WO2011052501A1 - Composition détergente liquide et son procédé de fabrication - Google Patents

Composition détergente liquide et son procédé de fabrication Download PDF

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Publication number
WO2011052501A1
WO2011052501A1 PCT/JP2010/068688 JP2010068688W WO2011052501A1 WO 2011052501 A1 WO2011052501 A1 WO 2011052501A1 JP 2010068688 W JP2010068688 W JP 2010068688W WO 2011052501 A1 WO2011052501 A1 WO 2011052501A1
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WIPO (PCT)
Prior art keywords
component
liquid detergent
detergent composition
mass
acid
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PCT/JP2010/068688
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English (en)
Japanese (ja)
Inventor
亮 兵藤
喜隆 宮前
雅貴 吉田
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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 JP2011538397A priority Critical patent/JP5743899B2/ja
Priority to CN2010800496685A priority patent/CN102597206A/zh
Publication of WO2011052501A1 publication Critical patent/WO2011052501A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/96—Stabilising an enzyme by forming an adduct or a composition; Forming enzyme conjugates

Definitions

  • the present invention relates to a liquid detergent composition and a method for producing the same.
  • powder type There are two types of cleaning agents for clothes used for washing at home: powder type and liquid type. Since powder detergent contains less moisture, it is advantageous in stably blending functional materials that are unstable in water and functional materials that react in water. Products have been developed.
  • enzymes are one of the important functional materials, especially in the harsh washing conditions in Japan (low temperature, low concentration, short time washing, etc.) It is used as an additive that demonstrates For this reason, enzymes are blended in many commercially available powder detergents for clothing, and many studies have been made to stably blend enzymes in detergents.
  • liquid detergents have been used not only in Japan but also in various countries in recent years because they are less likely to remain undissolved and can be applied directly to clothing.
  • the liquid detergent has a lower enzyme stability in the detergent than the powder detergent, and has not reached a satisfactory level. Therefore, improvement of the stability of the enzyme in the cleaning agent is an important issue for ensuring high detergency.
  • Examples of the enzyme stabilization technique in the liquid detergent include stabilization by adding a calcium salt that generates free calcium ions (see Patent Document 1), and short-chain carboxylates such as formate and lactate.
  • Stabilization see Patent Document 2, stabilization by blending a polyol and boric acid or a derivative thereof (see Patent Document 3), (meth) acrylic acid / (meth) acrylic ester copolymer And stabilization by blending polyethylene glycol with polyethylene glycol (see Patent Document 4), stabilization by bringing a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, guar gum or the like into contact with an enzyme (see Patent Document 5).
  • a method for stabilizing enzyme activity for example, a method of adding polyglutamic acid to an enzyme (see Patent Document 6) is known.
  • Patent Documents 1 to 5 do not satisfy sufficient storage stability of the enzyme.
  • the enzyme activity may be reduced to a level at which the performance cannot be sufficiently exhibited.
  • the liquid detergent containing a surfactant at a high concentration is prominent, and the enzyme activity tends to decrease.
  • the method described in Patent Document 6 is intended to impart resistance to temperature and pH to an enzyme, and is assumed to be applied in an environment where the enzyme is difficult to dissolve, such as a compact liquid detergent. Absent.
  • the present invention has been made in view of the above circumstances, and even when a surfactant is contained in a high concentration, a liquid detergent that can maintain the storage stability of the enzyme satisfactorily without reducing the enzyme activity. It aims at providing a composition and its manufacturing method.
  • a liquid detergent composition containing a surfactant suppresses a decrease in enzyme activity even when an enzyme is added, and in particular provides stable storage of the enzyme.
  • the present inventors have found that the storage stability of the enzyme can be maintained well even when the surfactant, which has been difficult to make, is contained at a high concentration and stored for a long period of time, has led to the completion of the present invention.
  • the liquid detergent composition of the present invention is characterized by containing the following components (A) to (D):
  • the content of the component (A) is preferably 45 to 65% by mass in 100% by mass of the liquid detergent composition.
  • the content of the component (D) is preferably 20 to 40% by mass in 100% by mass of the liquid detergent composition.
  • the homopolyamino acid is preferably polyglutamic acid and / or polyaspartic acid.
  • the liquid detergent composition of the present invention is particularly suitable for clothing.
  • the manufacturing method of the liquid cleaning composition of this invention mixes the remaining component, after mixing said (B) component, said (C) component, and a part or all of said (D) component. It is characterized by doing.
  • liquid detergent composition that can satisfactorily maintain the storage stability of an enzyme without reducing the enzyme activity and a method for producing the same. it can.
  • the liquid detergent composition of the present invention contains the components (A) to (D).
  • [(A) component] A component is surfactant and is used in order to provide detergency to a liquid detergent composition.
  • the content of the component (A) is preferably 10 to 70% by mass, more preferably 30 to 70% by mass, and particularly preferably 45 to 65% by mass in 100% by mass of the liquid detergent composition. If content of (A) component is 10 mass% or more, sufficient cleaning power can be provided to a liquid detergent composition. On the other hand, if content of (A) component is 70 mass% or less, high storage stability can be provided to a liquid detergent composition.
  • the content of the component (A) is in the range of 45 to 65% by mass, the component (A) is contained at a high concentration, so that the liquid detergent composition of the present invention is a compact type. While being able to use suitably as a washing
  • liquid detergent composition of the present invention contains the component (B), it is easy to form a complex with the component (B) and the component (C), and the component (C) is easily stabilized. Therefore, the liquid detergent composition of the present invention can maintain the storage stability of the enzyme well even when the component (A) is contained in a high concentration.
