WO2006131503A2 - Detergents with enzymatic builder and bleach systems - Google Patents

Detergents with enzymatic builder and bleach systems Download PDF

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Publication number
WO2006131503A2
WO2006131503A2 PCT/EP2006/062878 EP2006062878W WO2006131503A2 WO 2006131503 A2 WO2006131503 A2 WO 2006131503A2 EP 2006062878 W EP2006062878 W EP 2006062878W WO 2006131503 A2 WO2006131503 A2 WO 2006131503A2
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WO
WIPO (PCT)
Prior art keywords
detergent
builder
lactose
bleach
carbohydrate oxidase
Prior art date
Application number
PCT/EP2006/062878
Other languages
French (fr)
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WO2006131503A3 (en
Inventor
Carsten Lauridsen
Jesper Duus Nielsen
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Novozymes A/S
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Publication of WO2006131503A2 publication Critical patent/WO2006131503A2/en
Publication of WO2006131503A3 publication Critical patent/WO2006131503A3/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase

Definitions

  • the present invention relates to enzymatic methods for generating builder and bleach systems in a detergent.
  • Lactobionic acid is an alternative biodegradable builder agent.
  • lactobionic acid is formed in-situ along with an activated bleaching system, thus avoiding the need for separate hydrogen peroxide generating agents in detergent formulations.
  • the present invention provides an environmentally friendly method for in-situ generation of builder and bleach systems in a detergent.
  • the present invention provides a detergent composition
  • a detergent composition comprising a surfactant, a bleach activator, lactose and a carbohydrate oxidase, which is capable upon solution of forming simultaneously a builder and an activated bleach system.
  • the invention provides an enzymatic method for simultaneous formation of a builder and a bleach system in a detergent solution, which includes combining a bleach activator, lactose and a carbohydrate oxidase in an aqueous solution comprising a surfactant.
  • a carbohydrate oxidase enzyme is used to convert lactose to lactobionic acid in-situ in a detergent solution.
  • the reaction scheme may be described as:
  • the CAS reg. no. for lactobionic acid is 96-82-2.
  • a number of suitable carbohydrate oxidases, capable of converting lactose to lactobionic acid, are known and available to the skilled person. It may for instance be a hexose oxidase.
  • the carbohydrate oxidase is a microbial carbohydrate oxidase.
  • a suitable hexose oxidase (EC 1.1.3.5) is described in
  • WO 9640935 (BIOTEKNOLOGISK INS ⁇ TUT). 1996-12-19. . This document describes a suitable hexose oxidase from marine algal species more particular wherein the marine algal species is one selected from the group consisting of Chondrus crispus, Iridophycus flaccidum and Euthora cristate
  • carbohydrate oxidase may be derived, e.g., from a mitosporic
  • the carbohydrate oxidase is obtained from the source disclosed by
  • the carbohydrate oxidase is a carbohydrate oxidase obtained from a fungus belonging to the genus Microdochium, more preferably wherein the fungus is Microdochium nivale and even more preferably wherein the fungus is Microdochium nivale CBS 100236.
  • a preferred oxidase is described in details in WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
  • the amount of oxidase to be used will generally depend on the specific needs.
  • an amount of oxidase that is from 0.1 to 1000 OXU per liter of detergent solution, more preferably from 1 to 500 OXU per liter of detergent solution, and even more preferably from 5 to 100 OXU per liter of detergent solution.
  • Oxidase Unit is herein basically defined as the amount of enzyme that oxidizes one ⁇ mol lactose per minute under the incubation conditions of the method one specifically uses.
  • lactose is included in the detergent solution at a concentration of 0.05 g/L to 5.0 g/L, preferably 0.05 g/L to 4.0 g/L, more preferably 0.05 g/L to 3.0 g/L, even more preferably 0.05 g/L to 2.0 g/L, and most preferably 0.05 g/L to 1.0 g/L.
  • Hydrogen peroxide or a source of hydrogen peroxide (such as perborates or per- carbonates), may be used to oxidize and decolorize stains originating from natural substances (e.g. protein, tea, red wine, and fruit juice).
  • Peroxygen type bleaching agents are especially efficient at high temperatures, and an activator may be added to enhance the bleaching effect at lower temperatures.
