds (3.4)
    • C12N9/50Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces

Definitions

  • the present invention relates to an enzymatic reaction acceleration method, an enzyme reaction accelerator, an enzyme reaction accelerator composition, and a detergent composition for dishwashers.
  • Enzymes such as lipase, amylase, and protease are used in many industrial fields such as cleaning, food processing, and papermaking.
  • JP-A-2012-75378 describes a pulverization step (1) of pulverizing at least one kind of woody biomass selected from wood chips and waste building materials to obtain woody biomass powder, and a predetermined anionic activator,
  • An enzymatic saccharification method for woody biomass is disclosed, which includes a saccharification treatment step (2) in which woody biomass powder is hydrolyzed to obtain sugars in the presence of a hydrolase.
  • JP-A-2019-182911 (a) a sulfosuccinic acid alkyl ester having an alkyl group having 5 to 18 carbon atoms or a salt thereof, (b) a semipolar surfactant, and 1 selected from amphoteric surfactants Disclosed is a liquid detergent composition for tableware and/or hard items around the kitchen, containing at least one surfactant, (c) an enzyme and water under predetermined conditions.
  • JP-A-2020-100745 discloses an anionic interface containing at least one component (a1) selected from secondary alkanesulfonates, dialkylsulfosuccinates, and compounds represented by specific formulas as components (A).
  • a liquid dishwashing detergent composition having a weight ratio of 0.7 to 2.
  • stains adhering to tableware include oil stains, starch stains such as rice grain stains, protein stains such as eggs, pigment stains such as tea, and the like.
  • oil stains and starch stains are particularly difficult to remove, and there is a problem that stains re-adhere to tableware when washed with a dishwasher, causing the glass tableware to become cloudy. Therefore, in order to improve the detergency against the dirt and the anti-redeposition property, various formulations have been proposed in which active cleaning ingredients such as surfactants, enzymes, and chelating agents are combined.
  • Japanese Patent Application Laid-Open No. 4-72397 discloses a technique for exhibiting high detergency by blending alkaline pullulanase and lipase having ⁇ -amylase activity with a specific nonionic surfactant and a calcium-trapping chelating agent.
  • JP-A-2006-152287 describes a technique for preventing fogging of glass tableware and improving finish by combining a high amount of chelating agent and a low-foaming nonionic surfactant. ing.
  • 2019-182911 describes a cleaning method in which a liquid detergent composition containing an alkyl sulfosuccinate salt and an enzyme is brought into direct contact with the tableware to which greasy stains have adhered in the form of foam. is disclosed.
  • JP-A-2020-100745 discloses that a composition containing a dialkylsulfosuccinate, a protease and an amylase has excellent detergency and antifoaming properties.
  • the present invention provides a method for promoting an enzymatic reaction, for example, an enzymatic reaction in an aqueous medium.
  • the present invention provides a detergent composition for dishwashers that has excellent detergency and excellent finish of dishes.
  • the present invention provides a detergent composition for dishwashers, which is excellent in detergency against stubborn stains such as oil and starch, and excellent in finishing of tableware made of plastic or glass.
  • the present invention relates to a method for promoting an enzymatic reaction, comprising (a) reacting a substrate with an enzyme in the presence of a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof.
  • the present invention also relates to an enzyme reaction accelerator containing (a) a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof as an active ingredient.
  • the present invention provides (a) an enzyme reaction accelerator containing as an active ingredient a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof [hereinafter referred to as component (a)]; contains a surfactant other than component (a) [hereinafter referred to as component (b)], and when component (b) is contained, the content of component (a) and the content of component (b)
  • component (a) contains a surfactant other than component (a) [hereinafter referred to as component (b)]
  • component (b) a surfactant other than component (a)
  • the present invention relates to an enzyme reaction accelerator composition in which the mass ratio (a)/(b) is 0.001 or more and 50 or less.
  • the present invention provides (a) a branched alkyl ester of sulfosuccinic acid having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof [hereinafter referred to as component (a)], and (d) an enzyme [hereinafter referred to as component (d) It relates to a detergent composition for dishwashers containing.
  • a method for promoting an enzymatic reaction for example, an enzymatic reaction in an aqueous medium is provided.
  • a detergent composition for dishwashers that has excellent detergency and excellent finish of dishes.
  • a detergent composition for dishwashers which has excellent detergency against stubborn stains such as oil and starch, and excellent finishing of tableware made of plastic or glass.
  • the substrate and the enzyme are allowed to react in the presence of the component (a).
  • the substrate and the enzyme are reacted preferably in the presence of the component (a) and water.
  • a sulfosuccinic acid ester or a salt thereof is known as a component blended in a cleaning composition for hard articles, as described in Patent Document 3, for example.
  • a compound having a structure corresponding to the component (a) of the present invention can remarkably promote enzymatic reactions with respect to various enzymes such as proteases.
  • a compound having a branched-chain alkyl group with 8 carbon atoms exhibits excellent properties like component (a) of the present invention. The effect of improving the enzymatic reaction cannot be obtained.
  • the mechanism by which the enzyme reaction is promoted by the present invention is not limited to this, it is speculated as follows.
  • the extended wetting of the reaction substrate proceeds with high efficiency, which makes it possible to promote the reactivity between the enzyme contained in water and the substrate.
  • the use of other surfactants and solvents that cause a decrease in enzyme activity can be reduced to a minimum, so that high enzyme activity is maintained and the catalytic reaction by the enzyme can be sustained. can be done.
  • Component (a) is preferably a diester. That is, component (a) is preferably a di-branched alkyl sulfosuccinate or a salt thereof. Component (a) is preferably a sulfosuccinic acid branched alkyl ester having a branched alkyl group of 9 or 10 carbon atoms or a salt thereof. Component (a) is preferably a sulfosuccinic acid branched alkyl ester having a branched alkyl group of 10 carbon atoms or a salt thereof.
  • Component (a) is preferably a di-branched alkyl sulfosuccinate or a salt thereof, wherein the two branched-chain alkyl groups are each a branched-chain alkyl group having 9 or 10 carbon atoms.
  • Component (a) is a di-branched alkyl sulfosuccinate or a salt thereof, preferably a di-branched alkyl sulfosuccinate or a salt thereof, wherein each of the two branched-chain alkyl groups is a 10-carbon branched-chain alkyl group.
  • the method for promoting an enzymatic reaction of the present invention includes a method for promoting an enzymatic reaction in which these preferred components (a) are combined with the items described below.
  • the salt include alkali metal salts and alkanolamine salts.
  • the salt of component (a) is preferably an alkali metal salt or an alkanolamine salt, more preferably a salt selected from sodium salts, potassium salts, triethanolamine salts, diethanolamine salts, and monoethanolamine salts, and still more preferably a sodium salt. .
  • the (a) component includes compounds represented by the following formula 1.
  • R 1 and R 2 are each a branched alkyl group having 9 to 12 carbon atoms, and A 1 O and A 2 O are each an alkyleneoxy group having 2 to 4 carbon atoms.
  • x1 and x2 are the average number of moles added, each being a number of 0 or more and 10 or less, and M is a cation.
  • the number of carbon atoms in R 1 and R 2 may be the same or different.
  • a hydrocarbon residue obtained by removing a hydroxyl group from a secondary alcohol is included in the chain-branched hydrocarbon group.
  • a hydrocarbon chain having the largest number of carbon atoms counted from carbon atoms bonded to an oxygen atom is used as a main chain, and branched from the main chain is
  • the attached hydrocarbon chains are side chains.
  • the main chains are determined in the following order. 1.
  • the side chain branched from the longest hydrocarbon chain and having the larger number of carbon atoms is taken as the main chain. 2.
  • the side chain branched from the longest hydrocarbon chain with the larger number of side chains is taken as the main chain. 3.
  • the main chain is the side chain on the carbon atom closer to the oxygen atom, counting from the carbon atom bonded to the oxygen atom. do. 4.
  • the side chain closest to the oxygen atom with the greater number of carbon atoms is taken as the main chain.
  • two or more longest hydrocarbon chains have the same symmetrical structure, either of them may be the main chain.
  • each of R 1 and R 2 is preferably a branched alkyl group selected from a branched nonyl group, a branched decyl group and a branched dodecyl group, more preferably a branched decyl group.
  • a branched decyl group is preferably a 2-propylheptyl group.
  • a 1 O and A 2 O each have 2 or more and 4 or less carbon atoms, preferably an alkyleneoxy group having 2 or 3 carbon atoms from the viewpoint of lubricity to water.
  • x1 and x2 represent the average number of added moles of A 1 O and A 2 O, and are respectively 0 or more and 10 or less, preferably 6 or less, more preferably 4 or less from the viewpoint of lubricity against water, and further It is preferably a number of 2 or less, and more preferably 0.
  • M is a cation.