  • a nonionic surfactant is used as a component. Moreover, you may use together general surfactant used for cleaning agents, such as an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. In particular, it is preferable to use a nonionic surfactant and an anionic surfactant in combination in terms of superior cleaning performance.
  • the component (A-1) is a nonionic surfactant.
  • the component (A-1) is not particularly limited, but for example, a polyoxyalkylene type nonionic surfactant represented by the following general formula (I) is preferably used.
  • R 1 is a hydrophobic group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and may be linear or branched. Examples of the hydrophobic group include those derived from primary or secondary higher alcohols, higher fatty acids, higher fatty acid amides and the like.
  • —X— is a functional group such as —O—, —COO— or —CONH—.
  • EO represents an oxyethylene group [— (OCH 2 CH 2 ) —], which is a functional group obtained by addition reaction of ethylene oxide.
  • PO represents an oxypropylene group [— (OCH 2 CH (CH 3 )) —], which is a functional group obtained by addition reaction of propylene oxide.
  • R 2 is a hydrogen atom or an alkyl or alkenyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl or alkenyl group having 1 to 3 carbon atoms.
  • ethylene oxide and propylene oxide may be either random addition or block addition.
  • the addition order of ethylene oxide and propylene oxide is not particularly limited. If the average added mole number s of ethylene oxide is less than 3, odor tends to be generated or the liquid detergent composition tends to deteriorate. On the other hand, if the average added mole number s of ethylene oxide exceeds 20, the HLB value becomes too high, and it is disadvantageous especially for sebum cleaning, so that the cleaning function tends to be lowered. When the average added mole number t of propylene oxide exceeds 6, the storage stability of the liquid detergent composition at a high temperature tends to decrease.
  • HLB Hydrophilicity and lipophilicity of the surfactant molecule
  • the addition mole number distribution of ethylene oxide or propylene oxide is not particularly limited and is likely to vary depending on the reaction method in producing the nonionic surfactant.
  • the distribution of added moles of ethylene oxide or propylene oxide is compared when ethylene oxide or propylene oxide is added to a hydrophobic raw material using a general alkali catalyst such as sodium hydroxide or potassium hydroxide. Tend to be widely distributed.
  • specific alkoxylation such as magnesium oxide added with metal ions such as Al 3+ , Ga 3+ , In 3+ , Tl 3+ , Co 3+ , Sc 3+ , La 3+ , Mn 2+, etc. described in JP-B-6-15038
  • the distribution tends to be relatively narrow.
  • the nonionic surfactant when —X— is —O—, the nonionic surfactant is an alcohol ethoxylate.
  • the carbon number of the linear or branched alkyl group or alkenyl group of R 1 is 10 to 22, preferably 10 to 20, and more preferably 10 to 18.
  • R 1 may have an unsaturated bond.
  • R 2 is preferably a hydrogen atom.
  • the nonionic surfactant is a fatty acid ester type nonionic surfactant.
  • the carbon number of the linear or branched alkyl group or alkenyl group of R 1 is 9 to 21, preferably 11 to 21.
  • R 2 may have an unsaturated bond.
  • R 2 is preferably an alkyl group having 1 to 3 carbon atoms.
  • nonionic surfactant represented by the formula (I) include: Mitsubishi Chemical Co., Ltd .: trade name Diadol (C13, C represents the number of carbons; the same shall apply hereinafter); Shell Corporation: trade name Neodol (C12 / C13), manufactured by Sasol: a product obtained by adding 12 moles or 15 moles of ethylene oxide to an alcohol such as trade name Safol23 (C12 / C13), manufactured by P & G: trade names CO-1214 and CO An ethylene oxide equivalent to 7 moles of a C13 alcohol obtained by subjecting a C12 alkene obtained by adding a 12 mole equivalent or 15 mole equivalent of ethylene oxide to a natural alcohol such as 1270, or trimerizing butene to the oxo method (BASF brand name: Lutensol TO7), pentanol is added to the garbage.
  • Diadol C13, C represents the number of carbons; the same shall apply hereinafter
  • Shell Corporation trade name Neodol (C12 / C
  • nonionic surfactants other than the nonionic surfactant represented by the formula (I) may be used.
  • nonionic surfactants include, for example, alkylene oxide adducts such as alkylphenols, higher fatty acids or higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters or alkylene oxides thereof.
  • Examples include adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters, N-alkyl polyhydroxy fatty acid amides, and alkyl glycosides.
  • the component (A-1) a single type of nonionic surfactant may be used alone, or a plurality of types of nonionic surfactants may be used in combination. If the surfactant is contained in a high concentration, there are advantages that washing can be performed with a small amount of use and the detergent container can be made compact. In such a case, from the viewpoint of containing a surfactant in a high concentration, the component (A-1) includes, as a component, a compound obtained by adding ethylene oxide and propylene oxide to a primary or secondary alcohol, or a secondary alcohol.
  • Gelation region even at high concentrations such as compounds in which ethylene oxide is added to (secondary alcohol ethoxylates, Softanol series made by Nippon Shokubai Co., Ltd.) and compounds in which ethylene oxide is added to fatty acid methyl (MEE) Is preferably used.
  • a compound in which ethylene oxide and propylene oxide are added to a primary or secondary alcohol from the viewpoint of gelation at the time of dilution and the usability of the composition
  • the ratio is preferably 3/7 to 10/0, more preferably 5/5 to 10/0, and particularly preferably 7/3 to 10/0. is there.
  • the content of component (A-1) is 60% by mass or more, preferably 90% by mass or more, in 100% by mass of component (A). If the content of the component (A-1) is 60% by mass or more, the formation of a complex of the component (B) and the component (C) described later is not hindered. Good storage stability can be maintained.