  • hydrogen peroxide formed by reacting lactose and a carbohydrate oxidase is combined with a bleaching activator to make up an activated bleaching system.
  • bleach activators suitable in the present invention include, but are not limited to, tetra-acetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in
  • bleach activators 6-octanamido-caproyl) oxybenzene-sulfonate, C9 (6-nonanamido caproyl) oxybenzenesulfonate and ClO (6-decanamido caproyl) oxy- benzenesulfonate or mixtures thereof.
  • acylated citrate esters such as disclosed in EP 624154 (PROCTER & GAMBLE). 1994-11-17.
  • the carbohydrate oxidase, lactose and bleach activator may be added to and thus become components of a detergent composition.
  • the detergent composition of the invention may for example be formulated as a hand or machine laundry detergent composition including a laundry additive composition suitable for pre-treatment of stained fabrics and a rinse added fabric softener composition, or be formulated as a detergent composition for use in general household hard surface cleaning operations, or be formulated for hand or machine dishwashing operations.
  • the invention provides a detergent additive comprising a carbohydrate oxidase, lactose, a bleach activator and a surfactant.
  • the detergent additive as well as the detergent composition may comprise one or more other enzymes such as a protease, a lipase, a cutinase, an amylase, a carbohydrase, a cellulase, a pectinase, a mannanase, an arabinase, a galactanase, a xylanase, an oxidase (such as a laccase), and/or a peroxidase (such as a haloperoxidase).
  • enzymes such as a protease, a lipase, a cutinase, an amylase, a carbohydrase, a cellulase, a pectinase, a mannanase,
  • the properties of the chosen enzyme(s) should be compatible with the selected detergent, (i.e. pH-optimum, compatibility with other enzymatic and non- enzymatic ingredients, etc.), and the enzyme(s) should be present in effective amounts.
  • proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included.
  • the protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease.
  • alkaline proteases are subtilisins, especially those derived from Bacillus, e.g., subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (described in WO 89/06279).
  • trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270 and WO 94/25583.
  • Suitable Upases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful Upases include Upases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseu- doalcaligenes (EP 218 272), P. cepacia (EP 331 376), P.
  • lipase variants such as those described in WO 92/05249, WO
  • Amylases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839.
  • amylases are the variants described in WO 94/02597, WO
  • Cellulases include those of bacterial or fungal origin.
  • Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757 and WO 89/09259. [0031] Especially suitable cellulases are the alkaline or neutral cellulases having colour care benefits.
  • cellulases examples include cellulases described in EP 0495 257, EP 0 531 372, WO 96/11262, WO 96/29397, WO 98/08940.
  • cellulase variants such as those described in WO 94/07998, EP 0 531 315, US 5,457,046, US 5,686,593, US 5,763,254, WO 95/24471, WO 98/12307 and PCT/DK98/00299.
  • Peroxidases/Oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
  • the detergent enzyme(s) may be included in a detergent composition by adding separate additives containing one or more enzymes, or by adding a combined additive comprising all of these enzymes.
  • a detergent additive of the invention i.e. a separate additive or a combined additive, can be formulated e.g. as a granulate, a liquid, a slurry, etc.
  • Preferred detergent additive formulations are granulates, in particular non- dusting granulates, liquids, in particular stabilized liquids, or slurries.
  • Non-dusting granulates may be produced, e.g., as disclosed in US 4,106,991 and 4,661,452 and may optionally be coated by methods known in the art.
  • waxy coating materials are poly(ethylene oxide) products (polyethyleneglycol, PEG) with mean molar weights of 1000 to 20000; ethoxylated nonylphenols having from 16 to 50 ethylene oxide units; ethoxylated fatty alcohols in which the alcohol contains from 12 to 20 carbon atoms and in which there are 15 to 80 ethylene oxide units; fatty alcohols; fatty acids; and mono- and di- and triglycerides of fatty acids.
  • Liquid enzyme preparations may, for instance, be stabilized by adding a polyol such as propylene glycol, a sugar or sugar alcohol, lactic acid or boric acid according to established methods.
  • Protected enzymes may be prepared according to the method disclosed in EP 238,216.
  • the detergent composition of the invention may be in any convenient form, e.g., a bar, a tablet, a powder, a granule, a paste or a liquid.