  • M is preferably a cation other than a hydrogen ion.
  • M include alkali metal ions such as lithium ion, sodium ion and potassium ion, alkaline earth metal ions such as calcium ion and barium ion, triethanolammonium ion, diethanolammonium ion, monoethanolammonium ion, and trimethylammonium ion. , and organic ammonium ions such as monomethylammonium ion.
  • M is preferably an alkali metal ion or an alkanolammonium ion, more preferably a sodium ion, a potassium ion, a triethanolammonium ion, a diethanolammonium ion or a monoethanolammonium ion, and still more preferably a sodium ion.
  • the component (a) of the present invention is preferably a compound represented by the following formula 1-1.
  • the compound of formula 1-1 is a compound in which x1 and x2 are each 0 in formula 1.
  • R 1 and R 2 are each a branched alkyl group having 9 to 12 carbon atoms, and M is a cation.
  • Specific examples and preferred examples of R 1 , R 2 and M in formula 1-1 are the same as in formula 1.
  • the method for preparing compounds in Formula 1 or Formula 1-1 wherein R 1 and R 2 are the same is not particularly limited, but for example, the method described in US Pat. No. 2,028,091. and as a method for preparing an asymmetric compound having different R 1 and R 2 , for example, JP-A-58-24555 can be referred to.
  • a raw material for the component (a) an alcohol having a predetermined number of carbon atoms to which an alkylene oxide is added can also be used.
  • Alcohols suitable for use in the production of the component (a) of the present invention include (1) primary alcohols represented by 3,5,5-trimethylhexan-1-ol, 2-propylheptan-1-ol and (2) secondary alcohols typified by 5-nonanol, 2,6-dimethyl-4-heptanol and the like.
  • aqueous medium of the present invention it is preferable to bring an aqueous medium containing the component (a), the enzyme and water (hereinafter also referred to as the aqueous medium of the present invention) into contact with the substrate to allow the substrate and the enzyme to react.
  • the aqueous medium of the present invention may be a mixture of component (a), an enzyme and water.
  • the content of component (a) in the aqueous medium of the present invention is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass, and preferably 10% by mass. % or less, more preferably 5 mass % or less, still more preferably 2 mass % or less, and even more preferably 1 mass % or less.
  • the aqueous medium of the present invention can optionally contain a surfactant other than component (a) [hereinafter referred to as component (b)], but the content thereof should be such that component (a) has the effect of promoting the enzymatic reaction. From the viewpoint of maintenance, the smaller the number, the better.
  • the content of component (b) in the aqueous medium of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 1% by mass or less.
  • the aqueous medium of the present invention may not contain component (b).
  • the aqueous medium of the present invention When the aqueous medium of the present invention is applied to a substrate in the form of a foam, the effect of the enzyme may be efficiently exhibited due to the increased attachment efficiency of the enzyme whose activity has been improved. Therefore, when a surfactant is used in combination to adjust the foamability and foam properties of the aqueous medium, the content of component (b) in the aqueous medium of the present invention may exceed the above range.
  • Component (b) is preferably a surfactant that hardly inhibits the enzymatic reaction.
  • component (b) an optimal one can be selected as appropriate in consideration of the embodiment of the method for promoting an enzymatic reaction of the present invention.
  • component (b2) amphoteric surfactant [hereinafter referred to as component (b2)],
  • component (b3) anionic surfactant [hereinafter referred to as component (b3)]
  • component (b4) component includes amine oxide surfactants having one or more, preferably one, alkyl group having 8 to 14 carbon atoms.
  • Component (b2) includes a sulfobetaine-type surfactant having one or more, preferably one, alkyl group having 8 to 14 carbon atoms, and one or more, preferably one, alkyl group having 8 to 14 carbon atoms. and carbobetaine-type surfactants.
  • Component (b3) includes an alkyl sulfuric acid ester salt having an alkyl group having 8 to 14 carbon atoms, an alkylbenzene sulfonate having an alkyl group having 8 to 14 carbon atoms, and a polyoxyalkylene having an alkyl group having 8 to 14 carbon atoms.
  • Alkyl ether sulfate (oxyalkylene has 2 or 3 carbon atoms, preferably oxyethylene, and the average number of added moles of oxyalkylene is 0.5 or more and 5 or less, preferably 0.5 or more and 3 or less), carbon number 8 14 or less fatty acid soaps.
  • polyoxyalkylene alkyl ether for example, polyoxyalkylene alkyl ether having an alkyl group with 8 to 14 carbon atoms (oxyalkylene has 2 or 3 carbon atoms, preferably oxyethylene, and the average of oxyalkylene addition mole number is 3 or more and 50 or less, preferably 3 or more and 20 or less); , preferably 1 or more and 2 or less), alkyl glyceryl ethers such as alkyl glyceryl ethers having alkyl groups of 8 or more and 12 or less carbon atoms.
  • the mass ratio (a)/(b) between the content of the component (a) and the content of the component (b) is preferably 0.5. 001 or more and 50 or less.
  • (a)/(b) can be further selected from 0.01 or more and 40 or less, for example.
  • component (b) in an amount within a range where the total amount of component (a) does not affect the activity of the enzyme.
  • the mass ratio of the total mass of the components (a) and (b) to the total mass of the enzyme [(a) component + (b) component]/enzyme is preferably 0.1 or more, more preferably is 1 or more and 200 or less, preferably less than 100, more preferably 50 or less, even more preferably 25 or less.
  • the aqueous medium of the present invention contains water.
  • the content of water in the aqueous medium of the present invention is preferably 50% by mass or more, more preferably 70% by mass or more. Water is used as the balance of the aqueous medium.
  • the aqueous medium of the present invention can contain components other than the (a) component, enzymes, water, and optional (b) component.
  • it can contain solvents, hydrotropic agents, and the like.
  • the solvent includes (c1) a monohydric alcohol having 1 to 3 carbon atoms, (c2) a polyhydric alcohol having 2 to 4 carbon atoms, and (c3) an alkylene glycol unit having (c4) monoalkoxy (methoxy, ethoxy, propoxy, butoxy), phenoxy or benzooxy ether of di or tetraalkylene glycol having 2 to 4 carbon atoms in the alkylene glycol unit; can be done.
  • Component (c) is preferably a water-soluble organic solvent having 2 or more carbon atoms, preferably 3 or more carbon atoms, and 10 or less carbon atoms, preferably 8 or less carbon atoms.
  • the water-soluble organic solvent refers to a solvent having an octanol/water partition coefficient (LogPow) of 3.5 or less.
  • the component (c) includes ethanol and isopropyl alcohol as (c1), ethylene glycol, propylene glycol, glycerin and isoprene glycol as (c2), diethylene glycol and dipropylene glycol as (c3), and (c4 ) include propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether (also called butyl diglycol), phenoxyethanol, phenoxytriethylene glycol, and phenoxyisopropanol.
  • Component (c) is preferably a solvent selected from ethanol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, phenoxyethanol, phenyl glycol, and phenoxyisopropanol.
  • Component (c) preferably has an alkoxy group, and further preferably contains one or more selected from the above (c4), and the aqueous medium of the present invention may contain diethylene glycol monobutyl ether as component (c). more preferred.
  • the aqueous medium of the present invention can contain the component (c) in an amount of, for example, 0.1 mass % or more, further 0.2 mass % or more, and 10 mass % or less, further 8 mass %.
  • the hydrotrope agent is preferably a hydrotrope agent selected from alkylbenzenesulfonic acids having 1 to 3 alkyl groups having 1 to 3 carbon atoms and salts thereof, specifically toluenesulfonic acid, xylenesulfonic acid, and cumene.
  • Hydrotropic agents selected from sulfonic acids and salts thereof may be mentioned. Salts are preferably sodium salts, potassium salts and magnesium salts.
  • the hydrotropic agent is preferably p-toluenesulfonic acid or a salt thereof.
  • the aqueous medium of the present invention contains, for example, 0.1% by mass or more, further 0.2% by mass or more, and 10% by mass or less, further 8% by mass, more preferably 7% by mass or less, and more. More preferably 6% by mass or less, and even more preferably 5% by mass or less can be contained.
  • Component (a) has an enzyme/component (a) mass ratio of 0.001 or more, further 0.02 or more, further 0.05 or more, and 15 or less, further 9 or less, from the viewpoint of the enzymatic reaction promoting effect. , more preferably 5 or less, more preferably 1 or less.
  • the amount of an enzyme is the amount as an enzyme protein.
  • Enzymes include protease, amylase, and lipase. Enzymes are preferably one or more selected from protease, amylase, and lipase.
  • E. C. 3.1.1.3 triacylglycerol lipase, E. C. 3.1.1.13 cholesterol esterase, E. C. 3.1.23 monoacylglycerol lipase, E. C. Lipoprotein lipases of 3.1.1.34 are preferred.