  • Component (A-2) is an anionic surfactant.
  • the component (A-2) is not particularly limited, and a known anionic surfactant can be used and can be easily obtained on the market.
  • Examples of the component (A-2) include linear alkylbenzene sulfonic acid or a salt thereof; ⁇ -olefin sulfonate; linear or branched alkyl sulfate ester salt; alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt; And alkane sulfonate having a group; ⁇ -sulfo fatty acid ester salt and the like.
  • Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.
  • the component (A-2) the following are specifically preferable.
  • the linear alkylbenzene sulfonic acid or a salt thereof one having 8 to 16 carbon atoms in the linear alkyl group is preferable, and one having 10 to 14 carbon atoms is particularly preferable.
  • the ⁇ -olefin sulfonate those having 10 to 20 carbon atoms are preferable.
  • the alkyl sulfate ester salt preferably has 10 to 20 carbon atoms.
  • the alkyl ether sulfate ester salt or alkenyl ether sulfate ester salt has a linear or branched alkyl group or alkenyl group having 10 to 20 carbon atoms and an average of 1 to 10 moles of ethylene oxide added (that is, Polyoxyethylene alkyl ether sulfate ester salt or polyoxyethylene alkenyl ether sulfate ester salt) is preferred.
  • a secondary alkanesulfonate having an alkyl group having 10 to 20 carbon atoms, preferably 14 to 17 carbon atoms, is particularly preferable.
  • the ⁇ -sulfo fatty acid ester salt preferably has 10 to 20 carbon atoms.
  • linear alkylbenzene sulfonic acid or a salt thereof alkane sulfonate, polyoxyethylene alkyl ether sulfate, and ⁇ -olefin sulfonate are particularly preferable.
  • anionic surfactants include, for example, higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, carboxylic acid types such as acylamino carboxylates, Examples thereof include phosphoric acid ester type anionic surfactants such as alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phosphoric acid ester salts, polyoxyalkylene alkyl phenyl phosphoric acid ester salts and glycerin fatty acid ester monophosphoric acid ester salts.
  • the component (A-2) a single type of anionic surfactant may be used alone, or a plurality of types of anionic surfactants may be used in combination.
  • the content of the component (A-2) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, and particularly preferably 0 to 10% by mass in 100% by mass of the component (A).
  • the component (A-3) is a cationic surfactant.
  • Examples of the component (A-3) include alkyl trimethylammonium salts, dialkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylpyridinium salt cationic surfactants.
  • a single type of cationic surfactant may be used alone, or a plurality of types of cationic surfactants may be used in combination.
  • the content of the component (A-3) is preferably 0 to 20% by mass and more preferably 0 to 10% by mass in 100% by mass of the component (A).
  • Component (A-4) is an amphoteric surfactant.
  • Examples of the component (A-4) include alkyl betaine type, alkyl amide betaine type, imidazoline type, alkyl amino sulfone type, alkyl amino carboxylic acid type, alkyl amide carboxylic acid type, amide amino acid type, and phosphoric acid type amphoteric surfactant. Etc.
  • the component (A-4) a single type of amphoteric surfactant may be used alone, or a plurality of types of amphoteric surfactants may be used in combination.
  • the content of the component (A-4) is preferably 0 to 20% by mass and more preferably 0 to 10% by mass in 100% by mass of the component (A).
  • the component (B) is a homopolyamino acid and / or a salt thereof, containing a surfactant at a high concentration, or without reducing the enzyme activity even if the liquid detergent composition is stored for a long period of time. Used as a stabilizer for maintaining good storage stability of the enzyme.
  • a homopolyamino acid is a polymer composed of a single amino acid. Examples of homopolyamino acid salts include sodium salts, potassium salts, calcium salts, monoethanolamine salts, diethanolamine salts, and triethanolamine salts.
  • Typical examples of the homopolyamino acid include polylysine composed of lysine, polyglutamic acid composed of glutamic acid, polyaspartic acid composed of aspartic acid, and the like.
  • polyglutamic acid and / or polyaspartic acid is preferable, and polyglutamic acid ( ⁇ -polyglutamic acid) formed by condensing a part or all of the carboxyl group at the ⁇ position and / or the carboxyl at the ⁇ position
  • polyaspartic acid ( ⁇ -polyaspartic acid) formed by condensation of a part or all of the groups and ⁇ -polyglutamic acid and / or ⁇ -polyaspartic acid represented by the following general formula (II) Is particularly preferable, and ⁇ -polyglutamic acid represented by the following general formula (II) is most preferable.
  • R 3 is an alkylene group having 1 to 2 carbon atoms.
  • the formula (II) represents ⁇ -polyglutamic acid
  • R 3 is an alkylene group having 1 carbon atom
  • the formula (II) represents ⁇ -polyaspartic acid.
  • n is an integer of 4 to 200000. If n is 4 or more, the stability of the enzyme in the detergent composition tends to be improved. On the other hand, if n is 200,000 or less, component (B) or a premixed product containing component (B), which will be described later in detail, tends to suppress the occurrence of turbidity when blended with the remaining components.
  • ⁇ -polyglutamic acid represented by the formula (II) and / or a salt thereof is most preferable among the above-mentioned components.
  • the reason is estimated as shown below.
  • ⁇ -polyglutamic acid and its salts are not limited to the fact that the amide bond at the ⁇ -position can be stably present with almost no hydrolysis action on the enzyme (C), particularly protease, as the component (C). And by adjusting the content, it is difficult for the (A) component to inhibit the formation of the complex of the (B) component and the (C) component.