  • a liquid detergent may be aqueous, typically containing up to 70% water and 0-30% organic solvent, or nonaqueous.
  • the detergent composition comprises one or more surfactants, which may be non- ionic including semi-polar and/or anionic and/or cationic and/or zwitterionic.
  • the surfactants are typically present at a level of from 0.1% to 60% by weight.
  • the detergent When included therein the detergent will usually contain from about 1% to about 40% of an anionic surfactant such as linear alkylbenzenesulfonate, alpha- olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • an anionic surfactant such as linear alkylbenzenesulfonate, alpha- olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
  • the detergent When included therein the detergent will usually contain from about 0.2% to about 40% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid mo- noethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides").
  • a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid mo- noethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”).
  • glucamides N-acyl N-alkyl derivatives of glucosamine
  • the detergent may contain 0-50% of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
  • a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
  • the detergent may comprise one or more polymers.
  • examples are carboxymethyl- cellulose, poly(vinylpyrrolidone), poly (ethylene glycol), polyvinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as poly- acrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
  • the enzyme(s) of the detergent composition of the invention may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
  • a polyol such as propylene glycol or glycerol
  • a sugar or sugar alcohol lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid
  • the detergent may also contain other conventional detergent ingredients such as e.g. fabric conditioners including clays, foam boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, optical brighteners, hydrotropes, tarnish inhibitors, or perfumes.
  • fabric conditioners including clays, foam boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, optical brighteners, hydrotropes, tarnish inhibitors, or perfumes.
  • any enzyme, and the carbohydrate oxidase of the method and composition of invention may be added in an amount corresponding to 0.01-100 mg of enzyme protein per liter of wash liqour, preferably 0.05-10 mg of enzyme protein per liter of wash liqour, more preferably 0.1-5 mg of enzyme protein per liter of wash liqour, and most preferably 0.1-1 mg of enzyme protein per liter of wash liqour.
  • the pH of an aqueous solution of the detergent composition is in the range of from pH 6 to 11, preferably in the range of from pH 6.5 to 10.5, more preferably in the range of from pH 7 to 10.5, most preferably in the range of from pH 7 to 10.
  • the present invention provides an enzymatic method for simultaneous formation of a builder and a bleach system in a detergent solution, which includes combining a bleach activator, lactose and a carbohydrate oxidase in an aqueous solution comprising a surfactant.
  • formation of a builder and a bleach system is intended to mean that at least 2%, preferably at least 5%, more preferably at least 10%, even more preferably at least 20%, most preferably at least 50% of the lactose is converted to lactobionic acid, or a salt thereof, and hydrogen peroxide by the carbohydrate oxidase.
  • Lactobionic acid and salts thereof have calcium binding (builder) capabilities, as shown in
  • the formed lactobionic acid, or a salt thereof is used as a co- builder in conjunction with another builder, such as a zeolite or a phosphate.
  • the detergent solution does not contain any other hydrogen peroxide sources, such as perborates or percarbonates.
  • the surfactant of the method of the invention is described above in "detergent composition”.
  • the method of the invention is preferably carried out during a washing process, such as a laundry washing process or a dish washing process.
  • the method of the invention may be carried out at a temperature between 0 and 90 degrees Celsius, preferably between 5 and 80 degrees Celsius, more preferably between 10 and 70 degrees Celsius, and most preferably between 20 and 60 degrees
  • a model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate.
  • AEOS EO3 alkyl ethoxy sulfate
  • AEO 3EO alcohol ethoxylate
  • Lactose 10.2%
  • TAED bleach activator tetraacetylethylenediamine
  • protease protein derived from Bacillus clausii it further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
  • a Launder-O-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/ sebum, Wfk20LI redwine, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend and dirty motor oil, Ragu, Grass, Tomato puree, Asda chocolate ice cream, Cocoa, artificial menstrual fluid, Coffee, and Beta carotene from Equest were included for 800 mL wash liquor. Wash performance was measured as remission at 460 nm.
  • a model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate.
  • AEOS EO3 alkyl ethoxy sulfate
  • AEO 3EO alcohol ethoxylate
  • Lactose 10.2%
  • TAED bleach activator tetraacetylethylenediamine
  • protease protein derived from Bacillus clausii it further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 99/31990).