  • the origin of the lipase is not limited, animal-derived, plant-derived, or microbial-derived lipases may be mentioned.
  • lipases derived from microorganisms include the genus Rhizopus, the genus Aspergillus, the genus Mucor, the genus Pseudomonas, the genus Geotrichum, the genus Penicillium and the genus Candida. origin.
  • Lipase consists of Lipase A “Amano” 6, Lipase AY “Amano” 30SD, Lipase GS “Amano” 250G, Lipase R “Amano”, Lipase DF “Amano” 15, Lipase MER “Amano” (Amano Enzyme Co., Ltd.).
  • lipase (Nagase Sangyo Co., Ltd.), lipase MY, lipase OF, lipase PL, lipase PLC, lipase QLM, lipase QLC, phospholipase D (manufactured by Meito Sangyo Co., Ltd.), lipoprotein lipase (Oriental yeast Co., Ltd.), Lipase (manufactured by Toyo Jozo Co., Ltd.), Lipex, Lipolase, Lipase SP-225 (manufactured by Novo), Lipase (manufactured by Gist), Lipase A, Lipase B (manufactured by Sapporo Beer ( Co., Ltd.) can be used. In the present invention, Lipex and Lipolase (both manufactured by Novo) are suitable.
  • Proteases include proteases that can act in neutral or alkaline aqueous solutions.
  • Specific examples of preferred proteases include alkaline proteases described in WO 99/018218, preferably those in which 70% or more of the amino acid sequence shown in SEQ ID NO: 1 or 2 is conserved.
  • the alkaline protease described in JP-A-5-25492 preferably alkaline protease K-16 or alkaline protease K-14.
  • it is sold under the trade names of Savinase (registered trademark), Kannase (registered trademark), Evarase (registered trademark), Alcalase (registered trademark), Polarzyme (registered trademark), and Esperase (registered trademark) manufactured by Novozymes.
  • Proteases produced by Bacillus subtilisins supplied by DuPont under the trade names FN2 (registered trademark), FN3 (registered trademark) and FN4 (registered trademark), Plafect (registered trademark), and Plafect Prime (registered trademark). proteases or variants thereof, and the like. Among them, enzymes in which 80% or more of the amino acid sequence represented by SEQ ID NO: 1 or 2 described in WO 99/018218 is conserved, Novozymes Savinase, Evalase, Alcalase, Progress ( Novozymes), Plafect and Plafect Prime available from DuPont are more preferable.
  • Amylases include Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus cereus, Bacillus macerans bacteria such as macerans, Pseudomonas stutzeri, Klebsiella aerogenes, actinomycetes such as Streptomyces griseus, fungi such as Aspergillus oryzae and Aspergillus niger , seeds of grasses and legumes, digestive glands of animals such as humans and pigs, and many other organisms.
  • the amylase used in the present invention is a host cell or the like transformed with a recombinant vector having a DNA sequence encoding the above-mentioned microorganisms or their mutant strains, or these enzymes or their mutants.
  • the enzyme can be obtained by inoculating it in a medium containing the source and other essential nutrients, culturing it in a conventional manner, and following a general method of collecting and purifying the enzyme.
  • the enzyme solution obtained in this way can be used as it is, but it can also be used after purification, crystallization, powder preparation or liquid preparation by a known method.
  • the amylase used in the present invention is preferably ⁇ -amylase.
  • amylases examples include Rapidase (trade name) (manufactured by Gistbrokers), Termamyl, Duramil and Stainzyme (trade names) (manufactured by Novozymes Japan), Amplify (manufactured by Novozymes), Plaster ST and Plaster OxAm (trade names). (manufactured by Genencore International).
  • the enzyme described above can be used as the (d) component of the detergent composition for dishwashers of the present invention, which will be described later.
  • the substrate can be selected according to the enzyme, but preferably one or more selected from proteins, starches, and lipids.
  • the reaction conditions for the substrate and enzyme can be set as appropriate, taking into consideration the amount of substrate and the activity of the enzyme.
  • the temperature, pH, composition, amount used, contact time with the substrate, etc. of the aqueous medium of the present invention can be set in consideration of the optimum temperature, optimum pH, enzyme activity, and the like of the enzyme.
  • the conditions for contacting the aqueous medium of the present invention with the substrate are not limited, but the temperature of the aqueous medium of the present invention is, for example, 0°C or higher, further 10°C or higher, further 30°C or higher, further 35°C or higher, and , 100° C. or lower, 80° C. or lower, 70° C. or lower, and 50° C. or lower.
  • the contact time between the aqueous medium of the present invention and the substrate can be selected from, for example, 0.5 minutes or longer, or 1.0 minute or longer.
  • the present invention can target, for example, protein hydrolysis reactions by proteases, starch hydrolysis reactions by amylases, lipid hydrolysis reactions by lipases, and hydrolysis reactions including combinations thereof.
  • the aqueous medium of the present invention is preferably foamed and brought into contact with the substrate from the viewpoint of efficiently expressing the effect of the enzyme by increasing the attachment efficiency of the enzyme with improved activity. That is, in the present invention, it is preferable to bring the foam obtained by foaming the aqueous medium of the present invention into contact with the substrate.
  • two or more enzymes can be used. When two or more types of enzymes are used, they may be reacted separately with the substrate, or those integrated in the state of a complex enzyme may be reacted with the substrate. In any case, sufficient attention must be paid to deactivation due to reactions between enzymes. Moreover, multiple enzymes with different reactivities to substrates can be allowed to act stepwise on the complexed substrate. You may combine these methods.
  • the aqueous medium of the present invention contains component (a) at 0.01% by mass or more, further 0.1% by mass or more, and 2.0% by mass or less, further 1.0% by mass. % or less, 0.005% or more, further 0.01% or more of lipase, 1.0% or less, further 0.5% or less by weight, and water.
  • the aqueous medium of the present invention contains component (a) at 0.001% by mass or more, further 0.005% by mass or more, and 5.0% by mass, further 1 0% by mass, further 0.1% by mass or less, further 0.05% by mass or less, protease 0.00001% by mass or more, further 0.0001% by mass or more, and 1.0% by mass or less, further 0.05% by mass or less. It may be an aqueous medium containing 5 wt% or less, further 0.1 wt% or less, further 0.01 wt% or less, and water.
  • the hardness of the aqueous medium of the present invention is preferably 0° DH or higher, more preferably 4° DH or higher, and preferably 20° DH or lower, more preferably 10° DH, in German hardness, from the viewpoint of the enzyme reaction promoting effect. DH or less, more preferably 8° DH or less.
  • the content of component (a) in the aqueous medium of the present invention is low, for example, 0.02% by mass or less, the presence of the hardness component accelerates the extended wetting of the reaction substrate.
  • the aqueous medium of the present invention preferably has a low hardness, eg, 0° DH, as the effect of loss of effective amounts is greater.
  • the substrate may be present in soil attached to the article.
  • the substrate may be present in dirt adhering to hard surfaces of articles having hard surfaces.
  • the substrate may be present in soil attached to fibers (clothes, etc.).
  • a substrate is present in dirt adhering to an article, for example, an article having a hard surface or fibers, contacting the dirt with the aqueous medium of the present invention promotes the enzymatic reaction in situ. Since substrates such as proteins, starches, and lipids are often the soil itself, it is believed that the method of the present invention will also improve the soil removal efficiency.
  • An example of the enzymatic reaction promoting method of the present invention includes a method for promoting an enzymatic reaction in which lipid and lipase are reacted in the presence of component (a).
  • Another example of the method for promoting an enzymatic reaction of the present invention includes a method for promoting an enzymatic reaction, in which an aqueous medium containing the component (a), lipase, and water is brought into contact with a lipid to react the lipid with the lipase.
  • the present invention is based on the discovery that the component (a) promotes the enzymatic reaction.
  • TECHNICAL FIELD The present invention relates to an enzyme reaction accelerator containing component (a) as an active ingredient.
  • the enzymatic reaction accelerator of the present invention may be an enzyme reaction accelerator consisting essentially of component (a).
  • the present invention contains component (a) and optionally component (b), and when component (b) is contained, the mass ratio of the content of component (a) to the content of component (b) (a)/(b) is 0.001 or more and 50 or less.
  • the present invention relates to the use of component (a) as an enzyme reaction accelerator.
  • the present invention contains component (a) and optionally component (b), and when component (b) is contained, the mass ratio of the content of component (a) to the content of component (b)
  • the present invention relates to the use of a composition in which (a)/(b) is 0.001 or more and 50 or less as an enzyme reaction accelerator composition.
  • the enzymatic reaction accelerator composition and use of the present invention the items described in the enzymatic reaction accelerating method of the present invention can be appropriately applied.