  • a complex of the component (B) and the component (C) is more easily formed, and the surfactant is added at a high concentration. Even when it is contained or the liquid detergent composition is stored for a long period of time, the storage stability of the enzyme can be maintained well without reducing the enzyme activity.
  • ⁇ -polyglutamic acid and a salt thereof may partially have an amide bond at the ⁇ -position as long as the amide bond at the ⁇ -position is the main skeleton.
  • Cross-linking may be performed between molecules, and a part or all of the side chain carboxylic acid may be a salt or an ester.
  • the glutamic acid constituting the polyglutamic acid may be D-type or L-type, but a higher ratio of L-type is preferred from the viewpoint of enhancing the storage stability of the enzyme.
  • a higher ratio of L-type is preferred from the viewpoint of enhancing the storage stability of the enzyme.
  • the ratio of D type to L type is preferably 3/7 to 9/1, and 4/6 to 8 / 2 is more preferable, and 5/5 to 8/2 is particularly preferable.
  • homopolyamino acids and salts thereof tend to improve the storage stability of the enzyme as the mass average molecular weight increases.
  • a crosslinked homopolyamino acid obtained by irradiating ⁇ rays and a salt thereof can provide a remarkable effect even in a small amount.
  • a high molecular weight homopolyamino acid and / or a salt thereof is used as the component (B)
  • precipitation of the enzyme is less likely to occur, but the liquid detergent composition becomes cloudy compared to the case of using a low molecular weight one, There is a tendency that components other than enzymes are easily separated.
  • Homopolyamino acids and salts thereof are preferably those having a mass average molecular weight of 5 to 20 million, more preferably 15,000 to 10 million, and still more preferably 100,000 to 6 million.
  • the mass average molecular weight of homopolyamino acids and salts thereof can be measured by gel permeation chromatography (GPC).
  • ⁇ -polyglutamate sodium available from Nippon Polyglu trade name ⁇ -PGA series (D / L ratio is 8/2, low molecular weight; mass average molecular weight 200,000 to 400,000, high Molecular weight: weight average molecular weight 800,000 to 1,000,000, crosslinked type; mass average molecular weight 10 million or more), ⁇ -polyglutamic acid available from Yakult Pharmaceutical Co., Ltd .: Trade name PGA series (D / L ratio is 1/1, A type; mass average molecular weight 1.5 million, B type; mass average molecular weight 500,000 to 800,000, C type; mass average molecular weight 200,000 to 400,000, D type; mass average molecular weight 10,000 to 100,000), Wako Pure Chemical Industries Poly- ⁇ -glutamic acid and its sodium salt available from the company (D / L ratio is 7/3, weight average molecular weight 200,000 to 500,000, 1.5 million to 2.5 million, 4 million to 600 ⁇ -poly-D-glutamic acid and its
  • content of a component is not specifically limited, 0.01 mass% or more is preferable in 100 mass% of liquid cleaning composition at the point which acquires the effect of the storage stability of an enzyme, 2.00 mass% or less is preferable at the point which suppresses turbidity and precipitation of each component (point of aesthetics). More preferably, it is 0.1 to 1.0% by mass, particularly preferably 0.2 to 1.0% by mass, and most preferably 0.4 to 0.8% by mass.
  • Component (C) is an enzyme.
  • enzyme refers to an enzyme preparation.
  • the component (C) is not particularly limited as long as it is a general enzyme used in a cleaning agent. However, when the liquid cleaning composition of the present invention is used as a cleaning agent for clothing, protease, amylase, lipase, cellulase, Mannanase etc. are mentioned. Specific examples include the following.
  • protease preparations available from Novozymes Tradenames Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L Type EX 2.5, Ultra Ul 16L, Erase Ultra 16L, Esperase 8L , Liquidase Ultra 2.5L, Liquidase Ultra 2.5XL, Coronase 48L, Protease preparations available from Genencor Corporation: Tradenames Purefect L, Perfect Prime, Properase L and the like.
  • amylase preparations available from Novozymes trade name Termamyl 300L, Termamyl Ultra 300L, Duramyl 300L, Stainzyme 12L, Stainzyme Plus 12L, amylase preparation available from Genencor, Inc.
  • Examples include amylase preparations available from Enzyme: trade name Pullulanase Amano, and amylase preparations available from Seikagaku Corporation: trade name DB-250.
  • lipase include lipase preparations available from Novozymes: trade names Lipex 100L, Lipolase 100L, and the like.
  • cellulases examples include cellulase preparations available from Novozymes: trade names Endolase 5000L, Celluzyme 0.4L, Carzyme 4500L, cellulase preparations available from Genencor, Inc .: trade name Puradux EG L, and the like.
  • mannanase examples include mannanase preparations available from Novozymes: trade name Mannaway 4L.
  • Protease is an enzyme whose enzyme activity is likely to decrease due to self-digestion, but since the liquid detergent composition of the present invention contains the component (B) described above, it forms a complex with the component (B). By doing so, a decrease in enzyme activity can be suppressed, and the enzyme function of the protease can be fully exhibited.
  • proteases those shown below are particularly easy to self-digest and have a remarkable decrease in enzyme activity. However, in the present invention, sufficient effects can be obtained even if these proteases are used.
  • Specific examples of proteases in which the effects of the present invention are particularly prominent include trade names Savinase 16L, Savinase Ultra 16L, Savinase Ultra 16XL, Everase 16L, Everase Ultra 16L, Liquidase 2.5L, Liquidase UltraL 5XL and Coronase 48L are mentioned, and Everase 16L, Savinase 16L and Coronase 48L are particularly prominent.