  • a Tergo-To-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/ sebum, Wfk20LI redwine, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend and dirty motor oil, Ragu, Grass, Tomato puree, Asda chocolate ice cream, Cocoa, artificial menstrual fluid, Coffee, and Beta carotene from Equest were included for 800 mL wash liquor.
  • a model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate.
  • AEOS EO3 alkyl ethoxy sulfate
  • AEO 3EO alcohol ethoxylate
  • Lactose 10.2%
  • TAED bleach activator tetraacetylethylenediamine
  • protease protein derived from Bacillus clausii it further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
  • a Tergo-To-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/s ebum, Wfk20LI redwine, WfklOK coffee, Wfk20M motor oil, EMPAl 11 blood, Empa 112 milk/cocoa, EMPA160 Chocolate pudding, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend, and Ragu, Grass, and Tomato puree from Equest were included for 800 mL wash liquor.

Abstract

The invention provides a detergent composition comprising a surfactant, a carbohydrate oxidate, lactose and a bleach activator. The invention also provides a method for simultaneous formation of a builder and a bleach system in a detergent solution.

Description

Description
DETERGENTS WITH ENZYMATIC BUILDER AND BLEACH
SYSTEMS
Technical Field
[0001] The present invention relates to enzymatic methods for generating builder and bleach systems in a detergent. Background Art
[0002] Several of the known bleaching agents and calcium binders (builders) used in detergents for laundry and household cleaning include chemicals which are only slowly or not at all biodegradeable.
[0003] Lactobionic acid is an alternative biodegradable builder agent. By use of the present invention, lactobionic acid is formed in-situ along with an activated bleaching system, thus avoiding the need for separate hydrogen peroxide generating agents in detergent formulations.
[0004] Accordingly, the present invention provides an environmentally friendly method for in-situ generation of builder and bleach systems in a detergent.
Summary
[0005] In a first aspect, the present invention provides a detergent composition comprising a surfactant, a bleach activator, lactose and a carbohydrate oxidase, which is capable upon solution of forming simultaneously a builder and an activated bleach system.
[0006] In a second aspect the invention provides an enzymatic method for simultaneous formation of a builder and a bleach system in a detergent solution, which includes combining a bleach activator, lactose and a carbohydrate oxidase in an aqueous solution comprising a surfactant.
Detailed description Carbohydrate oxidase
[0007] In the present invention a carbohydrate oxidase enzyme is used to convert lactose to lactobionic acid in-situ in a detergent solution. The reaction scheme may be described as:
[0008] lactose + Vi O2 → lactobionic acid + H2O2. [0009] The CAS reg. no. for lactobionic acid is 96-82-2. [0010] A number of suitable carbohydrate oxidases, capable of converting lactose to lactobionic acid, are known and available to the skilled person. It may for instance be a hexose oxidase. [0011] Preferably, the carbohydrate oxidase is a microbial carbohydrate oxidase. [0012] A suitable hexose oxidase (EC 1.1.3.5) is described in
WO 9640935 (BIOTEKNOLOGISK INSΗTUT). 1996-12-19. . This document describes a suitable hexose oxidase from marine algal species more particular wherein the marine algal species is one selected from the group consisting of Chondrus crispus, Iridophycus flaccidum and Euthora cristate
[0013] Other suitable carbohydrate oxidase may be derived, e.g., from a mitosporic
Pyrenomycetes such as Acremonium, in particular, A. strictum, such as ATCC 34717 or Tl; A. fusidioides, such as IFO 6813; or A.potronii, such as IFO 31197. In a preferred embodiment, the carbohydrate oxidase is obtained from the source disclosed by
LIN, . Purification and characterization of a novel glucooligosaccharide oxidase from
Acremonium strictum Tl. Biochim. biophys. acta, 1991 vol. 1118, p. 41-47. ISSN
0006-3002. and in JP-A 5-84074.
[0014] In a preferred embodiment the carbohydrate oxidase is a carbohydrate oxidase obtained from a fungus belonging to the genus Microdochium, more preferably wherein the fungus is Microdochium nivale and even more preferably wherein the fungus is Microdochium nivale CBS 100236. Such a preferred oxidase is described in details in WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
[0015] The amount of oxidase to be used will generally depend on the specific needs.
