WO2010021398A1 - Liquid detergent composition for automatic dishwashing machines - Google Patents

Liquid detergent composition for automatic dishwashing machines Download PDF

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Publication number
WO2010021398A1
WO2010021398A1 PCT/JP2009/064704 JP2009064704W WO2010021398A1 WO 2010021398 A1 WO2010021398 A1 WO 2010021398A1 JP 2009064704 W JP2009064704 W JP 2009064704W WO 2010021398 A1 WO2010021398 A1 WO 2010021398A1
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WO
WIPO (PCT)
Prior art keywords
composition
mass
liquid detergent
detergent composition
enzyme
Prior art date
Application number
PCT/JP2009/064704
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French (fr)
Japanese (ja)
Inventor
雄二郎 相木
幸弘 段ノ上
大陽 原
Original Assignee
ライオン株式会社
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Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to JP2010525724A priority Critical patent/JP5398718B2/en
Publication of WO2010021398A1 publication Critical patent/WO2010021398A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • 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
    • C11D3/38663—Stabilised liquid enzyme compositions
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/40—Products in which the composition is not well defined

Definitions

  • the present invention relates to a liquid detergent composition, particularly a liquid detergent composition suitable for use in an automatic dishwasher.
  • Patent Documents 1 and 2 studies for improving detergency
  • Patent Document 3 studies for improving the storage stability of the compounded enzyme.
  • Patent Documents 1 and 2 do not consider any thickening effect for improving the storage stability and usability of the enzyme.
  • Patent Document 3 examines the storage stability of the enzyme, but does not consider any thickening effect.
  • JP 2007-23268 A Japanese Patent Laid-Open No. 2003-277800 JP 2006-257435 A
  • the liquid detergent composition described in the above-mentioned patent document improves the storage stability of the enzyme compounded to enhance the detergency, obtains a certain viscosity to improve usability, It does not simultaneously achieve power and maintain a transparent appearance after storage. Accordingly, the present invention provides a liquid detergent for an automatic dishwashing machine that improves the storage stability of an enzyme, has a viscosity in a suitable range for ease of use, has an excellent cleaning power, and maintains a transparent appearance even after storage. It is an object to provide a composition.
  • liquid detergent composition for an automatic dishwasher comprising a combination of sorbitol and a specific polyhydric alcohol and a non-crosslinked polycarboxylic acid or a salt thereof and an enzyme.
  • the present invention (A) Non-crosslinked polycarboxylic acid or a salt thereof, (B) sorbitol, (C) one or more selected from the group consisting of propylene glycol, glycerin, glucose, mannitol and alkyl glucoside, and (D) an enzyme, based on the total mass of the composition, (A) is 4 to 20% by mass, Provided is a liquid detergent composition for an automatic dishwasher in which (B) + (C) is 25 to 70% by mass and the mass ratio of (B) / (C) is in the range of 2 to 10.
  • the present invention also provides (A) a salt of a (meth) acrylic acid / maleic acid copolymer, (B) sorbitol, (C1) 2-ethylhexyl glucoside, (C2) one or more selected from the group consisting of propylene glycol and glycerin, and (d) amylolytic enzyme and / or proteolytic enzyme, And based on the total weight of the composition, (A) is 4 to 20% by mass, A liquid detergent composition for an automatic dishwasher in which (b) + (c1 + c2) is 25 to 70% by mass and the mass ratio of (b) / (c1 + c2) is in the range of 2 to 10. provide.
  • a novel liquid detergent for an automatic dishwasher that enhances the storage stability of an enzyme, has a viscosity in a suitable range for ease of use, has an excellent cleaning power, and maintains a transparent appearance even after storage.
  • a composition can be obtained.
  • the composition of the present invention is particularly excellent in tea astringency detergency, glass haze detergency, starch stain detergency, and protein stain detergency.
  • the detergent composition of the present invention can further stabilize the enzyme by reducing the water content of the entire system.
  • the composition of the present invention is also excellent in low temperature stability. According to this invention, when the composition of this invention contains a specific fragrance
  • the component (A) is a non-crosslinked polycarboxylic acid or a salt thereof.
  • the viscosity of the liquid detergent composition can be increased and the usability is improved.
  • tea astringency cleaning ability and glass fogging ability are improved.
  • the cleaning effect on tea astringency is particularly high.
  • the (A) non-crosslinked polymer polycarboxylic acid (salt) used in the present invention preferably has a weight average molecular weight of 1,000 or more as measured by gel permeation chromatography, and ranges from 1,500 to 200,000.
  • the range is more preferable, the range of 2,000 to 100,000 is more preferable, the range of 10,000 to 100,000 is more preferable, and the range of 40,000 to 60,000 is more preferable.
  • the weight average molecular weight is 1,000 or more, the performance of the glass as a cloudy cleaning agent is improved, and when it is 200,000 or less, an excessive increase in the viscosity of the liquid cleaning composition is suppressed, which is preferable.
  • the (A) non-crosslinked polymer polycarboxylic acid (salt) used in the present invention may be a homopolymer of a monomer having a carboxyl group, and a monomer having a carboxyl group and two or more kinds having a carboxyl group. Or a copolymer with two or more other monomers having no carboxyl group.
  • the homopolymer include poly (meth) acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyitaconic acid or a salt thereof, and the like.
  • Examples of the copolymer of a monomer having a carboxyl group and two or more other monomers having a carboxyl group include, for example, a (meth) acrylic acid-maleic acid copolymer or a salt thereof, an acrylic acid-crotonic acid copolymer, or The salt is given.
  • Examples of the copolymer of the monomer having a carboxyl group and two or more other monomers having no carboxyl group include an ethylene-maleic acid copolymer or a salt thereof, a methacrylic acid-ethyl acrylate copolymer or a salt thereof. Can be mentioned.
  • a (meth) acrylic acid / maleic acid copolymer or a salt thereof, an ethylene-maleic acid copolymer or a salt thereof is used.
  • a (meth) acrylic acid / maleic acid copolymer or a salt thereof is preferred.
  • An acrylic acid / maleic acid copolymer or a salt thereof is more preferable.
  • a salt of acrylic acid / maleic acid copolymer is more preferable.
  • the salt include sodium salt and potassium salt.
  • non-crosslinked polymer polycarboxylic acid can be used alone or in combination of two or more.
  • the component (A) used in the present invention may be synthesized or commercially available. Examples of commercially available products include Aqualic TL400 (acrylic acid / maleic acid copolymer, weight average molecular weight: 50000, viscosity: about 2000 mPa / s (temperature: 23 ° C., concentration: 40) manufactured by Nippon Shokubai Co., Ltd.
  • the viscosity of the non-crosslinked polycarboxylic acid or a salt thereof is measured using a BL type viscometer using, for example, rotor Nos. 1 to 4 at a rotor rotation speed of 6 to 60 rpm and a measurement time of 20 to 120 seconds. Can be measured under the following conditions.
  • Component (B) component is sorbitol.
  • the viscosity of the composition of the present invention can be increased and the usability is improved.
  • the storage stability of the enzyme, the detergency by the enzyme, especially the detergency by the enzyme after long-term storage, and the low temperature stability are improved. In addition, it contributes to maintaining a transparent appearance after storage of the composition.
  • the component (B) to be used may be synthesized or commercially available. Examples of products available on the market include NEOSORB 70 / 02B manufactured by ROQUETTE, Sorbit D-70 manufactured by Mitsubishi Corporation Foodtech, Sorbit AO-T manufactured by Sanei Sugar Chemical Co., and Sorbitol S manufactured by Nikken Kasei. Etc.
  • the component (C) is at least one selected from the group consisting of propylene glycol, glycerin, glucose, mannitol and alkyl glucoside.
  • blending component By mix
  • Propylene glycol, glycerin, glucose and mannitol, especially propylene glycol and glycerin contribute to improving the storage stability of the enzyme contained in the composition of the present invention and maintaining the transparent appearance after the composition is stored.
  • (C) is preferably a mixture of an alkyl glucoside and one or more selected from the group consisting of propylene glycol, glycerin, glucose and mannitol. More preferably, (C) is a mixture of an alkyl glucoside and one or more selected from the group consisting of propylene glycol and glycerin.
  • R 1 represents a linear or branched, preferably linear alkyl or alkenyl group having 2 to 10, preferably 4 to 10, more preferably 4 to 8 carbon atoms
  • R 2 is a linear or branched alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms
  • G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, preferably a residue derived from glucose
  • x has an average value of 0-5, preferably 0-2, more preferably 0,
  • y has an average value of 1.0-4.2, preferably 1.0-3.0, more preferably 1.0 (ie monosaccharide).
  • the compound represented by can be used suitably. It is particularly preferred that the alkyl glycoside is 2-ethylhexyl glucoside. It is particularly preferred that (C) is a mixture of (c1) 2-ethylhexyl glucoside and (c2) one or more selected from the group consisting of propylene glycol and glycerin.
  • Component (C) may be synthesized or commercially available.
  • 2-Ethylhexyl glucoside is commercially available, for example, as AG6202 manufactured by Lion Akzo.
  • Glycerin is commercially available, for example, as concentrated glycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.
  • Propylene glycol is commercially available, for example, as propylene glycol manufactured by Asahi Glass Co., Ltd., propylene glycol manufactured by Showa Denko KK, and propylene glycol manufactured by ADEKA.
  • the present invention by combining the (A) component, the (B) component and the (C) component, in particular, the (c1) component and the (c2) component, these can be used alone in the (D) component blending system.
  • the combination of the component (A), the component (B), the component (C), and particularly the component (c1) (c2) enables stable blending of the fragrance.
  • (D) component (D) component is an enzyme.
  • the enzyme By blending the enzyme, it is possible to improve the dirt cleaning ability of the article to be washed, particularly the ability to remove starch dirt and protein dirt adhered to the tableware.
  • One or more enzymes can be contained, but it is more preferable to blend one or more enzymes selected from the group consisting of amylolytic enzymes and proteolytic enzymes.
  • amylase and protease are preferably used in combination.
  • Termamyl Ultra 300L manufactured by Novozymes
  • Termamyl 300L Type DX manufactured by Novozymes
  • Steinzyme 12L manufactured by Novozymes
  • Steinzyme Plus 12L manufactured by Novozymes
  • Duramil 300L Type DX Novozymes
  • proteases examples include Everase 16L Type DX (Novozymes), Sabinase Ultra 16XL (Novozymes), Purefect Prime 4000L (Genencore), Purefect OX4000L (Genencore), Properase L (Genencore), Examples include Alcalase Ultra 2.5L (manufactured by Novozymes), Alcalase 2.5L Type DX (manufactured by Novozymes), and the like.
  • composition of the present invention may further contain a fragrance composition.
  • fragrance composition examples include 2-methylbutyl acetate, benzyl acetate, butyl acetate, butyl butyrate, camphene, decanal, dihydromyrsenol, ethyl 2-ethylbutyrate, and geranial.
  • the liquid detergent composition for an automatic dishwasher of the present invention can contain water as other components.
  • the water content in the composition of the present invention means the total water content in the composition. That is, it means the total amount of water added to balance the composition and the amount of water in the solution when the raw material is added as a solution.
  • the composition of the present invention may further contain components usually contained in a liquid detergent composition for an automatic dishwasher. In particular, it is preferable to include a nonionic surfactant, a cationic surfactant, and a preservative.
  • nonionic surfactant examples include polyoxyethylene polyoxypropylene alkyl ether represented by the following formula (2). It is preferable for the composition of the present invention to contain a nonionic surfactant since the oil stain detergency and stability over time of the composition are improved.
  • R1 is a hydrophobic group having 8 to 20 carbon atoms, preferably 8 to 16 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from higher alcohols, higher fatty acids, and higher fatty acid amides.
  • EO represents an ethylene oxide group
  • PO represents a propylene oxide group.
  • p and q are the average number of moles added of the ethylene oxide group and the propylene oxide group, and each of p and q is in the range of 1-6. If p exceeds 6, foaming will increase, placing a burden on the automatic dishwasher and possibly reducing the cleaning power. If q exceeds 6, the composition may have poor stability over time.
  • the total of p and q is preferably 3 to 10. If the total of p and q is less than 3, it is slightly inferior in terms of the effect of cleaning oil stains, and if it exceeds 10, foaming may increase or the composition may have poor stability over time, which is not preferable.
  • the nonionic surfactant polyoxyethylene polyoxypropylene alkyl ether of the formula (2) is particularly preferable.
  • Examples of the cationic surfactant include a compound represented by the following formula (3).
  • R 2 and R 3 are each independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, preferably 10 to 18 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, a phenyl group. And any one of benzyl groups. Particularly preferably, one of R 2 and R 3 is a combination of a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, and the other is a combination of a methyl group or a tolyl group.
  • EO represents an ethylene oxide group.
  • m and n are average added mole numbers of ethylene oxide groups, and each independently represents an integer of 0 or more.
  • M + n is 10 or more, preferably 10 to 50.
  • X ⁇ is an anion, a halogen atom ion such as chlorine ion, bromine ion, iodine ion, etc., or a general formula R 4 O— (where R 4 is an alkyl group having 1 to 3 carbon atoms, preferably A methyl group)) and the like.
  • R 4 is an alkyl group having 1 to 3 carbon atoms, preferably A methyl group
  • the cationic surfactant a compound represented by the formula (3) is preferable, and polyoxyethylene (15) alkylmethylammonium chloride is more preferable.
  • preservative examples include 2-bromo-2-nitro-1,3-propanediol, isothiazolone, and the like.
  • Other components include, for example, solvents such as ethanol, inorganic metal salts, plant extracts, antibacterial / bactericidal agents, deodorants, stabilizers, thickeners, ionic surfactants, polymers, inorganic salts Examples thereof include substances generally contained in liquid detergent compositions for automatic dishwashers.
  • Blending amount The composition of the present invention comprises 4 to 20% by mass, preferably 8 to 18% by mass, more preferably 10 to 14% by mass, based on the total mass of the composition.
  • content of the component (A) is 4% by mass or more, sufficient tea astringency washing ability and glass fogging ability can be exerted, which contributes to the improvement of the viscosity of the composition.
  • the viscosity of the composition can be kept in an appropriate range that is easy to use, the storage stability of the enzyme is improved, and the transparent appearance of the composition can be maintained even after storage.
  • the composition of the present invention contains (B) preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and further preferably 32 to 50% by mass based on the total mass of the composition.
  • content of (B) component 20 mass% or more it contributes to the improvement of the viscosity of a composition, the storage stability of an enzyme improves, and the transparent external appearance of a composition can be hold
  • the composition of the present invention contains (C) preferably 4.5 to 12% by mass, more preferably 5 to 8% by mass, based on the total mass of the composition.
  • (c1) is preferably contained in an amount of 0.5 to 5% by mass, more preferably 0.7 to 3% by mass, based on the total mass of the composition.
  • (C2) is preferably contained in an amount of 4 to 11% by mass, more preferably 4 to 7% by mass.
  • the cleaning composition of the present invention comprises (B) and (C) in a total amount of 25 to 70% by mass, preferably 30 to 60% by mass, more preferably 30 to 50%, based on the total mass of the composition. It is contained at 40% by mass, more preferably 40-50% by mass.
  • the total amount of component (B) and component (C) 25% by mass or more it has an appropriate viscosity that improves usability, improves the storage stability of the enzyme, and maintains a transparent appearance even after storage.
  • a composition is obtained. By setting it to 70% by mass or less, it has an appropriate viscosity for improved usability and improves low-temperature stability.
  • the total amount of (c1) and (c2) is preferably 4 to 12% by mass, more preferably 5 to 8% by mass .
  • the component (B) and the component (C) to be blended in the cleaning composition of the present invention have a mass ratio of (B) / (C) in the range of 2 to 10, preferably 4 to 9. Blend in. By setting the mass ratio in the above range, it has an appropriate viscosity for improving usability and an excellent cleaning power, the enzyme storage stability is improved, and the cleaning composition may become cloudy or separated. And a composition capable of maintaining a transparent appearance even after storage is obtained.
  • the enzyme as component (D) is preferably added in an amount of 0.05% to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.1 to 1% by mass.
  • the amylolytic enzyme in the composition is preferably 0.006 to 30 units / g (U / g), more preferably 0.012 to 15 units / g (U / g), and still more preferably 0.012 to 3 units / g (U / g). ) Can be blended. By setting it as this range, the washing
  • the proteolytic enzyme is preferably 0.00125 to 400 units / g (U / g), more preferably 0.0025 to 200 units / g (U / g), and still more preferably 0.0025 to 40 units / g (U / g). ) Can be blended. By setting it within this range, it is possible to improve the cleaning performance against protein stains.
  • Water is preferably added in an amount of 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, specifically 40 to 50% by mass with respect to the total mass of the composition. Is possible. If it exceeds 65%, the storage stability of the enzyme may be reduced.
  • the perfume composition can be blended in the range of preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.1% by mass, based on the total mass of the composition.
  • the nonionic surfactant can be added in an amount of preferably 0.01 to 0.1% by mass, more preferably 0.05 to 0.1% by mass, based on the total mass of the composition.
  • the cationic surfactant can be blended in the range of preferably 0.1 to 1.0% by mass, more preferably 0.5 to 1.0% by mass with respect to the total mass of the composition.
  • the preservative can be added in an amount of preferably 0.001 to 0.01% by mass, more preferably 0.005 to 0.01% by mass, based on the total mass of the composition.
  • the method for producing the composition of the present invention is not particularly limited, and any method for producing a conventional liquid detergent composition can be used.
  • any method for producing a conventional liquid detergent composition can be used.
  • the components (A) to (C) and other components are blended, the pH is adjusted with a pH adjuster, for example, between 6 and 8, and then the component (D) is blended.
  • the pH of the composition of the present invention is preferably in the range of 6-8. By adjusting the pH in the range of 6 to 8, the finish when washing dishes such as aluminum can be improved, and the storage stability of the enzyme can be improved.
  • the pH can be adjusted with a pH adjusting agent (for example, sodium hydroxide, sulfuric acid).
  • the viscosity of the composition of the present invention is preferably in the range of 100 to 2000 mPa ⁇ s, more preferably 200 to 1000 mPa ⁇ s. This range is an appropriate viscosity range in which the composition can be easily weighed and the composition can be easily put into an automatic dishwasher and is easy to use.
  • Viscosity can be measured, for example, using a BL type viscometer using rotor Nos. 1 to 4 at 25 ° C. under conditions of a rotor speed of 6 to 60 rpm and a measurement time of 20 to 120 seconds.
  • a BL type viscometer using rotor Nos. 1 to 4 at 25 ° C. under conditions of a rotor speed of 6 to 60 rpm and a measurement time of 20 to 120 seconds.
  • Detergency evaluation method> (4.1 Evaluation method of detergency by enzyme) Detergency of each composition before and after storage (storage conditions: room temperature, stored for 6 months) was evaluated by the following evaluation method. (4.1.1 Starch dirt cleaning power) After applying 5g of Sato rice made by Sato Food Industry Co., Ltd. to a tea bowl (diameter: 115mm, height: 50mm), it was washed and evaluated using a dish that was left overnight at 25 ° C and 50% RH for 24 hours. It was. The dishwasher was NP-40SX2 made by National Corporation, and the standard course was selected to wash the teacups. The state of the tea bowl after washing was evaluated according to the following criteria. Evaluation criteria: ⁇ to ⁇ are acceptable range ⁇ : Dirt is well removed ⁇ : Dirt is removed ⁇ : Fair dirt is removed ⁇ : Dirt is not removed at all
  • the detergent composition within the scope of the present invention achieves a good viscosity range, thereby achieving good usability.
  • the liquid detergent composition of the present invention has excellent enzyme storage stability not only by showing good detergency before storage but also by excellent detergency after storage. .
  • deviates from the range of this invention usability worsens because a viscosity becomes low excessively or becomes high. It can also be confirmed that the storage stability of the enzyme is reduced.