  • the content of the component (C) is not particularly limited from the viewpoint of storage stability, but is preferably 0.01% by mass or more in 100% by mass of the liquid detergent composition in terms of improving the cleaning performance. Considering enzyme precipitation and performance saturation in a small composition, 2.00% by mass or less is preferable. More preferred is 0.01 to 1.00% by mass, and particularly preferred is 0.03 to 0.80% by mass.
  • the mass ratio of the component (B) and the component (C) is not particularly limited, but considering the production cost and the storage stability of the enzyme, the component (B) / (C) component is 1 / 10.0 to 1/1 /. It is preferably 0.5, more preferably 1/4 to 1 / 0.5, and particularly preferably 1 / 1.0 to 1 / 0.5. If the mass ratio of (B) component and (C) component is in the said range, the effect of the storage stability of an enzyme will fully be acquired.
  • [(D) component] (D) A component is water.
  • the component (D) include purified water, distilled water, ion exchange water, pure water, and ultrapure water.
  • the content of the component (D) is preferably 15 to 75% by mass, more preferably 25 to 65% by mass, and particularly preferably 20 to 40% by mass in 100% by mass of the liquid detergent composition. If content of (D) component is 15 mass% or more, (C) component will become more difficult to precipitate. On the other hand, when the content of the component (D) is 75% by mass or less, the component (C) can be sufficiently stabilized by the component (B) while maintaining the cleaning performance.
  • the content of the component (D) is in the range of 20 to 40% by mass, the component (A) is contained at a high concentration, so that the liquid detergent composition of the present invention is a compact type. While being able to use suitably as a cleaning agent, the turbidity and isolation
  • content of (D) component means the total water content in a liquid detergent composition, the quantity mix
  • the liquid detergent composition of the present invention may contain, as necessary, usual optional components used for the liquid detergent within a range not impairing the effects of the present invention. Can do. Examples of the optional component include those shown below.
  • Water-miscible organic solvent examples include alcohols such as ethanol, 1-propanol, 2-propanol, and 1-butanol; glycols such as propylene glycol, butylene glycol, and hexylene glycol; diethylene glycol, triethylene glycol, and tetraethylene glycol.
  • the content of the water-miscible organic solvent is preferably 0.1 to 15% by mass in 100% by mass of the liquid detergent composition.
  • thinning agent and the solubilizer include aromatic sulfonic acids or salts thereof. Specific examples include toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, substituted or unsubstituted naphthalene sulfonic acid, toluene sulfonate, xylene sulfonate, cumene sulfonate, substituted or unsubstituted naphthalene sulfonate. . Examples of the salt include sodium salt, potassium salt, calcium salt, magnesium salt, ammonium salt, alkanolamine salt and the like.
  • the content of the thinning agent and the solubilizer is preferably 0.01 to 15% by mass in 100% by mass of the liquid detergent composition. If it is in the said range, in the liquid surface of a liquid cleaning composition, the effect which suppresses the production
  • alkaline agent examples include monoethanolamine, diethanolamine, triethanolamine and the like. These alkali agents can be used alone or in combination.
  • the content of the alkaline agent is preferably 0.5 to 5% by mass in 100% by mass of the liquid detergent composition.
  • the metal ion scavenger captures metals in tap water and can suppress a decrease in the activity of the anionic surfactant due to complex formation with these metals. In addition, it is generally used in liquid detergent compositions for the purpose of improving the stability of the dye contained in the liquid detergent composition and improving the pH buffering capacity. However, it is known that the activity tends to decrease with respect to the component (C) involving metal.
  • the metal ion scavenger include malonic acid, succinic acid, malic acid, diglycolic acid, tartaric acid, citric acid and the like.
  • the content of the metal ion scavenger is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and still more preferably 0.1 to 5% in 100% by mass of the liquid detergent composition. % By mass.
  • the antioxidant is not particularly limited, but a phenolic antioxidant is preferred because of its good detergency and liquid stability, and monophenolic antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole, Bisphenol antioxidants such as 2,2'-methylenebis (4-methyl-6-t-butylphenol) and polymer phenolic antioxidants such as dl- ⁇ -tocopherol are more preferred, and monophenol antioxidants More preferred are polymer type antioxidants. Of the monophenol antioxidants, dibutylhydroxytoluene is particularly preferred. Among the polymer type phenol antioxidants, dl- ⁇ -tocopherol is particularly preferable. An antioxidant can be used 1 type or in mixture of 2 or more types. The content of the antioxidant is preferably 0.01 to 2% by mass in 100% by mass of the liquid detergent composition.
  • Preservative> examples include Rohm and Haas: trade name Kaison CG.
  • the content of the preservative is preferably 0.001 to 1% by mass in 100% by mass of the liquid detergent composition.
  • the liquid detergent composition of the present invention comprises benzoic acid or a salt thereof (also effective as a preservative) for the purpose of improving the storage stability, boric acid, borax, formic acid or the like for the purpose of stabilizing the enzyme.
  • benzoic acid or a salt thereof also effective as a preservative
  • a fluorescent whitening agent such as a distyrylbiphenyl type, polyvinylpyrrolidone, etc.
  • polyacrylic acid acrylic acid-maleic acid It may contain 0 to 2% by mass of a re-contamination inhibitor such as a coalescence or carboxymethyl cellulose, a pearl agent, a soil release agent and the like.
  • the liquid detergent composition of the present invention may contain a flavoring agent, a coloring agent, an emulsifying agent, an extract such as a natural product, and the like for the purpose of improving the added value of goods.
  • a flavoring agent perfume compositions A, B, C and D described in Tables 11 to 18 of JP-A-2002-146399 can be used.