  • Specific examples and preferred examples of the (a) component, (b) component, enzyme, substrate, etc. in the enzymatic reaction accelerator, enzyme reaction accelerator composition and use of the present invention are also respectively Same as method.
  • the mass ratio (a)/(b) can be selected from, for example, 0.001 or more, further 0.01 or more, and preferably 50 or less, further 40 or less.
  • the dishwashing detergent composition of the present invention comprises (a) a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms [hereinafter referred to as component (a)], and (d) an enzyme [hereinafter (d) component].
  • the detergent composition for dishwashers of the present invention improves the detergency and finish of tableware is not clear, it is speculated as follows. It is believed that the detergent composition for dishwashing machines of the present invention exhibits the cleaning effect due to the ability to remove stains and the prevention of redeposition due to the inclusion of components (a) and (d). It should be noted that the detergent composition for dishwashers of the present invention is not limited to this mechanism of action.
  • Component (a) is a sulfosuccinic acid branched alkyl ester having a branched alkyl group having 9 to 12 carbon atoms. Specific examples and preferred embodiments of the component (a) can be selected from those described in the method for promoting an enzyme reaction of the present invention.
  • the branched alkyl group of component (a) has a main chain having 6 or 7 carbon atoms and one or more side chains, and the total number of carbon atoms in the side chains is A branched alkyl group having 2 or more and 4 or less is preferred.
  • the branched chain alkyl groups of component (a) are 2-propylheptyl group, 4-methyl-2-propylhexyl group, 5-methyl-2-propylhexyl group, and 3 ,5,5-trimethylhexyl group is preferable, and a branched chain alkyl group selected from 2-propylheptyl group and 3,5,5-trimethylhexyl group is more preferable.
  • the component (a) of the detergent composition for dishwashers of the present invention includes the compound represented by Formula 1 above and the compound represented by Formula 1-1 above.
  • the total number of carbon atoms constituting the side chains in each of the branched-chain alkyl groups represented by R 1 and R 2 in Formula 1 or Formula 1-1 is the same or It may be different, and from the viewpoint of detergency, it is preferably 3.
  • the total number of carbon atoms constituting a side chain is the total number of carbon atoms in all side chains other than the main chain in one branched alkyl group. It is the total number of carbon atoms in all side chains.
  • the number of side chains of R 1 and R 2 in Formula 1 or Formula 1-1 may be the same or different. above, and preferably 3 or less, more preferably 2 or less.
  • the number of side chains is the number of side chains branched from the main chain, and the number of side chains does not change even if the side chain further has a side chain branched from the side chain. .
  • the side chain may further have a side chain branched from the side chain.
  • the number of branched carbon atoms in R 1 and R 2 in Formula 1 or Formula 1-1 may be the same or different. above, and preferably 3 or less, and even more preferably 2 or less.
  • the number of branched carbon atoms is the total number of tertiary carbon atoms and quaternary carbon atoms in the chain branched hydrocarbon group.
  • a preferred embodiment of R 1 and R 2 in Formula 1 or Formula 1-1 is that the total number of carbon atoms of chain branched hydrocarbon groups of R 1 and R 2 is , each independently having 9 or more and 11 or less carbon atoms, further 9 or 10, each independently having 6 or 7 carbon atoms in the main chain, and each independently having 1 or more carbon atoms constituting the side chains. 3 or less, the number of side chains is independently 1.
  • the branched chain alkyl groups of R 1 and R 2 in Formula 1 or Formula 1-1 may be the same or different.
  • a branched chain alkyl group selected from a propylheptyl group, a 4-methyl-2-propylhexyl group, a 5-methyl-2-propylhexyl group, and a 3,5,5-trimethylhexyl group can be mentioned.
  • a 1 O and A 2 O each independently have 2 or more carbon atoms and 4 or less carbon atoms, preferably It is an alkyleneoxy group of 3 or less.
  • x1 and x2 in the formula 1 or formula 1-1 are the average number of added moles, and from the viewpoint of detergency, they are each independently 0 or more, and It is 6 or less, preferably 4 or less, more preferably 2 or less, and still more preferably 0.
  • x1+x2 is preferably 0 or more, preferably 12 or less, more preferably 6 or less, still more preferably 3 or less, and still more preferably 0, from the viewpoint of detergency.
  • M is a hydrogen ion, an inorganic cation such as sodium ion, ammonium ion, potassium ion, magnesium ion, or monoethanolammonium.
  • ions, organic cations such as diethanolammonium ions, triethanolammonium ions and morpholinium ions, preferably inorganic cations selected from sodium ions, ammonium ions, potassium ions and magnesium ions.
  • Component is an enzyme.
  • Component includes one or more enzymes selected from amylase, protease, and lipase. From the viewpoint of cleaning performance, component (d) is preferably two or more enzymes selected from amylase, protease, and lipase, and preferably two or more enzymes including at least amylase and protease. Specific examples and preferred embodiments of the component (d) can be selected from those described in the method for accelerating an enzyme reaction of the present invention.
  • the detergent composition for dishwashers of the present invention contains, from the viewpoint of detergency, the component (a), for example, 0.01% by mass or more, further 0.05% by mass or more, further 0.1% by mass or more, From the viewpoint of storage stability, the content may be, for example, 5% by mass or less, further 3% by mass or less, further 2% by mass or less, furthermore 1% by mass or less.
  • descriptions (mass %, etc.) regarding the amount of component (a) are based on the mass of the compound converted to sodium salt, for example, the mass when M in the above formula 1 is assumed to be sodium. do.
  • the component (d) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more as an enzyme protein, from the viewpoint of detergency and cost. , more preferably 0.01% by mass or more, and preferably 15% by mass or less, more preferably 9% by mass or less, and even more preferably 5% by mass or less.
  • the Lowry method can be used as the method for quantifying the enzyme protein.
  • the mass ratio (a)/(d) of the content of component (a) to the content of component (d) is preferably 0.00 from the viewpoint of cleaning performance. It is 1 or more, more preferably 1 or more, still more preferably 10 or more, and preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less.
  • the content of component (d) in the detergent composition for dishwashers of the present invention is the mass in terms of enzyme protein.
  • the dishwashing machine detergent composition of the present invention can optionally contain a surfactant other than the component (a) [the component (b) described above].
  • a surfactant other than the component (a) [the component (b) described above].
  • Specific examples and preferred embodiments of the component (b) can be selected from those described in the method for accelerating an enzyme reaction of the present invention.
  • components (b) include amphoteric surfactants [component (b2) described above], anionic surfactants (excluding component (a)) [component (b3) described above], and nonionic surfactants. agents [above-mentioned (b4) component] and the like.
  • the content of component (a) in the total surfactant contained in the detergent composition for dishwashers of the present invention is, for example, 5% by mass or more, further 8% by mass or more. Furthermore, it may be 10% by mass or more, and, for example, 100% by mass or less, further 50% by mass or less, and furthermore 30% by mass or less.
  • the dishwashing detergent composition of the present invention contains an anionic surfactant other than the component (a), among all the anionic surfactants contained in the dishwashing detergent composition of the present invention.
  • the content of component (a) is, for example, 8% by mass or more, preferably 50% by mass or more, more preferably 90% by mass or more, and 100% by mass. It is below.
  • the content of component (a) in the total anionic surfactant may be 100% by mass.
  • the detergent composition for dishwashers of the present invention can optionally contain (b4) a nonionic surfactant [hereinafter referred to as component (b4)].
  • component (b4) is a preferred component from the viewpoint of storage stability and detergency.
  • the component (b4) is preferably one or more nonionic surfactants selected from alkyl glycosides, alkyl glyceryl ethers and polyoxyalkylene alkyl ethers.
  • the number of carbon atoms in the alkyl group is preferably 8 or more, preferably 14 or less, more preferably 12 or less, still more preferably 10 or less.
  • the number of carbon atoms in the alkyl group is preferably 8 or more, preferably 14 or less, more preferably 12 or less, and still more preferably 10 or less.
  • Polyoxyalkylene alkyl ether the number of carbon atoms of the alkyl group is preferably 8 or more, and preferably 14 or less, more preferably 12 or less, still more preferably 10 or less, oxyalkylene group, more preferably oxyethylene group is preferably 3 or more, and preferably 20 or less, more preferably 10 or less.
  • Component (b4) is preferably a nonionic surfactant in which the alkyl group is derived from a secondary alcohol. Oxyalkylene alkyl ethers are preferred.
  • the component (b4) is preferably a foam-suppressing one.
  • the detergent composition for dishwashers of the present invention preferably contains component (b4) in an amount of 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.1% by mass or more, from the viewpoint of storage stability and detergency. is 0.3% by mass or more, and from the viewpoint of foam suppression properties, it is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1.0% by mass or less.
  • the dishwashing machine cleaning composition of the present invention may contain a foam suppressor.