Abstract

Provided is a liquid detergent composition for automatic dishwashing machines which comprises: (A) a non-crosslinked polycarboxylic acid or a salt thereof; (B) sorbitol; (C) one or more members selected from the group consisting of propylene glycol, glycerol, glucose, mannitol and an alkyl glucoside; and (D) an enzyme; wherein, relative to the total mass of the composition, the amount of (A) is 4 to 20 mass%; the amount of (B)+(C) is 25 to 70 mass %; and the ratio by mass of (B)/(C) ranges from 2 to 10. This composition shows an improved storage stability of the enzyme, has a viscosity falling within such an appropriate range as ensuring ease of use, exhibits a powerful detergency and sustains a transparent appearance even after storage.

Description

自動食器洗浄機用液体洗浄剤組成物Liquid detergent composition for automatic dishwashers
　本発明は、液体洗浄剤組成物、特に自動食器洗浄機で使用するのに適した液体洗浄剤組成物の発明に関する。 The present invention relates to a liquid detergent composition, particularly a liquid detergent composition suitable for use in an automatic dishwasher.
　食器を洗浄する際に使用する液体洗浄剤組成物は種々検討されており、例えば洗浄力を向上させるための検討（特許文献１及び２）、配合した酵素の貯蔵安定性を向上するための検討（特許文献３）がなされている。
　特許文献１及び２は酵素の貯蔵安定性の向上及び使い勝手をよくするための増粘効果について何ら検討していない。特許文献３は、酵素の貯蔵安定性に関して検討しているが、増粘効果については何ら検討していない。 Various liquid detergent compositions used for washing dishes have been studied. For example, studies for improving detergency (Patent Documents 1 and 2), studies for improving the storage stability of the compounded enzyme. (Patent Document 3) has been made.
Patent Documents 1 and 2 do not consider any thickening effect for improving the storage stability and usability of the enzyme. Patent Document 3 examines the storage stability of the enzyme, but does not consider any thickening effect.
特開２００７－２３２６８号公報JP 2007-23268 A 特開２００３－２７７８００号公報Japanese Patent Laid-Open No. 2003-277800 特開２００６－２５７４３５号公報JP 2006-257435 A
　しかし、上記特許文献に記載される液体洗浄剤組成物は、洗浄力を高めるために配合される酵素の貯蔵安定性を高めること、使い勝手をよくするために一定の粘度を得ること、優れた洗浄力を有すること、保存後も透明な外観を保持することを同時に達成するものではない。
　従って、本発明は、酵素の貯蔵安定性を高め、使い勝手の良い適正範囲の粘度を有し、優れた洗浄力を有し、保存後も透明な外観を保持する自動食器洗浄機用液体洗浄剤組成物を提供することを課題とする。 However, the liquid detergent composition described in the above-mentioned patent document improves the storage stability of the enzyme compounded to enhance the detergency, obtains a certain viscosity to improve usability, It does not simultaneously achieve power and maintain a transparent appearance after storage.
Accordingly, the present invention provides a liquid detergent for an automatic dishwashing machine that improves the storage stability of an enzyme, has a viscosity in a suitable range for ease of use, has an excellent cleaning power, and maintains a transparent appearance even after storage. It is an object to provide a composition.
　本発明者らが鋭意検討を行った結果、ソルビトールと特定の多価アルコールとを組み合わせた上、非架橋型ポリカルボン酸又はその塩と酵素とを含む自動食器洗浄機用液体洗浄剤組成物に含ませることにより、上記課題を同時に解決できることを見出し、本発明に至った。
　すなわち本発明は、
　（A）非架橋型ポリカルボン酸又はその塩、
　（B）ソルビトール、
　（C）プロピレングリコール、グリセリン、グルコース、マンニトール及びアルキルグルコシドからなる群から選ばれる１種以上、及び
　（D）酵素
を含み、組成物の全質量に基づいて、
　（A)が4～20質量％、
　（B)＋（C)が25～70質量％であり、かつ
　（B）/（C）の質量比率が２～１０の範囲である自動食器洗浄機用液体洗浄剤組成物を提供する。 As a result of intensive studies by the present inventors, a liquid detergent composition for an automatic dishwasher comprising a combination of sorbitol and a specific polyhydric alcohol and a non-crosslinked polycarboxylic acid or a salt thereof and an enzyme. By including, it discovered that the said subject could be solved simultaneously and came to this invention.
That is, the present invention
(A) Non-crosslinked polycarboxylic acid or a salt thereof,
(B) sorbitol,
(C) one or more selected from the group consisting of propylene glycol, glycerin, glucose, mannitol and alkyl glucoside, and (D) an enzyme, based on the total mass of the composition,
(A) is 4 to 20% by mass,
Provided is a liquid detergent composition for an automatic dishwasher in which (B) + (C) is 25 to 70% by mass and the mass ratio of (B) / (C) is in the range of 2 to 10.
　本発明はまた、
　（a）（メタ）アクリル酸／マレイン酸共重合体の塩、
　（b）ソルビトール、
　（c1）2-エチルヘキシルグルコシド、
　（c2）プロピレングリコール及びグリセリンからなる群から選ばれる１種以上、及び
　（d）デンプン分解酵素及び／又はタンパク質分解酵素、
を含み、組成物の全質量に基づいて、
　（a）が４～２０質量％、
　（b）＋（c1+c2）が２５～７０質量％であり、かつ
　（b）/（c1+c2）の質量比率が２～１０の範囲である自動食器洗浄機用液体洗浄剤組成物を提供する。 The present invention also provides
(A) a salt of a (meth) acrylic acid / maleic acid copolymer,
(B) sorbitol,
(C1) 2-ethylhexyl glucoside,
(C2) one or more selected from the group consisting of propylene glycol and glycerin, and (d) amylolytic enzyme and / or proteolytic enzyme,
And based on the total weight of the composition,
(A) is 4 to 20% by mass,
A liquid detergent composition for an automatic dishwasher in which (b) + (c1 + c2) is 25 to 70% by mass and the mass ratio of (b) / (c1 + c2) is in the range of 2 to 10. provide.
　本発明により、酵素の貯蔵安定性を高め、使い勝手の良い適正範囲の粘度を有し、優れた洗浄力を有し、保存後も透明な外観を保持する、新規自動食器洗浄機用液体洗浄剤組成物を得ることができる。本発明の組成物は特に、茶渋洗浄力、ガラスの曇り洗浄力、澱粉汚れ洗浄力、タンパク汚れ洗浄力に優れる。さらに、本発明の洗浄剤組成物は、系全体の水分量を低くして、酵素を更に安定化させることができる。本発明の組成物は低温安定性にも優れる。本発明によれば、本発明の組成物が特定の香料を含む場合に、その保存安定性を向上することができる。 According to the present invention, a novel liquid detergent for an automatic dishwasher that enhances the storage stability of an enzyme, has a viscosity in a suitable range for ease of use, has an excellent cleaning power, and maintains a transparent appearance even after storage. A composition can be obtained. The composition of the present invention is particularly excellent in tea astringency detergency, glass haze detergency, starch stain detergency, and protein stain detergency. Furthermore, the detergent composition of the present invention can further stabilize the enzyme by reducing the water content of the entire system. The composition of the present invention is also excellent in low temperature stability. According to this invention, when the composition of this invention contains a specific fragrance | flavor, the storage stability can be improved.
（A）成分
　(A)成分は、非架橋型ポリカルボン酸又はその塩である。（A）成分を配合することにより、液体洗浄剤組成物の粘度を上げることができ、使い勝手が良くなる。加えて、茶渋洗浄力及びガラスの曇り洗浄力も向上する。特に茶渋に対する洗浄効果が高い。
　本発明に用いる（Ａ）非架橋型高分子ポリカルボン酸（塩）は、ゲル浸透クロマトグラフィーにより測定される重量平均分子量が１，０００以上であるのが好ましく、１，５００～２００，０００の範囲がより好ましく、２，０００～１００，０００の範囲がさらに好ましく、１０，０００～１００，０００の範囲がさらに好ましく、４０，０００～６０，０００の範囲がさらに好ましい。重量平均分子量が１，０００以上であると、ガラスの曇り洗浄剤としての性能が向上し、２００，０００以下であると、液体洗浄剤組成物の粘度の過度の増加が抑制されるので好ましい。 Component (A) The component (A) is a non-crosslinked polycarboxylic acid or a salt thereof. By blending the component (A), the viscosity of the liquid detergent composition can be increased and the usability is improved. In addition, tea astringency cleaning ability and glass fogging ability are improved. The cleaning effect on tea astringency is particularly high.
The (A) non-crosslinked polymer polycarboxylic acid (salt) used in the present invention preferably has a weight average molecular weight of 1,000 or more as measured by gel permeation chromatography, and ranges from 1,500 to 200,000. The range is more preferable, the range of 2,000 to 100,000 is more preferable, the range of 10,000 to 100,000 is more preferable, and the range of 40,000 to 60,000 is more preferable. When the weight average molecular weight is 1,000 or more, the performance of the glass as a cloudy cleaning agent is improved, and when it is 200,000 or less, an excessive increase in the viscosity of the liquid cleaning composition is suppressed, which is preferable.
　本発明に用いる（Ａ）非架橋型高分子ポリカルボン酸（塩）は、カルボキシル基を有するモノマーのホモポリマーであってもよく、カルボキシル基を有するモノマーと、カルボキシル基を有する２種以上の他のモノマー又はカルボキシル基を有さない２種以上の他のモノマーとのコポリマーであってもよい。ホモポリマーとしては、例えば、ポリ（メタ）アクリル酸又はその塩、ポリクロトン酸又はその塩、ポリイタコン酸又はその塩等があげられる。カルボキシル基を有するモノマーと、カルボキシル基を有する２種以上の他のモノマーとのコポリマーとしては、例えば、（メタ）アクリル酸－マレイン酸共重合体又はその塩、アクリル酸－クロトン酸共重合体又はその塩があげられる。カルボキシル基を有するモノマーと、カルボキシル基を有さない２種以上の他のモノマーとのコポリマーとしては、エチレン－マレイン酸共重合体又はその塩、メタクリル酸－アクリル酸エチル共重合体又はその塩が挙げられる。 The (A) non-crosslinked polymer polycarboxylic acid (salt) used in the present invention may be a homopolymer of a monomer having a carboxyl group, and a monomer having a carboxyl group and two or more kinds having a carboxyl group. Or a copolymer with two or more other monomers having no carboxyl group. Examples of the homopolymer include poly (meth) acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyitaconic acid or a salt thereof, and the like. Examples of the copolymer of a monomer having a carboxyl group and two or more other monomers having a carboxyl group include, for example, a (meth) acrylic acid-maleic acid copolymer or a salt thereof, an acrylic acid-crotonic acid copolymer, or The salt is given. Examples of the copolymer of the monomer having a carboxyl group and two or more other monomers having no carboxyl group include an ethylene-maleic acid copolymer or a salt thereof, a methacrylic acid-ethyl acrylate copolymer or a salt thereof. Can be mentioned.
　好ましくは、（メタ）アクリル酸／マレイン酸共重合体又はその塩、エチレン－マレイン酸共重合体又はその塩が挙げられる。（メタ）アクリル酸／マレイン酸共重合体又はその塩が好ましい。アクリル酸／マレイン酸共重合体又はその塩がより好ましい。アクリル酸／マレイン酸共重合体の塩がさらに好ましい。とりわけ、共重合比（モル比）が７５／２５～５０／５０であって、重量平均分子量が１万～１０万、特に４万～６万であるアクリル酸／マレイン酸共重合体又はその塩が好ましい。塩としてはナトリウム塩、カリウム塩などが挙げられる。（A）成分としては、非架橋型高分子ポリカルボン酸（塩）を単独で又は２種以上を併用することができる。
　本発明で使用する（A)成分は、合成しても良く、又は市場で入手できるものを使用しても良い。市場で入手可能な物としては、例えば日本触媒(株)製のアクアリックTL400（アクリル酸/マレイン酸共重合体　重量平均分子量：50000、粘度：約2000mPa/s（温度：23℃、濃度：40%）、BASF社製のソカランCP7及びCP5（共にアクリル酸／マレイン酸共重合体　CP7の重量平均分子量：50000、粘度：約1500mPa/s（温度：23℃、濃度：40%）、CP5の重量平均分子量：70000、粘度：約2000mPa/s（温度：23℃、濃度：40%））等が挙げられる。