Preferably, there is used an amount of oxidase that is from 0.1 to 1000 OXU per liter of detergent solution, more preferably from 1 to 500 OXU per liter of detergent solution, and even more preferably from 5 to 100 OXU per liter of detergent solution.
[0016] An Oxidase Unit (OXU) is herein basically defined as the amount of enzyme that oxidizes one μmol lactose per minute under the incubation conditions of the method one specifically uses.
Lactose
[0017] According to the invention, lactose is included in the detergent solution at a concentration of 0.05 g/L to 5.0 g/L, preferably 0.05 g/L to 4.0 g/L, more preferably 0.05 g/L to 3.0 g/L, even more preferably 0.05 g/L to 2.0 g/L, and most preferably 0.05 g/L to 1.0 g/L.
Bleach activator
[0018] Hydrogen peroxide, or a source of hydrogen peroxide (such as perborates or per- carbonates), may be used to oxidize and decolorize stains originating from natural substances (e.g. protein, tea, red wine, and fruit juice). Peroxygen type bleaching agents are especially efficient at high temperatures, and an activator may be added to enhance the bleaching effect at lower temperatures. In the context of the present inven tion, hydrogen peroxide formed by reacting lactose and a carbohydrate oxidase is combined with a bleaching activator to make up an activated bleaching system. [0019] Examples of bleach activators suitable in the present invention include, but are not limited to, tetra-acetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in
US 4412934 (PROCTER & GAMBLE). 1983-11-01. ), 3,5-trimethyl-hexsanoloxybenzenesulfonate (ISONOBS, described in EP 120591 (PROCTER & GAMBLE). 1984-10-03.
) or pentaacetylglucose (PAG), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. In addition, very suitable are the bleach activators C8 (6-octanamido-caproyl) oxybenzene-sulfonate, C9 (6-nonanamido caproyl) oxybenzenesulfonate and ClO (6-decanamido caproyl) oxy- benzenesulfonate or mixtures thereof. Also suitable activators are acylated citrate esters such as disclosed in EP 624154 (PROCTER & GAMBLE). 1994-11-17.
Detergent composition
[0020] The carbohydrate oxidase, lactose and bleach activator may be added to and thus become components of a detergent composition.
[0021] The detergent composition of the invention may for example be formulated as a hand or machine laundry detergent composition including a laundry additive composition suitable for pre-treatment of stained fabrics and a rinse added fabric softener composition, or be formulated as a detergent composition for use in general household hard surface cleaning operations, or be formulated for hand or machine dishwashing operations.
[0022] In a specific aspect, the invention provides a detergent additive comprising a carbohydrate oxidase, lactose, a bleach activator and a surfactant. The detergent additive as well as the detergent composition may comprise one or more other enzymes such as a protease, a lipase, a cutinase, an amylase, a carbohydrase, a cellulase, a pectinase, a mannanase, an arabinase, a galactanase, a xylanase, an oxidase (such as a laccase), and/or a peroxidase (such as a haloperoxidase).
[0023] In general the properties of the chosen enzyme(s) should be compatible with the selected detergent, (i.e. pH-optimum, compatibility with other enzymatic and non- enzymatic ingredients, etc.), and the enzyme(s) should be present in effective amounts.
[0024] Proteases: Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically modified or protein engineered mutants are included. The protease may be a serine protease or a metallo protease, preferably an alkaline microbial protease or a trypsin-like protease. Examples of alkaline proteases are subtilisins, especially those derived from Bacillus, e.g., subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (described in WO 89/06279). Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease described in WO 89/06270 and WO 94/25583.
[0025] Examples of useful proteases are the variants described in WO 92/19729, WO
98/20115, WO 98/20116, and WO 98/34946, especially the variants with substitutions in one or more of the following positions: 27, 36, 57, 76, 87, 97, 101, 104, 120, 123, 167, 170, 194, 206, 218, 222, 224, 235 and 274.