  • foam inhibitors include polymeric compounds such as silicone and polypropylene glycol, and hydrophobic silica particles.
  • the foam inhibitor may be, for example, an oil compound obtained by blending silicone oil with hydrophobic silica fine powder.
  • the foam inhibitor may be selected from compounds that function as oils or solvents, and the compounds may be high-molecular compounds or low-molecular compounds.
  • the foam inhibitor is preferably a polymer compound, more preferably polypropylene glycol.
  • the weight average molecular weight of polypropylene glycol is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more from the viewpoint of foam suppression, and preferably 10 from the viewpoint of blending stability.
  • the weight average molecular weight of polypropylene glycol is calculated based on the measurement of the hydroxyl value (mgKOH/g). Specifically, the weight average molecular weight of polypropylene glycol can be calculated by (m ⁇ 1000 ⁇ 56/OHV).
  • m is the number of hydroxyl groups of polypropylene glycol
  • m is 2 when polypropylene glycol is diol type
  • m is 3 when it is triol type.
  • OHV (mgKOH/g) is a hydroxyl value measured according to JISK0070.
  • the detergent composition for dishwashers of the present invention contains preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% of the foam inhibitor from the viewpoint of storage stability. % by mass or more, and preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less from the viewpoint of foam suppression.
  • the detergent composition for dishwashers of the present invention can contain a chelating agent.
  • Chelating agents include citric acid, malic acid, tartaric acid, succinic acid, methylglycinediacetic acid, glutamic diacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, nitrilotriacetic acid, 1,3-propanediaminetriacetic acid, 1 , 3-diamino-2-hydroxypropanetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid.
  • salts of chelating agents include alkali metal salts such as sodium salts and potassium salts.
  • the chelating agent is preferably one or more selected from citric acid, malic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid, tripolyphosphoric acid, and salts thereof. More preferably one or more selected from acetic acid and salts thereof
  • the detergent composition for dishwashers of the present invention contains a chelating agent
  • the composition contains, for example, 2% by mass or more, further 5% by mass or more, further 10% by mass or more, and 30% by mass or more of the chelating agent. % by mass or less, further 25 mass % or less, and further 20 mass % or less.
  • the dishwashing detergent composition of the present invention can optionally contain a thickening agent such as xanthan gum, an antifoaming agent, a bleaching agent, and the like.
  • a thickening agent such as xanthan gum, an antifoaming agent, a bleaching agent, and the like.
  • the detergent composition for dishwashers of the present invention may be either a liquid detergent composition or a powder detergent composition.
  • the detergent composition for dishwashers of the present invention may contain water. Water may be the balance after removing components (a), (d), (b4) and other optional components.
  • the detergent composition for dishwashers of the present invention is powder, the detergent composition may contain Glauber's salt (sodium sulfate decahydrate). Glauber's salt may be the remainder excluding components (a), (d), (b4) and other optional components.
  • the pH of the detergent composition for dishwashing machines of the present invention at 25°C is preferably 5 or more, more preferably 6 or more, from the viewpoint of detergency. , more preferably 7 or more, and preferably 11 or less, more preferably 10 or less, and even more preferably 8 or less from the viewpoint of a sense of security during handling.
  • pH can be measured by a glass electrode method (the following pH can also be measured by the same method).
  • the viscosity of the detergent composition for dishwashing machines of the present invention at 25°C is preferably 10 mPa ⁇ s or more, It is more preferably 50 mPa ⁇ s or more, still more preferably 100 mPa ⁇ s or more, and from the viewpoint of suppressing undissolved detergent, preferably 5,000 mPa ⁇ s or less, more preferably 2,500 mPa ⁇ s or less.
  • This viscosity is a value measured with a Brookfield viscometer (rotor No. 2, 6 rpm, measurement time of 1 minute, liquid temperature of 25°C).
  • the detergent composition for dishwashers of the present invention may contain an alkaline agent.
  • Alkali agents include sodium carbonate, potassium carbonate, sodium hydrogencarbonate, ethanolamine, sodium silicate, potassium silicate and the like.
  • the dishwashing machine detergent composition of the present invention can be used as a cleaning liquid diluted with water (hereinafter referred to as the cleaning liquid of the present invention).
  • the cleaning liquid of the present invention may be a mixture comprising the dishwashing machine cleaning composition of the present invention and water.
  • the concentration (dilution concentration) of the detergent composition for dishwashing machines of the present invention when used is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably, from the viewpoint of cleaning performance. It is 0.1% by mass or more, and from the viewpoint of foaming, it is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.
  • the concentration of component (a) at the time of use of the detergent composition for dishwashers of the present invention is preferably 1 ppm or more, more preferably 2 ppm or more, still more preferably 5 ppm or more, from the viewpoint of detergency, and From the same point of view, it is preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 30 ppm or less.
  • the concentration of component (d) at the time of use of the detergent composition for dishwashers of the present invention is preferably 0.001 ppm or more, more preferably 0.005 ppm or more, and still more preferably 0.01 ppm, from the viewpoint of detergency. From the same point of view, it is preferably 5 ppm or less, more preferably 2 ppm or less, and even more preferably 1 ppm or less.
  • the mass of component (d) is the mass in terms of enzyme protein.
  • the detergent composition for dishwashing machines of the present invention can be used as a washing liquid diluted with water or the like.
  • the pH at 25° C. of a mixture of 0.2% by mass of the dishwashing machine detergent composition of the present invention and water is preferably 5 or higher, more preferably 6 or higher, still more preferably 6.5 or higher, and , preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less.
  • the detergent composition for dishwashing machines of the present invention can be used for dishwashing machines, further for automatic dishwashing machines, and more preferably for washing with commercial dishwashing machines.
  • Tableware includes cooking utensils, cleaning utensils, and the like.
  • the detergent composition for dishwashers of the present invention is used as a washing liquid mixed with water. At that time, the composition is arbitrarily transported in fixed amounts inside the dishwasher by means of a feeding device to maintain a proper washing liquid concentration.
  • the present invention provides a cleaning solution obtained by diluting the detergent composition for a dishwasher of the present invention with water, and a cleaning method for washing dishes with a dishwasher using the cleaning solution.
  • This cleaning method comprises the steps of diluting the detergent composition for dishwashers of the present invention with water to prepare a cleaning liquid, and using the cleaning liquid to wash dishes in a dishwasher, and further in an automatic dishwasher. may contain.
  • the concentrations of the detergent composition for dishwashing machines of the present invention, the components (a) and the components (d) in the washing liquid are respectively It is diluted to the concentration at the time of use of the product.
  • the range of pH of the washing liquid at 25°C is the same as the preferred range of pH at 25°C of the washing liquid obtained by diluting the detergent composition for dishwashers of the present invention.
  • the washing temperature of the washing liquid is preferably 30° C. or higher, more preferably 40° C. or higher, from the viewpoint of productivity and washability, and is preferably 80° C. or lower, more preferably 80° C. or lower, from the viewpoint of damage to the substrate of tableware. is below 70°C.
  • the washing liquid is typically pumped and used repeatedly.
  • the detergent composition for dishwashers of the present invention is used for washing dishes with a dishwasher.
  • tableware include items such as plates, bowls, cups, etc. used for storing food, and items such as chopsticks, forks, knives, spoons, etc. used for serving food.
  • tableware includes, in addition to these items, storage containers such as Tupperware and bottles, kitchen knives, cutting boards, pots, frying pans, cooking utensils such as fish grills, food processors, cooking appliances such as mixers, etc. It may mean an article or parts thereof that come into contact with and that can be washed in a dishwasher.
  • Materials for tableware include plastic (including silicone resin, etc.), metal, pottery, wood, and combinations thereof.
  • the detergent composition for dishwashers of the present invention is suitably used for washing tableware having a hydrophobic surface, such as plastic tableware. Washing using the detergent composition for dishwashers of the present invention follows washing by a normal dishwasher.
  • ⁇ 2> The method for promoting an enzymatic reaction according to ⁇ 1>, wherein the component (a) is a sulfosuccinic acid branched alkyl ester having a branched alkyl group of 9 or 10 carbon atoms or a salt thereof.
  • Component (a) is a di-branched sulfosuccinic acid di-branched alkyl ester or a salt thereof, wherein each of the two branched-chain alkyl groups is a branched-chain alkyl group having 9 or 10 carbon atoms. , ⁇ 1> or ⁇ 2>.
  • ⁇ 4> The method for accelerating an enzymatic reaction according to any one of ⁇ 1> to ⁇ 3>, wherein the branched-chain alkyl group of component (a) is a 2-propylheptyl group.
  • ⁇ 5> The method for promoting an enzyme reaction according to any one of ⁇ 1> to ⁇ 4>, wherein the component (a) is a sulfosuccinic acid branched alkyl ester represented by the following formula 1 or a salt thereof.