　なお、非架橋型ポリカルボン酸又はその塩の粘度は、例えばローターNo.１～４を用いたBL型粘度測定機を用い、25℃でローターの回転数6～60rpm、測定時間20～120秒の条件で測定できる。 Preferably, a (meth) acrylic acid / maleic acid copolymer or a salt thereof, an ethylene-maleic acid copolymer or a salt thereof is used. A (meth) acrylic acid / maleic acid copolymer or a salt thereof is preferred. An acrylic acid / maleic acid copolymer or a salt thereof is more preferable. A salt of acrylic acid / maleic acid copolymer is more preferable. In particular, an acrylic acid / maleic acid copolymer or a salt thereof having a copolymerization ratio (molar ratio) of 75/25 to 50/50 and a weight average molecular weight of 10,000 to 100,000, particularly 40,000 to 60,000. Is preferred. Examples of the salt include sodium salt and potassium salt. As the component (A), non-crosslinked polymer polycarboxylic acid (salt) can be used alone or in combination of two or more.
The component (A) used in the present invention may be synthesized or commercially available. Examples of commercially available products include Aqualic TL400 (acrylic acid / maleic acid copolymer, weight average molecular weight: 50000, viscosity: about 2000 mPa / s (temperature: 23 ° C., concentration: 40) manufactured by Nippon Shokubai Co., Ltd. %), Sokaran CP7 and CP5 manufactured by BASF (both acrylic acid / maleic acid copolymer CP7 weight average molecular weight: 50,000, viscosity: about 1500 mPa / s (temperature: 23 ° C., concentration: 40%), CP5 weight Average molecular weight: 70000, viscosity: about 2000 mPa / s (temperature: 23 ° C., concentration: 40%)).
The viscosity of the non-crosslinked polycarboxylic acid or a salt thereof is measured using a BL type viscometer using, for example, rotor Nos. 1 to 4 at a rotor rotation speed of 6 to 60 rpm and a measurement time of 20 to 120 seconds. Can be measured under the following conditions.
（B)成分
　（B)成分は、ソルビトールである。（B）成分を配合することにより、本発明の組成物の粘度を上げることができ、使い勝手が良くなる。酵素の貯蔵安定性、酵素による洗浄力、特に長期保存後の酵素による洗浄力、及び低温安定性が向上する。加えて、組成物の保存後の透明な外観保持に寄与する。
　使用する（B)成分は、合成しても良く、又は市場で入手できるものを使用しても良い。市場で入手可能な物としては、例えば、ROQUETTE社製のNEOSORB 70/02B、三菱商事フードテック社製のソルビットD-70、サンエイ糖化社製のソルビットAO-T、日研化成社製のソルビトールS等が挙げられる。 (B) Component (B) component is sorbitol. By blending the component (B), the viscosity of the composition of the present invention can be increased and the usability is improved. The storage stability of the enzyme, the detergency by the enzyme, especially the detergency by the enzyme after long-term storage, and the low temperature stability are improved. In addition, it contributes to maintaining a transparent appearance after storage of the composition.
The component (B) to be used may be synthesized or commercially available. Examples of products available on the market include NEOSORB 70 / 02B manufactured by ROQUETTE, Sorbit D-70 manufactured by Mitsubishi Corporation Foodtech, Sorbit AO-T manufactured by Sanei Sugar Chemical Co., and Sorbitol S manufactured by Nikken Kasei. Etc.
（C）成分
　（C）成分は、プロピレングリコール、グリセリン、グルコース、マンニトール及びアルキルグルコシドからなる群から選ばれる１種以上である。
　（C）成分を配合することにより、本発明の組成物に含まれる酵素の貯蔵安定性を向上する機能を発揮する。さらに、組成物の透明な外観保持にも寄与する。アルキルグルコシド、なかでも2-エチルヘキシルグルコシドは、特に液体洗浄剤組成物の透明な外観保持、酵素の貯蔵安定性向上の向上に寄与する。プロピレングリコール、グリセリン、グルコース及びマンニトール、なかでもプロピレングリコール、グリセリンは、本発明の組成物に含まれる酵素の貯蔵安定性向上、組成物保存後の透明外観保持に寄与する。 Component (C) The component (C) is at least one selected from the group consisting of propylene glycol, glycerin, glucose, mannitol and alkyl glucoside.
(C) By mix | blending component, the function which improves the storage stability of the enzyme contained in the composition of this invention is exhibited. Furthermore, it contributes to maintaining the transparent appearance of the composition. Alkyl glucoside, especially 2-ethylhexyl glucoside, contributes particularly to maintaining the transparent appearance of the liquid detergent composition and improving the storage stability of the enzyme. Propylene glycol, glycerin, glucose and mannitol, especially propylene glycol and glycerin contribute to improving the storage stability of the enzyme contained in the composition of the present invention and maintaining the transparent appearance after the composition is stored.
　（C）が、アルキルグルコシドと、プロピレングリコール、グリセリン、グルコース及びマンニトールからなる群から選ばれる１種以上との混合物であるのが好ましい。
　（C）がアルキルグルコシドと、プロピレングリコール及びグリセリンからなる群から選ばれる１種以上との混合物であるのがさらに好ましい。 (C) is preferably a mixture of an alkyl glucoside and one or more selected from the group consisting of propylene glycol, glycerin, glucose and mannitol.
More preferably, (C) is a mixture of an alkyl glucoside and one or more selected from the group consisting of propylene glycol and glycerin.
　前記アルキルグルコシドとしては、以下の式（１）：
　　　　　　　　　　　　　Ｒ1（ＯＲ2）xＧy　　　　　　　　　　　（１）
（式中、Ｒ1は炭素数２～１０、好ましくは４～１０、より好ましくは４～８の直鎖又は分枝の、好ましくは直鎖のアルキル基又はアルケニル基であり、
　Ｒ2は炭素数２～４、好ましくは２～３の直鎖又は分枝のアルキレン基であり、
　Ｇは炭素数５又は６の還元糖に由来する残基、好ましくはグルコースに由来する残基であり、
　ｘは平均値が０～５、好ましくは０～２であり、より好ましくは０であり、ｙは平均値が１．０～４．２、好ましくは１．０～３．０、より好ましくは１．０（即ち、単糖）である。）
で表される化合物を好適に用いることができる。
　前記アルキルグリコシドが、2-エチルヘキシルグルコシドであるのが特に好ましい。
　（C）が、（c1）2-エチルヘキシルグルコシドと、（c2）プロピレングリコール及びグリセリンからなる群から選ばれる１種以上との混合物であるのが更に特に好ましい。 As the alkyl glucoside, the following formula (1):
R 1 (OR 2 ) x G y (1)
(Wherein R 1 represents a linear or branched, preferably linear alkyl or alkenyl group having 2 to 10, preferably 4 to 10, more preferably 4 to 8 carbon atoms,
R 2 is a linear or branched alkylene group having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms,
G is a residue derived from a reducing sugar having 5 or 6 carbon atoms, preferably a residue derived from glucose;
x has an average value of 0-5, preferably 0-2, more preferably 0, and y has an average value of 1.0-4.2, preferably 1.0-3.0, more preferably 1.0 (ie monosaccharide). )
The compound represented by can be used suitably.
It is particularly preferred that the alkyl glycoside is 2-ethylhexyl glucoside.
It is particularly preferred that (C) is a mixture of (c1) 2-ethylhexyl glucoside and (c2) one or more selected from the group consisting of propylene glycol and glycerin.
　（C）成分は、合成しても良く、又は市場で入手できるものを使用しても良い。2-エチルヘキシルグルコシドは、例えば、ライオンアクゾ社製のAG6202として市販されている。グリセリンは、例えば、阪本薬品工業社製の濃グリセリン、日本油脂社製の局方濃グリセリンとして市販されている。プロピレングリコールは、例えば、旭硝子社製のプロピレングリコール、昭和電工社製のプロピレングリコール、ADEKA社製のプロピレングリコールとして市販されている。
　特に本発明においては、前記（A）成分、（B）成分及び（C）成分、なかでも（c1）成分及び（c2）成分を併用することにより、（D）成分配合系において、これらを単独で使用する場合と比較して、相乗的に、使い勝手をよくするための適正粘度、優れた洗浄力を得、酵素の貯蔵安定性向上、及び、組成物保存後の透明外観保持に寄与することができる。また、前記（A）成分、（B）成分及び（C）成分、なかでも（c1）成分（c2）を併用することにより、香料の安定配合が可能となる。 Component (C) may be synthesized or commercially available. 2-Ethylhexyl glucoside is commercially available, for example, as AG6202 manufactured by Lion Akzo. Glycerin is commercially available, for example, as concentrated glycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. Propylene glycol is commercially available, for example, as propylene glycol manufactured by Asahi Glass Co., Ltd., propylene glycol manufactured by Showa Denko KK, and propylene glycol manufactured by ADEKA.
In particular, in the present invention, by combining the (A) component, the (B) component and the (C) component, in particular, the (c1) component and the (c2) component, these can be used alone in the (D) component blending system. Compared to the case of using in a product, synergistically obtain an appropriate viscosity for improved usability and excellent detergency, contribute to improving the storage stability of the enzyme and maintaining the transparent appearance after storing the composition. Can do. In addition, the combination of the component (A), the component (B), the component (C), and particularly the component (c1) (c2) enables stable blending of the fragrance.
（D）成分
　（D）成分は酵素である。酵素を配合することにより、被洗物の汚れ洗浄能力、特に食器に付着したデンプン汚れ及びタンパク汚れを除去する能力を向上できる。
　酵素は、１種以上含むことができるが、デンプン分解酵素及びタンパク質分解酵素からなる群から選ばれる１種以上の酵素を配合することがより好ましい。
　酵素としては、例えば、アミラーゼ及びプロテアーゼからなる群から選ばれる１種以上を配合することが好ましい。特にアミラーゼとプロテアーゼを併用することが好ましい。
　アミラーゼとしては、ターマミルウルトラ ３００Ｌ（ノボザイムズ社製）、ターマミル ３００Ｌ Ｔｙｐｅ ＤＸ（ノボザイムズ社製）、ステインザイム１２Ｌ（ノボザイムズ社製）、ステインザイムプラス１２Ｌ（ノボザイムズ社製）、デュラミル ３００Ｌ Ｔｙｐｅ ＤＸ（ノボザイムズ社製）などが挙げられる。
　プロテアーゼとしては、エバラーゼ １６Ｌ　Ｔｙｐｅ　ＤＸ（ノボザイムズ社製）、サビナーゼウルトラ１６ＸＬ（ノボザイムズ社製）、ピュラフェクトプライム ４０００Ｌ（ジェネンコア社製）、ピュラフェクトOX4000L（ジェネンコア社製）、プロペラーゼL（ジェネンコア社製）、アルカラーゼウルトラ２．５Ｌ（ノボザイムズ社製）、アルカラーゼ２．５Ｌ Ｔｙｐｅ　ＤＸ（ノボザイムズ社製）などが挙げられる。 (D) component (D) component is an enzyme. By blending the enzyme, it is possible to improve the dirt cleaning ability of the article to be washed, particularly the ability to remove starch dirt and protein dirt adhered to the tableware.
One or more enzymes can be contained, but it is more preferable to blend one or more enzymes selected from the group consisting of amylolytic enzymes and proteolytic enzymes.
As an enzyme, it is preferable to mix | blend 1 or more types chosen from the group which consists of amylase and protease, for example. In particular, amylase and protease are preferably used in combination.
As amylase, Termamyl Ultra 300L (manufactured by Novozymes), Termamyl 300L Type DX (manufactured by Novozymes), Steinzyme 12L (manufactured by Novozymes), Steinzyme Plus 12L (manufactured by Novozymes), Duramil 300L Type DX (Novozymes) Manufactured).
Examples of proteases include Everase 16L Type DX (Novozymes), Sabinase Ultra 16XL (Novozymes), Purefect Prime 4000L (Genencore), Purefect OX4000L (Genencore), Properase L (Genencore), Examples include Alcalase Ultra 2.5L (manufactured by Novozymes), Alcalase 2.5L Type DX (manufactured by Novozymes), and the like.
香料組成物