  • the content of the flavoring agent is preferably 0.1 to 1% by mass in 100% by mass of the liquid detergent composition.
  • the content of the colorant is preferably about 0.00005 to 0.005% by mass in 100% by mass of the liquid detergent composition.
  • the emulsion examples include polystyrene emulsion and polyvinyl acetate emulsion, and usually an emulsion having a solid content of 30 to 50% by mass is preferably used. Specific examples include polystyrene emulsion (manufactured by Syden Chemical Co., Ltd .: trade name: Cybinol RPX-196 PE-3, solid content: 40% by mass). The content of the emulsion is preferably 0.01 to 0.5% by mass in 100% by mass of the liquid detergent composition.
  • extracts such as natural products include Inuenju, Uwaurushi, Echinacea, Koganebana, Yellowfin, Ouren, Allspice, Oregano, Enju, Chamomile, Honeysuckle, Clara, Keigai, Kay, Bay bay, Honoki, Burdock, Comfrey, Jasho, Waremokou, Peonies, Ginger, Solidago, Elderberry, Sage, Mistletoe, Prunus, Thyme, Prunus, Clove, Satsuma Mandarin, Tea Tree, Barberry, Dokudami, Nanten, Nyuko, Yorigusa, Shirogaya, Bow Fu, Dutch Hyu, Mountain, Gray , Murasakitagayasan, yamahakka, cypress, yamajiso, eucalyptus, lavender, rose, rosemary, balun, cedar, gilead balsamno , Ringworm, kochia, Polygonum aviculare, Jingyou,
  • the liquid detergent composition of the present invention preferably has a pH of 4 to 9 at 25 ° C., more preferably 6 to 9. If pH is in the said range, the storage stability of a liquid detergent composition can be maintained favorable.
  • the pH of the liquid detergent composition can be adjusted with a pH adjuster.
  • the pH adjuster is optional as long as the effects of the present invention are not impaired, but hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, alkanolamine and the like are preferable from the viewpoint of stability.
  • the pH of the liquid detergent composition (temperature adjusted to 25 ° C.) indicates a value measured by a pH meter or the like.
  • the liquid detergent composition of the present invention can be obtained by mixing the above-described components (A) to (D) and optional components as necessary, but the components (B), (C), ( It is preferable to manufacture by the method of mixing the remaining component, after preparing the premix by mixing (premixing) part or all of D) component.
  • the premixing procedure is preferably a procedure in which the component (B) is added to the component (D) and then the component (C) is added thereto.
  • the component (B) can be mixed with the component (C) in a state where the component (B) is completely hydrated (dissolved in water). Even in such a difficult-to-handle form, it can be uniformly mixed with the component (C).
  • the amount of the component (D) in the premixing is preferably 8 to 18 times by mass ratio with respect to the component (B). If it is 8 times or more, the component (B) can be sufficiently dissolved.
  • the liquid detergent composition thus obtained can be suitably used as a detergent for clothing.
  • a normal method of use can be adopted.
  • the liquid detergent composition of the present invention (this composition) is poured into water together with the laundry at the time of washing, mud dirt And a method of directly applying the present composition to sebum stains, a method of previously dissolving the present composition in water and immersing clothes.
  • the present composition is applied to the laundry and then allowed to stand as appropriate, followed by normal washing using a normal laundry solution. In that case, the usage-amount of this composition can be made smaller than the usage-amount of the conventional liquid cleaning composition.
  • the liquid detergent composition of the present invention described above contains the specific component (A), component (B), component (C), and component (D), the surfactant is contained in a high concentration. Even in this case, the storage stability of the enzyme can be maintained well without reducing the enzyme activity. Therefore, the liquid detergent composition of the present invention can be suitably used as a compact detergent. Moreover, even if the liquid detergent composition of this invention preserve
  • A-1-1 C 11 H 23 CO (OCH 2 CH 2 ) 15 OCH 3 and C 13 H 27 CO (OCH 2 CH 2 ) 15 OCH 3 in a mass ratio of 8/2, narrow ratio 33% synthetic.
  • A-1-1 was produced according to Production Example 1 in Examples described in JP-A No. 2000-144179. That is, alumina hydroxide / magnesium hydroxide having a chemical composition of 2.5 MgO.Al 2 O 3 .nH 2 O (trade name: Kyoward 300, manufactured by Kyowa Chemical Industry Co., Ltd.) at 600 ° C. for 1 hour in a nitrogen atmosphere.
  • a calcined alumina hydroxide / magnesium (unmodified) catalyst (2.2 g) obtained by calcining, 2.9 mL of 0.5 N potassium hydroxide ethanol solution, 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, was charged into a 4 liter autoclave and the catalyst was reformed in the autoclave. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, and while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa, 1052 g of ethylene oxide was introduced and reacted while stirring.
  • reaction solution was cooled to 80 ° C., 159 g of water and 5 g of activated clay and diatomaceous earth as filter aids were added, respectively, and the catalyst was filtered off to obtain A-1-1.
  • the narrow ratio of A-1-1 was 33% by controlling the amount of alkali added to the catalyst.
  • the narrow rate of A-1-1 was obtained as follows.
  • n max represents the number of moles of alkylene oxide added in the alkylene oxide adduct most present in the entire alkylene oxide adduct.
  • i represents the number of added moles of alkylene oxide.
  • Yi represents the proportion (%) of an alkylene oxide adduct in which the number of moles of alkylene oxide present in the entire alkylene oxide adduct is i.