  • R 1 and R 2 are each a branched alkyl group having 9 to 12 carbon atoms, and A 1 O and A 2 O are each an alkyleneoxy group having 2 to 4 carbon atoms.
  • x1 and x2 are the average number of moles added, each being a number of 0 or more and 10 or less, and M is a cation.
  • each of R 1 and R 2 is a branched alkyl group selected from a branched nonyl group, a branched decyl group and a branched dodecyl group, preferably a branched decyl group, ⁇ 5> A method for promoting an enzymatic reaction as described.
  • a 1 O and A 2 O in Formula 1 are each an alkyleneoxy group having 2 or more and 4 or less carbon atoms, preferably 2 or 3 carbon atoms. .
  • x1 and x2 are each a number of 0 or more and 10 or less, preferably 6 or less, more preferably 4 or less, still more preferably 2 or less, still more preferably 0, ⁇ 5 > to ⁇ 7>, the enzymatic reaction promotion method according to any one of the above.
  • M is an alkali metal ion or an alkanolammonium ion, preferably a sodium ion, a potassium ion, a triethanolammonium ion, a diethanolammonium ion, or a monoethanolammonium ion, more preferably a sodium ion.
  • ⁇ 10> (a) The method for promoting an enzyme reaction according to any one of ⁇ 1> to ⁇ 9>, wherein an aqueous medium containing the component, the enzyme, and water is brought into contact with the substrate to allow the substrate and the enzyme to react.
  • the content of component (a) in the aqueous medium is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.05% by mass, and preferably 10% by mass or less,
  • the method for promoting an enzyme reaction according to ⁇ 10> which is more preferably 5% by mass or less, still more preferably 2% by mass or less, and even more preferably 1% by mass or less.
  • ⁇ 12> The method for promoting an enzyme reaction according to ⁇ 10> or ⁇ 11>, wherein the content of component (a) in the aqueous medium is 0.01% by mass or more and 2% by mass or less, and further 1% by mass or less.
  • the aqueous medium optionally contains a surfactant other than the component (a) [hereinafter referred to as the component (b)], and the content of the component (b) in the aqueous medium is 5.0% by mass or less ⁇ 10>
  • component is (b1) semipolar surfactant [hereinafter referred to as (b1) component], (b2) amphoteric surfactant [hereinafter referred to as (b2) component], (b3) anionic surfactant [ The method for accelerating an enzymatic reaction according to ⁇ 13> or ⁇ 14>, wherein the enzyme reaction is at least one selected from (b3) hereinafter] and (b4) nonionic surfactants [hereinafter referred to as (b4) component].
  • ⁇ 16> The method for promoting an enzyme reaction according to ⁇ 15>, wherein the component (b1) is an amine oxide surfactant having one or more, preferably one, alkyl group having 8 to 14 carbon atoms.
  • Component (b2) is a sulfobetaine-type surfactant having one or more, preferably one, alkyl group having 8 to 14 carbon atoms, and one or more, preferably one, alkyl group having 8 to 14 carbon atoms.
  • Component (b3) is an alkyl sulfuric acid ester salt having an alkyl group with 8 to 14 carbon atoms, an alkylbenzene sulfonate having an alkyl group with 8 to 14 carbon atoms, or a polyoxyalkylene alkyl having an alkyl group with 8 to 14 carbon atoms.
  • Ether sulfate (oxyalkylene has 2 or 3 carbon atoms, preferably oxyethylene, and the average number of added moles of oxyalkylene is 0.5 or more and 5 or less, preferably 0.5 or more and 3 or less), and 8 carbon atoms
  • the aqueous medium contains the component (b), and the mass ratio (a)/(b) of the content of the component (a) to the content of the component (b) is 0.001 or more, further 0.01
  • the aqueous medium contains the component (b), and the mass ratio of the total mass of the components (a) and (b) to the total mass of the enzyme [(a) component + (b) component]/enzyme is preferably 0. 1 or more, more preferably 1 or more, and 200 or less, preferably less than 100, more preferably 50 or less, according to any one of ⁇ 13> to ⁇ 19>.
  • ⁇ 21> The method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 20>, wherein the content of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more.
  • ⁇ 22> The method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 21>, wherein the aqueous medium contains a solvent [hereinafter referred to as component (c)].
  • component is (c1) a monohydric alcohol having 1 to 3 carbon atoms, (c2) a polyhydric alcohol having 2 to 4 carbon atoms, (c3) a di- or trialkylene glycol, (c4) selected from monoalkoxy (alkoxy is methoxy, ethoxy, propoxy or butoxy), phenoxy or benzooxy ether of di- or tetra-alkylene glycol having 2 to 4 carbon atoms in the alkylene glycol unit;
  • the method for promoting an enzymatic reaction according to ⁇ 22> which is one or more.
  • ⁇ 24> The method for promoting an enzyme reaction according to ⁇ 22> or ⁇ 23>, wherein the aqueous medium contains, as the component (c), a water-soluble organic solvent having an octanol/water partition coefficient (LogPow) of 3.5 or less.
  • a water-soluble organic solvent having an octanol/water partition coefficient (LogPow) of 3.5 or less.
  • the aqueous medium contains, as the component (c), (c1) ethanol, isopropyl alcohol, (c2) ethylene glycol, propylene glycol, glycerin, isoprene glycol, (c3) diethylene glycol, dipropylene glycol, (c4) propylene glycol.
  • One or more selected from monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, phenoxyethanol, phenoxytriethylene glycol, and phenoxyisopropanol preferably ethanol, propylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, phenoxyethanol, phenyl glycol, and phenoxyisopropanol, more preferably diethylene glycol monobutyl ether.
  • ⁇ 26> Any one of ⁇ 22> to ⁇ 25>, containing 0.1% by mass or more, more preferably 0.2% by mass or more, and 10% by mass or less, more preferably 8% by mass of component (c) The enzymatic reaction acceleration method of.
  • the aqueous medium is a hydrotrope agent, preferably one or more hydrotrope agents selected from alkylbenzenesulfonic acids and salts thereof having 1 to 3 alkyl groups having 1 to 3 carbon atoms, more preferably toluenesulfone.
  • the method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 26>, which contains one or more hydrotropic agents selected from acids, xylenesulfonic acid, cumenesulfonic acid, and salts thereof.
  • ⁇ 28> The method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 27>, wherein the aqueous medium is brought into contact with the substrate in the form of foam.
  • the temperature of the aqueous medium when the aqueous medium and the substrate are brought into contact is 0°C or higher, further 10°C or higher, further 30°C or higher, further 35°C or higher, and 100°C or lower, further 80°C or lower, and further 70°C or lower. , 50° C. or lower, and the contact time is selected from 0.5 minutes or longer, or 1.0 minute or longer, according to any one of ⁇ 10> to ⁇ 28>.
  • the aqueous medium contains lipase as an enzyme, and the aqueous medium contains component (a) at 0.01% by mass or more, further 0.1% by mass or more, and 2.0% by mass or less, further 1.0% by mass or less, ⁇ 10> to ⁇ 29, which is an aqueous medium containing 0.005% by mass or more, further 0.01% by mass or more, and 1.0% by mass or less, further 0.5% by mass or less of lipase, and water
  • the method for promoting an enzyme reaction according to any one of >.
  • the aqueous medium contains protease as an enzyme, and the aqueous medium contains component (a) at 0.001 mass% or more, further 0.005 mass% or more, and 5.0 mass%, further 1.0 mass%, further 0 .1% by mass or less, further 0.05% by mass or less, protease 0.00001% by mass or more, further 0.0001% by mass or more, and 1.0% by mass or less, further 0.5% by mass or less, further 0
  • the method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 30>, wherein the aqueous medium contains 0.01% by mass or less, and water.
  • the hardness of the aqueous medium in German hardness, is preferably 0° DH or higher, more preferably 4° DH or higher, and preferably 20° DH or lower, more preferably 10° DH or lower, and even more preferably 8° DH or lower.
  • the method for promoting an enzyme reaction according to any one of ⁇ 10> to ⁇ 31>.
  • the mass ratio of component (a) to enzyme/component (a) is 0.001 or more, preferably 0.02 or more, more preferably 0.05 or more, and 15 or less, preferably 9 or less, more preferably 5.
  • ⁇ 34> The method for promoting an enzymatic reaction according to any one of ⁇ 1> to ⁇ 33>, wherein the enzyme is one or more selected from protease, amylase, and lipase.
  • Lipase is E. C. 3.1.1.3 triacylglycerol lipase, E. C. 3.1.1.13 cholesterol esterase, E. C. 3.1.23 monoacylglycerol lipase, E. C. 3. The method for promoting an enzymatic reaction according to ⁇ 34>, wherein the lipoprotein lipase is one or more selected from the lipoprotein lipases of 3.1.1.34.