  本発明の組成物は更に香料組成物を含有することができる。本発明の組成物に用いることができる香料組成物としては、例えば2-メチルブチルアセテート、ベンジルアセテート、ブチルアセテート、ブチルブチレート、カンフェン、デカナール、ジヒドロミルセノール、エチル2-エチルブチレート、ゲラニアール、ゲラニオール、ゲラニルアセテート、ヘキシルアセテート、ヘキシルシンナミックアルデヒド、へキシルサリシレート、L-カルボン、リモネン、リナロール、L-メントール、ミルセン、オクタナール、ターピノレン、α－ピネン及びα-タ－ピネオールからなる群から選ばれる香料を含有する組成物があげられる。これらの香料を全て含む香料組成物が好ましい。 Fragrance composition The composition of the present invention may further contain a fragrance composition. Examples of the fragrance composition that can be used in the composition of the present invention include 2-methylbutyl acetate, benzyl acetate, butyl acetate, butyl butyrate, camphene, decanal, dihydromyrsenol, ethyl 2-ethylbutyrate, and geranial. , Geraniol, geranyl acetate, hexyl acetate, hexylcinnamic aldehyde, hexyl salicylate, L-carvone, limonene, linalool, L-menthol, myrcene, octanal, terpinolene, α-pinene and α-tapineol And a composition containing a perfume. A fragrance composition containing all of these fragrances is preferred.
その他の成分
　本発明の自動食器洗浄機用液体洗浄剤組成物は、その他の成分として水を配合できる。なお、本発明の組成物における水分の含有量は、組成物中の全水分量を意味する。即ち、組成物のバランスをとるのに配合される水の量と、原料が溶液として配合される際の該溶液中の水の量とを合わせた量を意味する。
　本発明の組成物は、さらに、自動食器洗浄機用液体洗浄剤組成物に通常含まれている成分を含むことができる。特に、ノニオン性界面活性剤、カチオン性界面活性剤、防腐剤を含むのが好ましい。 Other Components The liquid detergent composition for an automatic dishwasher of the present invention can contain water as other components. The water content in the composition of the present invention means the total water content in the composition. That is, it means the total amount of water added to balance the composition and the amount of water in the solution when the raw material is added as a solution.
The composition of the present invention may further contain components usually contained in a liquid detergent composition for an automatic dishwasher. In particular, it is preferable to include a nonionic surfactant, a cationic surfactant, and a preservative.
　ノニオン性界面活性剤としては、例えば、下記式（２）で表されるポリオキシエチレンポリオキシプロピレンアルキルエーテル等があげられる。本発明の組成物がノニオン性界面活性剤を含有することにより、油汚れ洗浄力、組成物の経時安定性が向上するので好ましい。
　　　　　　　　　　Ｒ１－Ｏ－（ＥＯ）ｐ（ＰＯ）ｑ－Ｈ　　　　（２）
　Ｒ１は炭素数８～２０、好ましくは８～１６の疎水基であり、直鎖であっても分岐鎖であってもよい。疎水基としては高級アルコール、高級脂肪酸、高級脂肪酸アミドを原料とするものが挙げられる。ＥＯはエチレンオキサイド基を、ＰＯはプロピレンオキサイド基を示す。ｐ及びｑはエチレンオキサイド基及びプロピレンオキサイド基の平均付加モル数であり、かつｐ及びｑそれぞれが１～６の範囲である。ｐが６を超えると泡立ちが高くなり、自動食器洗い乾燥機に負担をかけてしまい洗浄力も低下するおそれある。またｑが６を超えると組成物の経時安定性に劣る場合がある。また、ｐとｑの合計は、好ましくは３～１０である。ｐとｑの合計が３に満たないと油汚れ洗浄効果の点でやや劣り、また１０を超えると泡立ちが高くなる、または組成物の経時安定性に劣る場合が生じるため好ましくない。ノニオン性界面活性剤としては、特に、式（２）のポリオキシエチレンポリオキシプロピレンアルキルエーテルが好ましい。 Examples of the nonionic surfactant include polyoxyethylene polyoxypropylene alkyl ether represented by the following formula (2). It is preferable for the composition of the present invention to contain a nonionic surfactant since the oil stain detergency and stability over time of the composition are improved.
R1-O- (EO) p (PO) q-H (2)
R1 is a hydrophobic group having 8 to 20 carbon atoms, preferably 8 to 16 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from higher alcohols, higher fatty acids, and higher fatty acid amides. EO represents an ethylene oxide group, and PO represents a propylene oxide group. p and q are the average number of moles added of the ethylene oxide group and the propylene oxide group, and each of p and q is in the range of 1-6. If p exceeds 6, foaming will increase, placing a burden on the automatic dishwasher and possibly reducing the cleaning power. If q exceeds 6, the composition may have poor stability over time. The total of p and q is preferably 3 to 10. If the total of p and q is less than 3, it is slightly inferior in terms of the effect of cleaning oil stains, and if it exceeds 10, foaming may increase or the composition may have poor stability over time, which is not preferable. As the nonionic surfactant, polyoxyethylene polyoxypropylene alkyl ether of the formula (2) is particularly preferable.
　カチオン性界面活性剤としては、例えば、下記式（３）で表される化合物等が挙げられる。 Examples of the cationic surfactant include a compound represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式中、Ｒ2及びＲ3は各々独立に、炭素数１～２０、好ましくは炭素数１０～１８の直鎖又は分岐鎖のアルキル基又はアルケニル基、長鎖ヒドロキシアルキル基、トリル基、フェニル基、ベンジル基のうちいずれかを示す。特に好ましくは、Ｒ2、Ｒ3のうち一方が炭素数１０～１８の直鎖又は分岐鎖のアルキル基又はアルケニル基、他方がメチル基又はトリル基の組み合わせである。ＥＯはエチレンオキサイド基を示す。ｍ及びｎはエチレンオキサイド基の平均付加モル数であり、各々独立に０以上の整数を示す。また、ｍ＋ｎは１０以上、好ましくは１０～５０である。ｍ＋ｎが１０以上であると、茶渋汚れに対する洗浄力がさらに向上する。Ｘ-は、陰イオンであり、塩素イオン、臭素イオン、ヨウ素イオン等のハロゲン原子イオンや、一般式Ｒ4Ｏ－（但し、Ｒ4は、炭素数１～３のアルキル基であり、好ましくはメチル基である。）で表されるイオン等が挙げられる。
　カチオン界面活性剤としては、式（３）で表される化合物が好ましく、塩化ポリオキシエチレン（１５）アルキルメチルアンモニウムがより好ましい。 In the formula, R 2 and R 3 are each independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, preferably 10 to 18 carbon atoms, a long-chain hydroxyalkyl group, a tolyl group, a phenyl group. And any one of benzyl groups. Particularly preferably, one of R 2 and R 3 is a combination of a linear or branched alkyl group or alkenyl group having 10 to 18 carbon atoms, and the other is a combination of a methyl group or a tolyl group. EO represents an ethylene oxide group. m and n are average added mole numbers of ethylene oxide groups, and each independently represents an integer of 0 or more. M + n is 10 or more, preferably 10 to 50. When m + n is 10 or more, the cleaning power against tea astringent stains is further improved. X − is an anion, a halogen atom ion such as chlorine ion, bromine ion, iodine ion, etc., or a general formula R 4 O— (where R 4 is an alkyl group having 1 to 3 carbon atoms, preferably A methyl group)) and the like.
As the cationic surfactant, a compound represented by the formula (3) is preferable, and polyoxyethylene (15) alkylmethylammonium chloride is more preferable.
　本発明の組成物に用いることができる防腐剤としては、２－ブロモ－２－ニトロ－１，３－プロパンジオール、イソチアゾロン等があげられる。
　その他の成分としては、例えば、エタノール等の溶媒類や、無機金属塩、植物抽出物、抗菌・殺菌剤、消臭剤、安定剤、増粘剤、イオン性界面活性剤、高分子、無機塩類等、自動食器洗浄機用液体洗浄剤組成物中に一般的に含有されている物質が挙げられる。 Examples of the preservative that can be used in the composition of the present invention include 2-bromo-2-nitro-1,3-propanediol, isothiazolone, and the like.
Other components include, for example, solvents such as ethanol, inorganic metal salts, plant extracts, antibacterial / bactericidal agents, deodorants, stabilizers, thickeners, ionic surfactants, polymers, inorganic salts Examples thereof include substances generally contained in liquid detergent compositions for automatic dishwashers.
配合量
　本発明の組成物は、組成物の全質量に基づいて（A)を4～20質量％、好ましくは8～18質量％、より好ましくは10～14質量％含む。（A）成分の含有量を4質量％以上とすることで十分な茶渋洗浄力及びガラスの曇り洗浄力が発揮でき、組成物の粘度の向上にも寄与する。20質量％以下とすることで、使い勝手の良い適度な範囲に組成物の粘度を収めることができ、酵素の貯蔵安定性が向上し、保存後も組成物の透明外観を保持できる。
　本発明の組成物は、組成物の全質量に基づいて、（B）を好ましくは２０～６０質量％、より好ましくは３０～５５質量％、さらに好ましくは３２～５０質量％含む。（B）成分の含有量を２０質量％以上とすることで、組成物の粘度の向上に寄与し、酵素の貯蔵安定性が向上し、保存後も組成物の透明外観を保持できる。５５質量％以下とすることで、使い勝手の良い適度な範囲に組成物の粘度を収めることができ、低温安定性が向上する。
　本発明の組成物は、組成物の全質量に基づいて、（C）を好ましくは４．５～１２質量％、より好ましくは５～８質量％含む。
　（C）として（c1）及び／又は（c2）を使用する場合、組成物の全質量に基づいて、（c1）を好ましくは0.5～５質量％、より好ましくは0.7～３質量％含む。（c2）を好ましくは４～１１質量％、より好ましくは４～７質量％含む。（c1）を0.5質量％以上とすることで、酵素の貯蔵安定性が向上し、保存後も組成物の透明外観を保持できる。（c1）を５質量％以下とすることで、酵素の貯蔵安定性が向上し、保存後も組成物の透明外観を保持できる。（c2）を４質量％以上とすることで、酵素の貯蔵安定性が向上し、保存後も組成物の透明外観を保持できる。（c2）を１１質量％以下とすることで、保存後も組成物の透明外観を保持できる。 Blending amount The composition of the present invention comprises 4 to 20% by mass, preferably 8 to 18% by mass, more preferably 10 to 14% by mass, based on the total mass of the composition. When the content of the component (A) is 4% by mass or more, sufficient tea astringency washing ability and glass fogging ability can be exerted, which contributes to the improvement of the viscosity of the composition. When the content is 20% by mass or less, the viscosity of the composition can be kept in an appropriate range that is easy to use, the storage stability of the enzyme is improved, and the transparent appearance of the composition can be maintained even after storage.
The composition of the present invention contains (B) preferably 20 to 60% by mass, more preferably 30 to 55% by mass, and further preferably 32 to 50% by mass based on the total mass of the composition. By making content of (B) component 20 mass% or more, it contributes to the improvement of the viscosity of a composition, the storage stability of an enzyme improves, and the transparent external appearance of a composition can be hold | maintained after a preservation | save. By setting it as 55 mass% or less, the viscosity of a composition can be stored in the moderate range with ease of use, and low temperature stability improves.
The composition of the present invention contains (C) preferably 4.5 to 12% by mass, more preferably 5 to 8% by mass, based on the total mass of the composition.
When (c1) and / or (c2) is used as (C), (c1) is preferably contained in an amount of 0.5 to 5% by mass, more preferably 0.7 to 3% by mass, based on the total mass of the composition. (C2) is preferably contained in an amount of 4 to 11% by mass, more preferably 4 to 7% by mass. By setting (c1) to 0.5% by mass or more, the storage stability of the enzyme is improved, and the transparent appearance of the composition can be maintained after storage. By setting (c1) to 5% by mass or less, the storage stability of the enzyme is improved, and the transparent appearance of the composition can be maintained after storage. By setting (c2) to 4% by mass or more, the storage stability of the enzyme is improved, and the transparent appearance of the composition can be maintained after storage. By setting (c2) to 11% by mass or less, the transparent appearance of the composition can be maintained even after storage.