  • A-1-2 was produced as follows. That is, 224.4 g of natural alcohol CO-1270 manufactured by P & G and 2.0 g of 30% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C. While stirring the alcohol, 760.4 g of ethylene oxide (gaseous) was gradually added to the alcohol solution while adjusting the addition rate so that the reaction temperature did not exceed 180 ° C. using a blowing tube.
  • ethylene oxide After completion of the addition of ethylene oxide, aging was performed at a temperature of 180 ° C. and a pressure of 0.3 MPa or less for 30 minutes, and then unreacted ethylene oxide was distilled off at a temperature of 180 ° C. and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling the temperature to 100 ° C. or lower, 70% p-toluenesulfonic acid was added to neutralize so that the pH of the 1% aqueous solution of the reaction was about 7, to obtain A-1-2. .
  • (A-1-4) uses 280 g of lauric acid methyl ester and 70 g of myristic acid methyl ester, introduces 1052 g of ethylene oxide and 93 g of propylene oxide, and adjusts the amount of alkali added to the catalyst so that the narrow ratio is 37% by mass.
  • (A-1-4) was produced in the same manner as in the synthesis method (A-1-1) except that the amount was adjusted.
  • 224.4 g of “CO-1270” manufactured by P & G and 2.0 g of 30 mass% NaOH aqueous solution were collected in a pressure-resistant reaction vessel, and the inside of the vessel was purged with nitrogen. Next, after dehydrating for 30 minutes at a temperature of 100 ° C. and a pressure of 2.0 kPa or less, the temperature was raised to 160 ° C.
  • A-2-1 linear alkylbenzene sulfonic acid (LAS) (manufactured by Lion Corporation: trade name Rypon LH-200, carbon number 10-14, average molecular weight 322).
  • B Sodium ⁇ -polyglutamate (low molecular weight) (trade name ⁇ -PGA (Low molecular weight) manufactured by Polyglu Japan).
  • B-2 sodium ⁇ -polyglutamate (high molecular weight) (manufactured by Nippon Polyglu, trade name: ⁇ -PGA (High molecular weight)).
  • B-3 sodium ⁇ -polyglutamate (cross-linked) (manufactured by Nippon Polyglu Co., Ltd .: trade name ⁇ -PGA (close link)).
  • B-4 ⁇ -polyglutamic acid (manufactured by Yakult Pharmaceutical Co., Ltd .: trade name PGA C type).
  • B-5 Sodium polyaspartate (Lanxess: trade name Baypure) DS100).
  • B-6 ⁇ -poly-D-glutamic acid (manufactured by Sigma: trade name Poly-D-glutamic acid (Mol wt 15000-50000)).
  • B-7 ⁇ -poly-L-glutamic acid (manufactured by Sigma: trade name Poly-L-glutamic acid, (Mol wt 15000 to 50000)).
  • C As the component (C), the following compounds were used.
  • C-1 Everase 16L (manufactured by Novozymes: trade name Everlase 16L Type EX).
  • C-2 Sabinase 16L (manufactured by Novozymes: trade name Savinase 16L).
  • C-3 Coronase 48L (manufactured by Novozymes: trade name Coronase 48L).
  • the following reagents were used as optional components.
  • -Ethanol Ethanol (99.5) (manufactured by Kanto Chemical Co., Inc.).
  • Citric acid anhydrous citric acid (manufactured by Iwata Chemical).
  • MEA monoethanolamine (manufactured by Kanto Chemical Co., Inc.)
  • NaOH Sodium hydroxide (manufactured by Kanto Chemical Co., Inc.)
  • HCl hydrochloric acid (manufactured by Kanto Chemical Co., Inc.)
  • 1 g of the liquid detergent composition after storage for a predetermined period was diluted 25 times with calcium chloride (calcium chloride (special grade), manufactured by Kanto Chemical Co., Inc.) 3 ° DH hard water to obtain a diluted solution.
  • 5 g of the protease substrate was added to 1 g of the diluted solution, and after 10 seconds of vortexing, the mixture was allowed to stand at 37 ° C. for 30 minutes to proceed the enzyme reaction. Thereafter, 5 g of TCA (trichloroacetic acid (special grade), manufactured by Kanto Chemical Co.) 0.44M aqueous solution was added as an enzyme reaction terminator, vortexed for 10 seconds, allowed to stand at 20 ° C.
  • TCA trichloroacetic acid
  • the concentration (absorbance A) of the enzyme-decomposed substrate present in the liquid after removal by the filter was quantified using a UV-visible spectrophotometer (manufactured by Shimadzu Corporation: product name UV-160) at a measurement wavelength of 275 nm.
  • the absorbance B at 275 nm of the sample solution containing no protease substrate was measured.
  • the same operation as described above was performed to react with the protease substrate, the precipitate was removed, and the absorbance C at 275 nm of the filtrate was measured. This was measured and used as the initial value of the enzyme activity.
  • the enzyme activity (%) was determined from the absorbances A to C by the following formula.
  • the absorbance values A to C were used by subtracting the 600 nm absorbance value measured at the same time in order to exclude scattered light such as bubbles from the absorbance.
  • Enzyme activity (%) (absorbance A ⁇ absorbance B) / absorbance C ⁇ 100
  • the washing rate was calculated for each of the five artificial soil cloths, and the average value was calculated as the washing rate of the liquid detergent composition. And detergency was evaluated based on the following reference
  • the cleaning rate was similarly calculated for the liquid detergent composition after being stored in a constant temperature bath at 35 ° C. for 2 weeks, and the cleaning power was evaluated.
  • component (C) An amount (mass%) of the component (C) was added and further premixed by stirring to obtain a premixed product.
  • component (D) is 20.0%
  • ethanol is 7.0%
  • citric acid is 0.3%
  • MEA is 1.0% as optional components.