  • Lipase is Lipase A “Amano” 6, Lipase AY “Amano” 30SD, Lipase GS “Amano” 250G, Lipase R “Amano”, Lipase DF “Amano” 15, Lipase MER “Amano” (Amano Enzyme Co., Ltd.) ), lipase (Nagase Sangyo Co., Ltd.), lipase MY, lipase OF, lipase PL, lipase PLC, lipase QLM, lipase QLC, phospholipase D (manufactured by Meito Sangyo Co., Ltd.), lipoprotein lipase (Oriental yeast Co., Ltd.), Lipase (manufactured by Toyo Jozo Co., Ltd.), Lipex, Lipolase, Lipase SP-225 (manufactured by Novo), Lipase (manufactured by Nov
  • the protease is an alkaline protease described in WO99/018218, preferably in which 70% or more of the amino acid sequence shown in SEQ ID NO: 1 or 2 is conserved, or JP-A-5-25492.
  • Amylase is produced by Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus cereus, Bacillus macerans ), bacteria such as Pseudomonas stutzeri and Klebsiella aerogenes, actinomycetes such as Streptomyces griseus, fungi such as Aspergillus oryzae and Aspergillus niger, one or more amylases obtained from the seeds of grasses and legumes, the digestive glands of animals such as humans and pigs, preferably ⁇ -amylase, more preferably the trade name Rapidase (manufactured by Gist Brokers); One or more selected from trade names Termamyl, Duramil and Stainzyme (manufactured by Novozymes Japan Co., Ltd.), Amplify (manufactured by Novozymes), trade names Plaster ST
  • ⁇ 39> The method for accelerating an enzymatic reaction according to any one of ⁇ 1> to ⁇ 38>, wherein the substrate is one or more selected from proteins, starches, and lipids.
  • the substrates are two or more substrates, and two or more substrates selected from proteins, starches, and lipids, and (1) using two or more enzymes and allowing the enzymes to separately react with the substrates; One or more of (2) allowing two or more enzymes integrated in the state of a composite enzyme to react with a substrate, and (3) allowing a plurality of enzymes with different reactivities to act on a substrate stepwise.
  • the method for promoting an enzymatic reaction according to any one of ⁇ 1> to ⁇ 39>, wherein
  • ⁇ 41> The method for promoting an enzyme reaction according to any one of ⁇ 1> to ⁇ 40>, wherein the substrate is present in dirt adhering to the article.
  • ⁇ 42> The method for promoting an enzyme reaction according to any one of ⁇ 1> to ⁇ 41>, wherein the substrate is present in dirt adhering to a hard surface of an article having a hard surface.
  • ⁇ 43> The method for promoting an enzyme reaction according to any one of ⁇ 1> to ⁇ 41>, wherein the substrate is present in dirt adhering to the fiber.
  • An enzyme reaction accelerator comprising, as an active ingredient, a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof.
  • component (a) an enzyme reaction accelerator containing as an active ingredient a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms or a salt thereof [hereinafter referred to as component (a)], and optionally other than component (a) of the surfactant [hereinafter referred to as component (b)], and when the component (b) is included, the mass ratio of the content of the component (a) to the content of the component (b) (a )/(b) is 0.001 or more and 50 or less.
  • a dishwasher containing (a) a branched alkyl sulfosuccinate having a branched alkyl group having 9 to 12 carbon atoms [hereinafter referred to as component (a)] and (d) an enzyme [hereinafter referred to as component (d)]. cleaning composition.
  • branched alkyl group of component (a) has a main chain of 6 or 7 carbon atoms and one or more side chains, and the total number of carbon atoms of the side chains is 2 or more and 4 or less.
  • branched chain alkyl group of component (a) is one or more branched chain alkyl groups selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.
  • a detergent composition for dishwashers is one or more branched chain alkyl groups selected from a 2-propylheptyl group and a 3,5,5-trimethylhexyl group.
  • R 1 and R 2 are each a branched alkyl group having 9 to 12 carbon atoms, and A 1 O and A 2 O are each an alkyleneoxy group having 2 to 4 carbon atoms.
  • x1 and x2 are the average number of moles added, each being a number of 0 or more and 10 or less, and M is a cation.
  • the total number of carbon atoms in the branched chain hydrocarbon groups of R 1 and R 2 is each independently 9 or 10, and the number of carbon atoms in the main chain is each independently 6 or 7.
  • the number of carbon atoms constituting the side chain is each independently 1 or more and 3 or less, and the number of side chains is each independently 1.
  • the branched-chain alkyl groups of R 1 and R 2 are the same or different and are groups selected from 2-propylheptyl and 3,5,5-trimethylhexyl groups ⁇ 50> to ⁇ 52 >
  • component (d) is preferably two or more enzymes selected from amylase, protease, and lipase, and two or more enzymes including at least amylase and protease.
  • the detergent composition for dishwashers according to .
  • Component (a) contains 0.05% by mass or more, preferably 0.1% by mass or more, and 3% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less, ⁇ 47> to ⁇ 58>, the detergent composition for a dishwasher.
  • Component (d) is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and preferably 15% by mass or less, more preferably as an enzyme protein.
  • the mass ratio (a)/(d) of the content of component (a) to the content of component (d) is preferably 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and preferably
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 61>, further comprising (b4) a nonionic surfactant [hereinafter referred to as component (b4)].
  • the (b4) component is preferably a polyoxyalkylene alkyl ether in which the alkyl group is derived from a secondary alcohol, and 1 or more and 10 or less oxyethylene groups are added to the secondary alcohol in terms of the average number of added moles, ⁇ 62 > or the detergent composition for dishwashers according to ⁇ 63>.
  • Component (b4) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 65>, further comprising one or more foam inhibitors selected from silicone oil, polypropylene glycol, and hydrophobic silica particles.
  • the weight-average molecular weight of the foam inhibitor polypropylene glycol is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and preferably 10,000 or less, more preferably 8,000.
  • the detergent composition for dishwashers according to ⁇ 66> which is 5,000 or less, more preferably 5,000 or less.
  • the content of component (a) in the total surfactant contained in the dishwasher detergent composition is 5% by mass or more, further 8% by mass or more, further 10% by mass or more, and 100% by mass or more.
  • the dishwashing detergent composition of the present invention optionally contains an anionic surfactant other than the component (a), and the content of the component (a) in the total anionic surfactant is preferably
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 68>, which is 50% by mass or more, more preferably 90% by mass or more, and 100% by mass or less.
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 69>, further comprising one or more chelating agents selected from citric acid, glutamic diacetic acid, and salts thereof.
  • the dishwashing machine detergent composition is liquid, and the pH of the composition at 25° C. is preferably 5 or higher, more preferably 6 or higher, still more preferably 7 or higher, and more preferably 11 or lower, and more preferably
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 70>, which is 10 or less, more preferably 8 or less.
  • the dishwashing machine detergent composition is liquid, and the viscosity of the composition at 25° C. is preferably 10 mPa ⁇ s or more, more preferably 50 mPa ⁇ s or more, still more preferably 100 mPa ⁇ s or more, and preferably
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 71>, which has a viscosity of 5,000 mPa ⁇ s or less, more preferably 2,500 mPa ⁇ s or less.
  • a detergent composition for dishwashers is powder, and the composition contains an alkaline agent, and the alkaline agent is selected from sodium carbonate, potassium carbonate, sodium hydrogen carbonate, ethanolamine, sodium silicate, and potassium silicate.
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 72>, which is one or more.
  • the concentration (dilution concentration) of the dishwashing detergent composition at the time of use is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more,
  • the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 73> which is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less. .
  • the concentration of component (a) at the time of use of the dishwashing detergent composition is preferably 1 ppm or more, more preferably 2 ppm or more, still more preferably 5 ppm or more, and preferably 100 ppm or less, more preferably 50 ppm.
  • the concentration of component (d) at the time of use of the dishwashing detergent composition is preferably 0.001 ppm or more, more preferably 0.005 ppm or more, still more preferably 0.01 ppm or more, and preferably 5 ppm.
  • a mixture of 0.2% by mass of the detergent composition for dishwashers and water has a pH at 25°C of preferably 5 or more, more preferably 6 or more, still more preferably 6.5 or more, and preferably 12 or less. , more preferably 11.5 or less, still more preferably 11 or less, the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 76.
  • a method for washing dishes which comprises washing dishes in a dishwasher using the detergent composition for dishwashers according to any one of ⁇ 47> to ⁇ 77>.
  • the washing temperature of the washing liquid is preferably 30° C. or higher, more preferably 40° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower. cleaning method.
  • composition according to any one of ⁇ 47> to ⁇ 77> as a detergent for dishwashers.