　さらに本発明の洗浄組成物は、組成物の全質量に基づいて（B)及び(C)をその合計量で、25～70質量％、好ましくは30～60質量％、より好ましくは30～50質量％、さらに好ましくは40～50質量％で含む。（B）成分と（C）成分の合計量を25質量％以上とすることにより、使い勝手をよくする適正粘度を有し、酵素の貯蔵安定性が向上し、保存後も透明な外観を保持できる組成物が得られる。70質量％以下とすることにより、使い勝手をよくするための適正粘度を有し、低温安定性が向上する。（C）として（c1）及び（c2）の組み合わせを使用する場合、（c1）と（c2）との合計の配合量は好ましくは４～１２質量％、より好ましくは５～８質量％である。
  また、本発明の洗浄剤組成物に配合する（B）成分及び（C）成分は、（B）／（C）の質量比率が２～１０の範囲、好ましくは４～９の範囲となるように配合する。質量比率を前記範囲とすることにより、使い勝手をよくするための適正粘度及び優れた洗浄力を有し、酵素の貯蔵安定性が向上し、洗浄剤組成物が濁ったり、分離したりすることが無く、保存後も透明な外観を保持できる組成物が得られる。 Furthermore, the cleaning composition of the present invention comprises (B) and (C) in a total amount of 25 to 70% by mass, preferably 30 to 60% by mass, more preferably 30 to 50%, based on the total mass of the composition. It is contained at 40% by mass, more preferably 40-50% by mass. By making the total amount of component (B) and component (C) 25% by mass or more, it has an appropriate viscosity that improves usability, improves the storage stability of the enzyme, and maintains a transparent appearance even after storage. A composition is obtained. By setting it to 70% by mass or less, it has an appropriate viscosity for improved usability and improves low-temperature stability. When the combination of (c1) and (c2) is used as (C), the total amount of (c1) and (c2) is preferably 4 to 12% by mass, more preferably 5 to 8% by mass .
Further, the component (B) and the component (C) to be blended in the cleaning composition of the present invention have a mass ratio of (B) / (C) in the range of 2 to 10, preferably 4 to 9. Blend in. By setting the mass ratio in the above range, it has an appropriate viscosity for improving usability and an excellent cleaning power, the enzyme storage stability is improved, and the cleaning composition may become cloudy or separated. And a composition capable of maintaining a transparent appearance even after storage is obtained.
　（D）成分である酵素は、好ましくは0.05%～10質量％、より好ましくは、0.1～5質量％、さらに好ましくは0.1～1質量％配合することが可能である。この合計含有量が0.05質量％～10質量％の範囲とすることにより洗浄性能を向上できる。
　デンプン分解酵素は、組成中、好ましくは0.006～30単位／g（U／g）、より好ましくは0.012～15単位／g（U／g）、さらに好ましくは0.012～3単位／g（U／g）配合することが可能である。この範囲とすることによりデンプン汚れに対する洗浄性能を向上できる。
　タンパク分解酵素は、組成中、好ましくは0.00125～400単位／g（U／g）、より好ましくは0.0025～200単位／g（U／g）、さらに好ましくは0.0025～40単位／g（U／g）配合することが可能である。この範囲とすることによりタンパク汚れに対する洗浄性能を向上できる。 The enzyme as component (D) is preferably added in an amount of 0.05% to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.1 to 1% by mass. When the total content is in the range of 0.05% by mass to 10% by mass, the cleaning performance can be improved.
The amylolytic enzyme in the composition is preferably 0.006 to 30 units / g (U / g), more preferably 0.012 to 15 units / g (U / g), and still more preferably 0.012 to 3 units / g (U / g). ) Can be blended. By setting it as this range, the washing | cleaning performance with respect to starch dirt can be improved.
In the composition, the proteolytic enzyme is preferably 0.00125 to 400 units / g (U / g), more preferably 0.0025 to 200 units / g (U / g), and still more preferably 0.0025 to 40 units / g (U / g). ) Can be blended. By setting it within this range, it is possible to improve the cleaning performance against protein stains.
　水は、組成物の全質量に対して、好ましくは65質量％以下、より好ましくは60質量％以下、さらに好ましくは55質量％以下、具体的には40～50質量％の範囲で配合することが可能である。65％を超えると、酵素の貯蔵安定性を低下させる場合がある。
　香料組成物は、組成物の全質量に対して、好ましくは0.01～0.1質量％、より好ましくは0.03～0.1質量％の範囲で配合することが可能である。
　ノニオン性界面活性剤は、組成物の全質量に対して、好ましくは0.01～0.1質量％、より好ましくは0.05～0.1質量％の範囲で配合することが可能である。
　カチオン性界面活性剤は、組成物の全質量に対して、好ましくは0.1～1.0質量％、より好ましくは0.5～1.0質量％の範囲で配合することが可能である。
　防腐剤は、組成物の全質量に対して、好ましくは0.001～0.01質量％、より好ましくは0.005～0.01質量％の範囲で配合することが可能である。 Water is preferably added in an amount of 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, specifically 40 to 50% by mass with respect to the total mass of the composition. Is possible. If it exceeds 65%, the storage stability of the enzyme may be reduced.
The perfume composition can be blended in the range of preferably 0.01 to 0.1% by mass, more preferably 0.03 to 0.1% by mass, based on the total mass of the composition.
The nonionic surfactant can be added in an amount of preferably 0.01 to 0.1% by mass, more preferably 0.05 to 0.1% by mass, based on the total mass of the composition.
The cationic surfactant can be blended in the range of preferably 0.1 to 1.0% by mass, more preferably 0.5 to 1.0% by mass with respect to the total mass of the composition.
The preservative can be added in an amount of preferably 0.001 to 0.01% by mass, more preferably 0.005 to 0.01% by mass, based on the total mass of the composition.
本発明の組成物の製造方法
　本発明の組成物の製造方法は特に制限を受けることなく、従来の液体洗浄剤組成物を製造する際のいかなる方法も使用できる。例えば、（A）～（C）成分及びその他の成分を配合し、ｐH調整剤で任意のｐH、例えば６から８の間にｐHを調整後、（D）成分を配合することが好ましい。 Method for Producing the Composition of the Present Invention The method for producing the composition of the present invention is not particularly limited, and any method for producing a conventional liquid detergent composition can be used. For example, it is preferable that the components (A) to (C) and other components are blended, the pH is adjusted with a pH adjuster, for example, between 6 and 8, and then the component (D) is blended.
本発明の組成物の物性
　本発明の組成物のｐHは6から8の範囲であることが好ましい。ｐHを6から8の範囲とすることにより、アルミ製などの食器を洗浄する際の仕上がり性を向上でき、また酵素の貯蔵安定性を向上できる。ｐHはｐH調整剤（例えば、水酸化ナトリウム、硫酸）で調整できる。
　本発明の組成物の粘度は、好ましくは100～2000mPa・s、より好ましくは200～1000 mPa・sの範囲である。この範囲は、組成物を容易に計量でき、自動食器洗浄機へ組成物を容易に投入できる、使い勝手が良好な適正粘度範囲である。粘度は、例えばローターNo.１～４を用いたBL型粘度測定機を用い、25℃でローターの回転数6～60rpm、測定時間20～120秒の条件で測定できる。
　以下に、実施例により本発明をより詳細に説明する。なお、以下の実施例が本発明の範囲を何ら制限しないことは言うまでもない。 Physical properties of the composition of the present invention The pH of the composition of the present invention is preferably in the range of 6-8. By adjusting the pH in the range of 6 to 8, the finish when washing dishes such as aluminum can be improved, and the storage stability of the enzyme can be improved. The pH can be adjusted with a pH adjusting agent (for example, sodium hydroxide, sulfuric acid).
The viscosity of the composition of the present invention is preferably in the range of 100 to 2000 mPa · s, more preferably 200 to 1000 mPa · s. This range is an appropriate viscosity range in which the composition can be easily weighed and the composition can be easily put into an automatic dishwasher and is easy to use. Viscosity can be measured, for example, using a BL type viscometer using rotor Nos. 1 to 4 at 25 ° C. under conditions of a rotor speed of 6 to 60 rpm and a measurement time of 20 to 120 seconds.
Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the following examples do not limit the scope of the present invention.
　実施例、比較例で使用した各成分は、以下のものである。
（Ａ）成分
・マレイン酸アクリル酸ポリマー（アクアリックTL４００：日本触媒）　有効成分：４０％、水分：６０％、重量平均分子量：50,000
・マレイン酸アクリル酸ポリマー（ソカランCP７：BASF）　有効成分：９２％、水分：８％、重量平均分子量：50,000
・マレイン酸アクリル酸ポリマー（ソカランCP５：BASF）　有効成分：９２％、水分：８％、重量平均分子量：70,000 Each component used in Examples and Comparative Examples is as follows.
Component (A): Maleic acid acrylic acid polymer (AQUALIC TL400: Nippon Shokubai) Active ingredient: 40%, moisture: 60%, weight average molecular weight: 50,000
-Maleic acid acrylic acid polymer (Socaran CP7: BASF) Active ingredient: 92%, moisture: 8%, weight average molecular weight: 50,000
-Maleic acid acrylic acid polymer (Socaran CP5: BASF) Active ingredient: 92%, moisture: 8%, weight average molecular weight: 70,000
（Ｂ）成分
・ソルビトール（NEOSORB 70/02B：ROQUETTE社）　有効成分：７０％、水分：３０％
（Ｃ）成分
・２エチルヘキシルグルコシド（AG6202：ライオンアクゾ）　有効成分：６５％、水分：３５％
・グリセリン（濃グリセリン：阪本薬品工業(株)）　有効成分：１００％
・プロピレングリコール（旭硝子(株)）　有効成分：１００％
（Ｄ）成分
・アミラーゼ（ターマミルウルトラ３００L：ノボザイムズ社）　１００％品として配合。力価は300KNU(L)/g。
・プロテアーゼ（サビナーゼウルトラ１６XL：ノボザイムズ社）　１００％品として配合。力価は16KNPU-S/g。 (B) Ingredients Sorbitol (NEOSORB 70 / 02B: ROQUETTE) Active ingredient: 70%, moisture: 30%
(C) Ingredient 2-ethylhexyl glucoside (AG6202: Lion Akzo) Active ingredient: 65%, moisture: 35%
・ Glycerin (concentrated glycerin: Sakamoto Pharmaceutical Co., Ltd.) Active ingredient: 100%
・ Propylene glycol (Asahi Glass Co., Ltd.) Active ingredient: 100%
Component (D) Amylase (Termamyl Mill 300L: Novozymes) Blended as 100% product. The titer is 300KNU (L) / g.
・ Protease (Sabinase Ultra 16XL: Novozymes) Contains 100% product. The titer is 16KNPU-S / g.
・香料組成物
2-メチルブチルアセテート：1%、ベンジルアセテート：1%、ブチルアセテート：2%、ブチルブチレート：0.5%、カンフェン：0.5%、デカナール：0.5%、ジヒドロミルセノール：2%、エチル2-エチルブチレート：1%、ゲラニアール：3%、ゲラニオール：6%、ゲラニルアセテート：4%、ヘキシルアセテート：2%、ヘキシルシンナミックアルデヒド：2%、へキシルサリシレート：3%、L-カルボン：1%、リモネン：55%、リナロール：8%、L-メントール：3.5%、ミルセン：0.5%、オクタナール：0.5%、ターピノレン：1%、α－ピネン：1%、α-タ－ピネオール：1%（各香料の後ろの「％」は、これらの総量を基準とする割合を示す） ・ Perfume composition
2-methylbutyl acetate: 1%, benzyl acetate: 1%, butyl acetate: 2%, butyl butyrate: 0.5%, camphene: 0.5%, decanal: 0.5%, dihydromyrsenol: 2%, ethyl 2-ethyl Butyrate: 1%, Geranial: 3%, Geraniol: 6%, Geranyl Acetate: 4%, Hexyl Acetate: 2%, Hexylcinnamic Aldehyde: 2%, Hexyl Salicylate: 3%, L-Carvone: 1%, Limonene: 55%, linalool: 8%, L-menthol: 3.5%, myrcene: 0.5%, octanal: 0.5%, turpinolene: 1%, α-pinene: 1%, α-tapineol: 1% (each fragrance) "%" After the number indicates the percentage based on the total amount)
（任意成分）
・ＣnＨ2n+1Ｏ（ＥＯ）3（ＰＯ）3Ｈ　（ｎ＝１２／１３混合物（質量比６５／３５））。有効成分：９６．５％、水分：３．５％。Ｎｅｏｄｏｌ－２３（Ｓｈｅｌｌ製、分岐率２０％のアルコール)の平均ＥＯ３ＰＯ３モル付加物。合成は特開２００７－２３２６８号公報の段落００６３の記載に従って行った。）
・塩化ポリオキシエチレン（１５）アルキルメチルアンモニウム（（エソカードＣ／２５：ライオンアクゾ）　有効成分：９５％、水分：２％）
・２－ブロモ－２－ニトロ－１，３－プロパンジオール（(プロテクトールBN：ＢＡＳＦ社製)　有効成分：９９％以上)
・イソチアゾロン液（（ケーソンCG：ローム・アンド・ハース製）有効成分：1.5%、マグネシウム塩：23%、水：75.5%）