  • component (A) component in a blending amount (mass%) were added and stirred to dissolve these components.
  • pH meter manufactured by Toa DKK Corporation, product name HM-30G
  • the pH of the solution was adjusted to 7 at 25 ° C. using sodium hydroxide and hydrochloric acid as pH adjusting agents.
  • a pre-mixture was added to this, and the liquid detergent composition was obtained by adding (D) component which adjusted the compounding quantity so that the total amount of the liquid detergent composition which is a final product might be 100%. .
  • the obtained liquid detergent composition was evaluated for enzyme activity, storage stability, and detergency. The results are shown in Tables 1 to 3.
  • Example 2 and Comparative Examples 1 and 3 ⁇ Preparation of liquid detergent composition>
  • component (D) is 20.0%
  • ethanol is 7.0%
  • citric acid is 0.3%
  • MEA is 1.0% as optional components.
  • Components (A) and (B) in amounts (mass%) were added and stirred to dissolve these components.
  • a pH meter product name: HM-30G, manufactured by Toa DKK Co., Ltd.
  • the pH of the solution was adjusted to 7 at 25 ° C. using sodium hydroxide and hydrochloric acid as pH adjusting agents.
  • the obtained liquid detergent composition was evaluated for enzyme activity, storage stability, and detergency. The results are shown in Tables 1 to 3.
  • nonionic content refers to the content (mass%) of the nonionic surfactant in 100 mass% of component (A).
  • the liquid detergent composition obtained in each example was able to suppress a decrease in enzyme activity even when stored for a long period of time. In addition, the storage stability of the enzyme could be maintained well and excellent detergency could be demonstrated.
  • the liquid detergent composition obtained in Comparative Example 1 containing no component (B) was liable to have reduced enzyme activity. Comparing Comparative Examples 2 and 3 in which the content of the nonionic surfactant in the component (A) is 24%, Comparative Example 2 in which the component (B), the component (C), and the component (D) are premixed and blended.
  • liquid detergent composition that can satisfactorily maintain the storage stability of an enzyme without reducing the enzyme activity and a method for producing the same. it can.

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Abstract

L'invention concerne : une composition détergente liquide qui ne subit pas la détérioration de l'activité d'une enzyme qu'elle contient et peut maintenir la stabilité au stockage de l'enzyme à un bon niveau même lorsqu'elle contient un tensioactif en une concentration élevée ; et un procédé de fabrication de la composition détergente liquide. La composition détergente liquide est caractérisée en ce qu'elle comprend les composants (A) à (D) suivants : (A) un tensioactif (un tensioactif non ionique représentant 60 % en masse ou plus du composant (A)) ; (B) un homopolyaminoacide et/ou un de ses sels ; (C) une enzyme ; et (D) de l'eau.
PCT/JP2010/068688 2009-11-02 2010-10-22 Composition détergente liquide et son procédé de fabrication WO2011052501A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN103351960A (zh) * 2012-04-06 2013-10-16 启东复联电子有限公司 一种洗涤剂
JP2015224327A (ja) * 2014-05-29 2015-12-14 花王株式会社 繊維製品用洗浄剤組成物
JP2016006172A (ja) * 2014-05-27 2016-01-14 ライオン株式会社 液体洗浄剤
JP2018511664A (ja) * 2015-02-12 2018-04-26 ホワイトリー コーポレイション ピーティーワイ リミテッド 医療器具用洗浄剤

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6607715B2 (ja) * 2015-07-03 2019-11-20 ライオン株式会社 液体洗浄剤
CN108372163B (zh) * 2018-02-24 2021-02-09 广州清新环保科技有限公司 中央空调清洗机器人

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JPH08196274A (ja) * 1995-01-24 1996-08-06 Japan Synthetic Rubber Co Ltd 固定化酵素
JPH09235588A (ja) * 1996-02-28 1997-09-09 Lion Corp 液体洗浄組成物
JPH09235589A (ja) * 1996-02-28 1997-09-09 Lion Corp 液体洗浄組成物
JP2007097586A (ja) * 2005-09-12 2007-04-19 Kochi Univ 酵素活性の安定化方法および酵素組成物
JP2009007451A (ja) * 2007-06-27 2009-01-15 Lion Corp 液体洗浄剤組成物

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JPH06299192A (ja) * 1993-02-24 1994-10-25 Enichem Spa 繊維材料洗浄組成物
JPH08196274A (ja) * 1995-01-24 1996-08-06 Japan Synthetic Rubber Co Ltd 固定化酵素
JPH09235588A (ja) * 1996-02-28 1997-09-09 Lion Corp 液体洗浄組成物
JPH09235589A (ja) * 1996-02-28 1997-09-09 Lion Corp 液体洗浄組成物
JP2007097586A (ja) * 2005-09-12 2007-04-19 Kochi Univ 酵素活性の安定化方法および酵素組成物
JP2009007451A (ja) * 2007-06-27 2009-01-15 Lion Corp 液体洗浄剤組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103351960A (zh) * 2012-04-06 2013-10-16 启东复联电子有限公司 一种洗涤剂
JP2016006172A (ja) * 2014-05-27 2016-01-14 ライオン株式会社 液体洗浄剤
JP2015224327A (ja) * 2014-05-29 2015-12-14 花王株式会社 繊維製品用洗浄剤組成物
JP2018511664A (ja) * 2015-02-12 2018-04-26 ホワイトリー コーポレイション ピーティーワイ リミテッド 医療器具用洗浄剤
US10017719B2 (en) 2015-02-12 2018-07-10 Whiteley Corporation Pty. Ltd. Detergent for medical instrumentation

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