  • a model stain was evenly applied to a 75 mm (horizontal) x 100 mm (vertical) x 1 mm (thickness) polypropylene test piece so that the coating amount was 0.1 g, and the chloroform was evaporated and dried to obtain a soiled piece. .
  • the aqueous medium of Table 1 was placed in a beaker and the soiled piece was immersed in such a way that the entire area to which the model soil was applied was in contact with the aqueous medium.
  • the temperature of the aqueous medium was 25°C. After immersion for 10 minutes, hydrochloric acid was added to deactivate the enzyme. The soiled piece was removed and rinsed under running distilled water for 15 seconds. At this time, all of the water used for rinsing was recovered. After rinsing, the stain remaining on the soiled piece was washed away with 50 ml of chloroform, placed in a separating funnel together with the water recovered during rinsing, shaken several times, and then the lower chloroform layer was recovered. Then, 25 ml of chloroform was added again, and after shaking again several times, the chloroform layer was recovered.
  • the ingredients in the table are as follows. In addition, mass % of each component in the table is based on the amount as an active ingredient (the same shall apply hereinafter).
  • the (a') component is a comparative component for the (a) component.
  • ⁇ a-1 bis-(2-propylheptyl) sodium sulfosuccinate
  • ⁇ a′-1 bis-(2-ethylhexyl) sodium sulfosuccinate
  • ⁇ LAS sodium dodecylbenzenesulfonate, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
  • ⁇ AS Sodium dodecyl sulfate, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.
  • FA Sodium laurate, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. AG: Alkyl polyglucoside, product name "Plantacare 2000UP", manufactured by BASF SE, alkyl Group carbon number 8 or more and 16 or less, condensation degree of glucose 1 or more and 2 or less
  • Betaine Lauryl hydroxysulfobetaine, Amphithol 20HD, manufactured by Kao Corporation
  • Amine oxide (2) octyldimethylamine oxide, Amphithol 08N, manufactured by Kao Corporation Lipase: product name "Lipex Evity 100L", manufactured by Novozymes, molecular weight of about 30000
  • Example 2a The aqueous medium shown in Table 2 was filled in an accumulator type foam discharge trigger type spray container (Cucute Clear Foam Spray, manufactured by Kao Corporation) and sprayed 5 times on a soiled piece prepared in the same manner as in Example 1a.
  • the aqueous medium was discharged in the form of foam.
  • the total discharge amount of the aqueous medium was about 3 g.
  • Each component in Table 2 is the same as that used in Example 1a. After contacting the discharged foam with the soiled piece for 1 minute, it was rinsed with running distilled water for 15 seconds. At this time, the ambient temperature was 25°C. In addition, the entire amount of water during rinsing was recovered.
  • Triglyceride decomposition rate (II) (%) ⁇ (c) + (d) + (e) + (f) + (g) + (h) + (i) ⁇ / ⁇ (a) + (b) + ( c) + (d) + (e) + (f) + (g) + (h) + (i) ⁇ x 100
  • the triglyceride decomposition rate (II) is high in the examples using the aqueous medium in combination with the component (b). It is believed that this is because the quality of the foam formed from the aqueous medium differs depending on the presence or absence of component (b). That is, the foam produced from the aqueous medium containing the component (b) has a finer texture and is more durable than the foam produced from the aqueous medium containing the component (b). ), it is presumed that the opportunity of contact between the enzyme whose activity was enhanced by the component and the substrate increased, and the triglyceride decomposition rate (II) increased.
  • Example 3a and Comparative Example 3a (1) Compounding Components Components used in Example 3a (Examples 3a-1 to 3a-10) and Comparative Example 3a (Comparative Examples 3a-1 to 3a-10) are as follows.
  • the (a') component is a comparative component for the (a) component.
  • component (a′)] ⁇ a′-1 bis-(2-ethylhexyl) sodium sulfosuccinate AS: sodium dodecyl sulfate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • reaction solution and 2 ⁇ Ez-Apply sample buffer containing 10 mM phenylmethylsulfonyl fluoride (manufactured by ATTO Corporation) were mixed at a ratio of 1:1, stirred for 3 seconds with a vortex mixer, and then heated at 100° C. for 5 minutes. incubated.
  • 2 ⁇ Ez-Apply sample buffer containing 10 mM phenylmethylsulfonyl fluoride manufactured by ATTO Corporation
  • electrophoresis was performed at 40 mA for 80 minutes (WSE-1100PageRun- R (manufactured by ATTO Co., Ltd.)).
  • WSE-1100PageRun- R manufactured by ATTO Co., Ltd.
  • One-step for gel staining Ruby was used. A fluorescence image of the gel was taken, and the band intensity in the 50-80 kDa region was measured from the obtained image using image analysis software (manufactured by Biorad).
  • the BSA decomposition rate was calculated from the following formula, and the values of the BSA decomposition rate were judged as follows. Table 3 shows the results. In this evaluation, the BSA decomposition rate is preferably 30% or more, and a larger value is more preferable.
  • ⁇ BSA decomposition rate (%) 100 - (band intensity after decomposition / undecomposed band intensity) x 100
  • the hardness of the aqueous medium is the German hardness (°dH) measured by the following method.
  • the hardness in the table was obtained by mixing 1 L of water, 83.9 g of calcium chloride dihydrate, and 29.0 g of magnesium chloride hexahydrate, and using the mother liquor of a 4000° DH hardness aqueous solution, the required aqueous medium was used. The hardness was adjusted by dilution.
  • the concentrations of calcium and magnesium for this German hardness are determined by chelate titration using ethylenediaminetetraacetic acid disodium salt.
  • a specific method for measuring the German hardness of the aqueous medium in the present specification is shown below.
  • ⁇ Method for measuring German hardness of aqueous medium> ⁇ reagent ⁇ ⁇ 0.01 mol/l EDTA/2Na solution: 0.01 mol/l aqueous solution of disodium ethylenediaminetetraacetate (solution for titration, 0.01 M EDTA-Na2, manufactured by SIGMA-ALDRICH) ⁇ Universal BT indicator (product name: Universal BT manufactured by Dojindo Laboratories) - Ammonia buffer solution for hardness measurement (solution of 67.5 g of ammonium chloride dissolved in 570 ml of 28 w/v% ammonia water and made up to 1000 ml with deionized water) [Measurement of hardness] (1)
  • Examples 1b, 2b and Comparative Examples 1b, 2b> detergent compositions for dishwashers were prepared containing the following components (a), (d) and (b4) in the proportions shown in Tables 4 and 5, The cleaning performance for rice stains, the protein cleaning performance (finishability), and the cleaning performance for oil stains were evaluated.
  • Method for evaluating cleaning performance of rice soil A soiled rice bowl was prepared by applying 0.5 g of rice soil to a ceramic bowl and drying overnight. In an automatic dishwasher (manufactured by Panasonic, model number: NP-45MS8S), two contaminated tea bowls and the same uncontaminated tea bowl were placed inside so that water would not hit them directly. 6 g of the dishwashing machine detergent composition shown in the table was added, and washing was performed in a standard course. After washing, the fabric was dyed with iodine to visualize residual stains, and then rated according to the following criteria.
  • the concentration of component (a) in the cleaning solution applied to tableware was 10 ppm when the amount of composition input was 6 g. rice field.
  • *Evaluation criteria 3 for cleaning performance of soiled rice Dirt is removed cleanly. 2: Most stains are removed, but some stains remain. 1: Dirt remains and is visible in most areas.
  • Example 1b-1 and Comparative Examples 1b-1 and 1b-3 show that the component (a) of the present invention further improves the decomposition reaction of the substrate (dirt) by the component (d). It is inferred that In Table 4, an enzyme (lipase) that acts on oil is not blended, but the high oil cleaning performance of Example 1b-1 and Comparative Example 1b-2 is due to the fact that washing of automatic dishwashers This is believed to be due to the high temperature and the removal and dispersing effects of oil stains based on the blending of component (a).
  • an enzyme lipase
  • Example 2b-1 and Comparative Examples 2b-2 and 2b-5 show that the component (a) of the present invention further improves the decomposition reaction of the substrate (dirt) by the component (d). It is inferred that In this evaluation, there was no difference in the cleaning performance of rice stains between Examples 2b-1 to 2b-3 and Comparative Example 2b-5. In this evaluation, there was no apparent difference because the performance was relatively easy to exhibit. For example, when evaluating under more severe washing conditions (such as when the washing solution does not easily come into contact with the substrate in clogging washing, or when targeting mixed soiling of rice and lipids), there is a difference between these examples and comparative examples. can occur. In addition, in Table 5, no enzyme (lipase) that acts on oil is blended. It is believed that this is due to the high washing temperature of the automatic dishwasher and the removal and dispersing effect of oil stains based on the blending of component (a).
  • component (d) is mass% in terms of enzyme protein.

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