・水酸化ナトリウム又は硫酸（ｐＨ調整剤）：適量
・精製水：バランス (Optional component)
· C n H 2n + 1 O (EO) 3 (PO) 3 H (n = 12/13 mixture (weight ratio 65/35)). Active ingredient: 96.5%, moisture: 3.5%. Average EO3PO3 molar adduct of Neodol-23 (Shell, 20% branched alcohol). The synthesis was carried out according to the description in paragraph 0063 of JP2007-23268. )
・ Polyoxyethylene chloride (15) alkylmethylammonium (Esocard C / 25: Lion Akzo) Active ingredient: 95%, moisture: 2%
・ 2-Bromo-2-nitro-1,3-propanediol (Protectol BN: manufactured by BASF) Active ingredient: 99% or more)
・ Isothiazolone (Caisson CG: Rohm & Haas) active ingredient: 1.5%, magnesium salt: 23%, water: 75.5%
-Sodium hydroxide or sulfuric acid (pH adjuster): appropriate amount-Purified water: balance
　上に示した（A）～（C）成分及び任意成分を混合し、ｐH調整剤で該混合物のｐHを7.3に調整した後、（D）成分を加えさらに混合し、精製水を加えてバランスをとることにより、実施例及び比較例の自動食器洗浄機用液体洗浄剤組成物を得た。各成分の量は以下の表１及び２に記載したとおりであり、純分量としての量である。ｐＨは、２５℃においてガラス電極を用いて測定した。このようにして得られた組成物を、以下の各試験により評価した。結果を表１及び表２に示す。 Mix components (A) to (C) and optional components shown above, adjust the pH of the mixture to 7.3 with a pH adjuster, add component (D), mix, and add purified water to balance. As a result, liquid detergent compositions for automatic dishwashers of Examples and Comparative Examples were obtained. The amount of each component is as described in Tables 1 and 2 below, and is the amount as a pure component. The pH was measured using a glass electrode at 25 ° C. The composition thus obtained was evaluated by the following tests. The results are shown in Tables 1 and 2.
《評価方法》
＜１．組成物の粘度の測定方法＞
（測定条件）BL型粘度測定機（DIGITAL　VISMETRON　VDA）
　測定温度：２５℃、回転数：６～６０rpm、測定時間：２０～１２０秒、ローターNo：１～４ "Evaluation methods"
<1. Method for Measuring Viscosity of Composition>
(Measurement conditions) BL type viscosity measuring machine (DIGITAL VISMETRON VDA)
Measurement temperature: 25 ° C., rotation speed: 6 to 60 rpm, measurement time: 20 to 120 seconds, rotor No .: 1 to 4
＜２．使い勝手の評価方法＞
　各組成物８０ｍＬを１００ｍＬガラスビーカに入れ、２５℃恒温槽で組成物の温度を25℃に調整した後、パネラー５名に組成物６ｇを１０ｍＬビーカに投入させ、下記基準により使い勝手を評価した。
　　　　　　　液の投入がし易く、投入液量の調節もし易い。　　　　３点
　　　　　　　液の投入がし易く、投入液量の調節はやや難しい。　　２点
　　　　　　　液の投入が難しく、投入液量の調節も難しい。　　　　１点
　５名の評点の平均値を算出し、下記の様に評価結果を設定した。
評価基準：○～◎が合格範囲
　　　　　　　◎；平均点２．８以上
　　　　　　　○；平均点２．６以上２．８未満
　　　　　　　△；平均点２．０以上２．６未満
　　　　　　　×；平均点２．０未満 <2. Usability evaluation method>
After putting 80 mL of each composition into a 100 mL glass beaker and adjusting the temperature of the composition to 25 ° C. in a 25 ° C. constant temperature bath, 5 panelists were charged with 6 g of the composition in a 10 mL beaker, and the usability was evaluated according to the following criteria.
It is easy to charge the liquid, and it is easy to adjust the liquid volume. 3 points It is easy to add the liquid, and it is slightly difficult to adjust the amount of the liquid. Two points It is difficult to charge the liquid and it is difficult to adjust the amount of liquid. 1 point The average value of the scores of 5 people was calculated, and the evaluation results were set as follows.
Evaluation criteria: ○ to ◎ are acceptable ◎; Average score 2.8 or higher ○; Average score 2.6 or higher and lower than 2.8 Δ; Average score 2.0 or higher and lower than 2.6 ×;
＜３．４０℃保存後の外観観察＞
　各組成物８０ｍＬをPS11の瓶（100ml）に入れ、40℃で1ヶ月保存後の外観を目視で観察し、下記基準により評価した。
　　　　　　　○；透明である
　　　　　　　△；やや濁っている
　　　　　　　×；濁っている <Appearance observation after storage at 40 ° C.>
80 mL of each composition was placed in a PS11 bottle (100 ml), and the appearance after storage for 1 month at 40 ° C. was visually observed and evaluated according to the following criteria.
○: Transparent △: Slightly cloudy ×: Cloudy
＜４．洗浄力評価方法＞
（４．１　酵素による洗浄力の評価方法）
　各組成物の保存前と保存後（保存条件：室温、６ヶ月保存）の洗浄力を、下記の評価方法にて評価した。
（４．１．１　澱粉汚れ洗浄力）
　佐藤食品工業（株）製サトウのごはん５ｇを茶碗(直径１１５mm、高さ５０mm)に塗布した後に、２５℃、５０％ＲＨ条件下に一昼夜（24時間）放置したものを用いて洗浄評価を行った。食器洗浄機はナショナル社製のNP-40SX2を用い、標準コースを選択して茶碗を洗浄した。洗浄後の茶碗の状態を以下の基準で評価した。
評価基準：○～◎が合格範囲
　　　　　　　◎：汚れが良く落ちている
　　　　　　　○：汚れが落ちている
　　　　　　　△：まあまあ汚れが落ちている
　　　　　　　×：全く汚れが落ちていない <4. Detergency evaluation method>
(4.1 Evaluation method of detergency by enzyme)
Detergency of each composition before and after storage (storage conditions: room temperature, stored for 6 months) was evaluated by the following evaluation method.
(4.1.1 Starch dirt cleaning power)
After applying 5g of Sato rice made by Sato Food Industry Co., Ltd. to a tea bowl (diameter: 115mm, height: 50mm), it was washed and evaluated using a dish that was left overnight at 25 ° C and 50% RH for 24 hours. It was. The dishwasher was NP-40SX2 made by National Corporation, and the standard course was selected to wash the teacups. The state of the tea bowl after washing was evaluated according to the following criteria.
Evaluation criteria: ○ to ◎ are acceptable range ◎: Dirt is well removed ○: Dirt is removed △: Fair dirt is removed ×: Dirt is not removed at all
（４．１．２　蛋白汚れ洗浄力）
　卵／水＝１／９を均一に攪拌したものを１００ｍｌビーカーへ５０ｇ注ぎ、蒸し器で２０分蒸した。その後、内溶液を廃棄し、乾燥したビーカーを用いて洗浄評価を行った。食器洗浄機はナショナル社製のNP-40SX2を用い、標準コースを選択してビーカーを洗浄した。洗浄後のビーカーの状態を以下の基準で評価した。
評価基準：○～◎が合格範囲
　　　　　　　◎：汚れが良く落ちている
　　　　　　　○：汚れが落ちている
　　　　　　　△：まあまあ汚れが落ちている
　　　　　　　×：全く汚れが落ちていない (4.1.2 Detergent power of protein stains)
50 g of egg / water = 1/9 with uniform stirring was poured into a 100 ml beaker and steamed with a steamer for 20 minutes. Thereafter, the inner solution was discarded, and cleaning evaluation was performed using a dried beaker. The NP-40SX2 made by National Corporation was used as the dishwasher, and the standard course was selected and the beaker was washed. The state of the beaker after washing was evaluated according to the following criteria.
Evaluation criteria: ○ to ◎ are acceptable range ◎: Dirt is well removed ○: Dirt is removed △: Fair dirt is removed ×: Dirt is not removed at all
（４．２　茶渋洗浄力の評価法）
　紅茶を飲み干してから２５℃、５０％ＲＨ条件下に５日間放置した紅茶汚垢の付いたコーヒーカップ（内径７０ｍｍ、高さ７０ｍｍ）３個を自動食器洗い乾燥機「松下電器産業（株）製、機種ＮＰ－４０ＳＸ２」に装填し、調製した組成物６ｇを使用して標準コース洗浄を行い、仕上がり具合を以下の評価基準に基づいて官能評価した。
　評価基準：
　　◎：汚れは全く残留しておらず、ざらつき等の違和感も感じられない。
　　○：汚れの残留は目視では認められないが、触ると若干のざらつき等の違和感を感じる。
　　△：汚れの残留が目視で若干認められる。
　　×：汚れが落ちていない。 (4.2 Evaluation Method for Tea Astringent Detergency)
Three cups of coffee with tea stains (inner diameter 70 mm, height 70 mm) left for 5 days at 25 ° C and 50% RH after drinking and drinking tea are automatically washed by the dishwasher “Matsushita Electric Industrial Co., Ltd. The model NP-40SX2 ”was loaded, 6 g of the prepared composition was used for standard course cleaning, and the finished condition was subjected to sensory evaluation based on the following evaluation criteria.
Evaluation criteria:
(Double-circle): A stain | pollution | contamination does not remain | survive at all and the discomfort, such as roughness, is not felt.
○: Residue of dirt is not visually recognized, but feels uncomfortable, such as slight roughness when touched.
Δ: Residue of dirt is slightly recognized visually.
X: Dirt is not removed.
（４．３　ガラスの曇り洗浄力の評価法）
　ガラスコップ（上径６３ｍｍ、下径５３ｍｍ、高さ１００ｍｍ）を自動食器洗い乾燥機に充填し、炭酸ナトリウム１．２ｇを機内に入れ、洗浄～すすぎの全行程を３０度硬水で行うことにより得られた白化したコップを自動食器洗い乾燥機「松下電器産業（株）製、機種ＮＰ－４０ＳＸ２」に装填し、調製した組成物６ｇを使用して標準コース洗浄を行い、仕上がり具合を以下の評価基準に基づいて官能評価した。
　評価基準：
　　◎：白化物は全く残留しておらず、ざらつき等の違和感も感じられない。
　　○：部分的にかすかに白化物の残留が認められる。
　　△：白化物の残留が目視で若干認められ、全体的に透明感が失われている。
　　×：白化物が落ちていない。 (4.3 Evaluation method for fogging detergency of glass)
It is obtained by filling a glass cup (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) into an automatic dishwasher, placing 1.2 g of sodium carbonate in the machine, and performing the entire process of washing and rinsing with 30 degree hard water. The whitened cup was loaded into an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2”, and the standard composition was washed using 6 g of the prepared composition. Based on the sensory evaluation.
Evaluation criteria:
A: No whitened material remains and no discomfort such as roughness is felt.
○: Some whitening residue is slightly observed.
Δ: A slight amount of whitened product was visually observed, and the overall transparency was lost.
X: The whitened material has not fallen.
＜５．低温安定性評価＞
　各組成物８０ｍＬをPS11の瓶（100ml）に入れ、－５℃で１ヶ月保存後の外観を目視で観察し、以下の基準で評価した。
　　　　　　　○；透明である
　　　　　　　△；濁っている
　　　　　　　×；析出物がある <5. Low temperature stability evaluation>
80 mL of each composition was placed in a PS11 bottle (100 ml), and the appearance after storage for 1 month at −5 ° C. was visually observed and evaluated according to the following criteria.
○: Transparent △: Cloudy ×: Precipitates
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　上記表１及び表２に示すように、本発明の範囲にある洗浄剤組成物は良好な粘度範囲を達成し、それにより良好な使い勝手を達成することができる。また、保存前の良好な洗浄性を示すだけでなく、保存後においても優れた洗浄性を示すことにより、本発明の液体洗浄剤組成物が優れた酵素の貯蔵安定性を有することが確認できる。これに対して、本発明の範囲を外れる比較例については、粘度が過剰に低く又は高くなることにより、使い勝手が悪くなる。また、酵素の保存安定性が低下していることも確認できる。 As shown in Table 1 and Table 2 above, the detergent composition within the scope of the present invention achieves a good viscosity range, thereby achieving good usability. Moreover, it can be confirmed that the liquid detergent composition of the present invention has excellent enzyme storage stability not only by showing good detergency before storage but also by excellent detergency after storage. . On the other hand, about the comparative example which remove | deviates from the range of this invention, usability worsens because a viscosity becomes low excessively or becomes high. It can also be confirmed that the storage stability of the enzyme is reduced.

Claims (9)

  1. 　（A）非架橋型ポリカルボン酸又はその塩、
    　（B）ソルビトール、
    　（C）プロピレングリコール、グリセリン、グルコース、マンニトール及びアルキルグルコシドからなる群から選ばれる１種以上、及び
    　（D）酵素
    を含み、組成物の全質量に基づいて、
    　（A)が4～20質量％、
    　（B)＋（C)が25～70質量％であり、かつ
    　（B）/（C）の質量比率が２～１０の範囲である自動食器洗浄機用液体洗浄剤組成物。     (A) Non-crosslinked polycarboxylic acid or a salt thereof,
    (B) sorbitol,
    (C) one or more selected from the group consisting of propylene glycol, glycerin, glucose, mannitol and alkyl glucoside, and (D) an enzyme, based on the total mass of the composition,
    (A) is 4 to 20% by mass,
    A liquid detergent composition for an automatic dishwasher, wherein (B) + (C) is 25 to 70% by mass and the mass ratio of (B) / (C) is in the range of 2 to 10.
  2. 　（C）が、アルキルグルコシドと、プロピレングリコール、グリセリン、グルコース及びマンニトールからなる群から選ばれる１種以上との混合物である請求項１記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to claim 1, wherein (C) is a mixture of alkyl glucoside and at least one selected from the group consisting of propylene glycol, glycerin, glucose and mannitol.
  3. 　（C）が2-エチルヘキシルグルコシドと、プロピレングリコール及びグリセリンからなる群から選ばれる１種以上との混合物である、請求項１又は２記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to claim 1 or 2, wherein (C) is a mixture of 2-ethylhexyl glucoside and one or more selected from the group consisting of propylene glycol and glycerin.
  4. 　非架橋型ポリカルボン酸又はその塩が、アクリル酸／マレイン酸共重合体の塩である、請求項１～３のいずれか１項記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 3, wherein the non-crosslinked polycarboxylic acid or a salt thereof is an acrylic acid / maleic acid copolymer salt.
  5. 　水分含有量が65質量％以下である、請求項１～４のいずれか１項記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the water content is 65% by mass or less.
  6. 　前記酵素が、デンプン分解酵素及びタンパク質分解酵素からなる群から選ばれる１種以上である、請求項１～５のいずれか１項記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 5, wherein the enzyme is one or more selected from the group consisting of amylolytic enzymes and proteolytic enzymes.
  7. 　更に、2-メチルブチルアセテート、ベンジルアセテート、ブチルアセテート、ブチルブチレート、カンフェン、デカナール、ジヒドロミルセノール、エチル2-エチルブチレート、ゲラニアール、ゲラニオール、ゲラニルアセテート、ヘキシルアセテート、ヘキシルシンナミックアルデヒド、へキシルサリシレート、L-カルボン、リモネン、リナロール、L-メントール、ミルセン、オクタナール、ターピノレン、α－ピネン及びα-タ－ピネオールからなる群から選ばれる香料を含有する請求項１～６のいずれか１項記載の自動食器洗浄機用液体洗浄剤組成物。 In addition, 2-methylbutyl acetate, benzyl acetate, butyl acetate, butyl butyrate, camphene, decanal, dihydromyrsenol, ethyl 2-ethylbutyrate, geranial, geraniol, geranyl acetate, hexyl acetate, hexylcinnamic aldehyde, 7. A fragrance selected from the group consisting of xyl salicylate, L-carvone, limonene, linalool, L-menthol, myrcene, octanal, terpinolene, α-pinene and α-terpineol. The liquid detergent composition for automatic dishwashers as described.
  8. 　25℃における組成物の粘度が100～2000mPa・sの範囲である請求項１～７のいずれか１項記載の自動食器洗浄機用液体洗浄剤組成物。 The liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 7, wherein the viscosity of the composition at 25 ° C is in the range of 100 to 2000 mPa · s.
  9. 　（a）（メタ）アクリル酸／マレイン酸共重合体の塩、
    　（b）ソルビトール、
    　（c1）2-エチルヘキシルグルコシド、
    　（c2）プロピレングリコール及びグリセリンからなる群から選ばれる１種以上、及び
    　（d）デンプン分解酵素及び／又はタンパク質分解酵素、
    を含み、組成物の全質量に基づいて、
    　（a）が４～２０質量％、
    　（b）＋（c1+c2）が２５～７０質量％であり、かつ
    　（b）/（c1+c2）の質量比率が２～１０の範囲である自動食器洗浄機用液体洗浄剤組成物。     (A) a salt of a (meth) acrylic acid / maleic acid copolymer,
    (B) sorbitol,
    (C1) 2-ethylhexyl glucoside,
    (C2) one or more selected from the group consisting of propylene glycol and glycerin, and (d) amylolytic enzyme and / or proteolytic enzyme,
    And based on the total weight of the composition,
    (A) is 4 to 20% by mass,
    A liquid detergent composition for an automatic dishwasher, wherein (b) + (c1 + c2) is 25 to 70% by mass and the mass ratio of (b) / (c1 + c2) is in the range of 2 to 10.
PCT/JP2009/064704 2008-08-22 2009-08-24 Liquid detergent composition for automatic dishwashing machines WO2010021398A1 (en)

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EP2380963A1 (en) * 2010-04-23 2011-10-26 The Procter & Gamble Company Method of perfuming
JP2012001663A (en) * 2010-06-18 2012-01-05 Kao Corp Liquid detergent composition for automatic dishwasher
JP2012082253A (en) * 2010-10-07 2012-04-26 Niitaka:Kk Detergent for automatic dishwasher
JP2012140484A (en) * 2010-12-28 2012-07-26 Kao Corp Cleanser composition for medical equipment
JP2012214655A (en) * 2011-04-01 2012-11-08 Lion Corp Detergent for dishwasher
JP2014227443A (en) * 2013-05-20 2014-12-08 ライオン株式会社 Detergent for dishwasher
WO2017046050A1 (en) * 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Liquid cleaning agent having optimized scent
JP2019505629A (en) * 2015-12-22 2019-02-28 ザ プロクター アンド ギャンブル カンパニー Automatic dishwashing composition

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BE1023885B1 (en) * 2016-06-29 2017-09-04 Realco Support impregnated with at least one composition for the removal of microorganisms present on a surface
KR102028590B1 (en) * 2018-03-29 2019-10-04 황병철 Eco-friendly high performance detergent composition for dishwasher

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JP2005089603A (en) * 2003-09-17 2005-04-07 Kao Corp Detergent composition
JP2008133340A (en) * 2006-11-28 2008-06-12 Kao Corp Liquid detergent composition for automatic dishwasher
JP2008163292A (en) * 2006-12-06 2008-07-17 Kao Corp Thickened liquid detergent composition and its manufacturing method

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JPH09241696A (en) * 1996-03-06 1997-09-16 Toray Ind Inc Liquid composition and cleaning of contact lens using the same
JP2005089603A (en) * 2003-09-17 2005-04-07 Kao Corp Detergent composition
JP2008133340A (en) * 2006-11-28 2008-06-12 Kao Corp Liquid detergent composition for automatic dishwasher
JP2008163292A (en) * 2006-12-06 2008-07-17 Kao Corp Thickened liquid detergent composition and its manufacturing method

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2380963A1 (en) * 2010-04-23 2011-10-26 The Procter & Gamble Company Method of perfuming
EP2380963B1 (en) 2010-04-23 2015-12-23 The Procter and Gamble Company Method of perfuming
JP2012001663A (en) * 2010-06-18 2012-01-05 Kao Corp Liquid detergent composition for automatic dishwasher
JP2012082253A (en) * 2010-10-07 2012-04-26 Niitaka:Kk Detergent for automatic dishwasher
JP2012140484A (en) * 2010-12-28 2012-07-26 Kao Corp Cleanser composition for medical equipment
JP2012214655A (en) * 2011-04-01 2012-11-08 Lion Corp Detergent for dishwasher
JP2014227443A (en) * 2013-05-20 2014-12-08 ライオン株式会社 Detergent for dishwasher
WO2017046050A1 (en) * 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Liquid cleaning agent having optimized scent
JP2019505629A (en) * 2015-12-22 2019-02-28 ザ プロクター アンド ギャンブル カンパニー Automatic dishwashing composition

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