[0026] Lipases: Suitable Upases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful Upases include Upases from Humicola (synonym Thermomyces), e.g. from H. lanuginosa (T. lanuginosus) as described in EP 258 068 and EP 305 216 or from H. insolens as described in WO 96/13580, a Pseudomonas lipase, e.g. from P. alcaligenes or P. pseu- doalcaligenes (EP 218 272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluoresce™, Pseudomonas sp. strain SD 705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), a. Bacillus lipase, e.g. from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64/744992) or B. pumilus (WO 91/16422).
[0027] Other examples are lipase variants such as those described in WO 92/05249, WO
94/01541, EP 407 225, EP 260 105, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202.
[0028] Amylases: Suitable amylases (alpha and/or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases obtained from Bacillus, e.g. a special strain of B. licheniformis, described in more detail in GB 1,296,839.
[0029] Examples of useful amylases are the variants described in WO 94/02597, WO
94/18314, WO 96/23873, and WO 97/43424, especially the variants with substitutions in one or more of the following positions: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.
[0030] Cellulases: Suitable cellulases include those of bacterial or fungal origin.
Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, e.g. the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757 and WO 89/09259. [0031] Especially suitable cellulases are the alkaline or neutral cellulases having colour care benefits. Examples of such cellulases are cellulases described in EP 0495 257, EP 0 531 372, WO 96/11262, WO 96/29397, WO 98/08940. Other examples are cellulase variants such as those described in WO 94/07998, EP 0 531 315, US 5,457,046, US 5,686,593, US 5,763,254, WO 95/24471, WO 98/12307 and PCT/DK98/00299.
[0032] Peroxidases/Oxidases: Suitable peroxidases/oxidases include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of useful peroxidases include peroxidases from Coprinus, e.g. from C. cinereus, and variants thereof as those described in WO 93/24618, WO 95/10602, and WO 98/15257.
[0033] The detergent enzyme(s) may be included in a detergent composition by adding separate additives containing one or more enzymes, or by adding a combined additive comprising all of these enzymes. A detergent additive of the invention, i.e. a separate additive or a combined additive, can be formulated e.g. as a granulate, a liquid, a slurry, etc. Preferred detergent additive formulations are granulates, in particular non- dusting granulates, liquids, in particular stabilized liquids, or slurries.
[0034] Non-dusting granulates may be produced, e.g., as disclosed in US 4,106,991 and 4,661,452 and may optionally be coated by methods known in the art. Examples of waxy coating materials are poly(ethylene oxide) products (polyethyleneglycol, PEG) with mean molar weights of 1000 to 20000; ethoxylated nonylphenols having from 16 to 50 ethylene oxide units; ethoxylated fatty alcohols in which the alcohol contains from 12 to 20 carbon atoms and in which there are 15 to 80 ethylene oxide units; fatty alcohols; fatty acids; and mono- and di- and triglycerides of fatty acids. Examples of film-forming coating materials suitable for application by fluid bed techniques are given in GB 1483591. Liquid enzyme preparations may, for instance, be stabilized by adding a polyol such as propylene glycol, a sugar or sugar alcohol, lactic acid or boric acid according to established methods. Protected enzymes may be prepared according to the method disclosed in EP 238,216.
[0035] The detergent composition of the invention may be in any convenient form, e.g., a bar, a tablet, a powder, a granule, a paste or a liquid. A liquid detergent may be aqueous, typically containing up to 70% water and 0-30% organic solvent, or nonaqueous.
[0036] The detergent composition comprises one or more surfactants, which may be non- ionic including semi-polar and/or anionic and/or cationic and/or zwitterionic. The surfactants are typically present at a level of from 0.1% to 60% by weight.
[0037] When included therein the detergent will usually contain from about 1% to about 40% of an anionic surfactant such as linear alkylbenzenesulfonate, alpha- olefinsulfonate, alkyl sulfate (fatty alcohol sulfate), alcohol ethoxysulfate, secondary alkanesulfonate, alpha-sulfo fatty acid methyl ester, alkyl- or alkenylsuccinic acid or soap.
[0038] When included therein the detergent will usually contain from about 0.2% to about 40% of a non-ionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid mo- noethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine ("glucamides").
[0039] The detergent may contain 0-50% of a detergent builder or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, carbonate, citrate, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl- or alkenylsuccinic acid, soluble silicates or layered silicates (e.g. SKS-6 from Hoechst).
[0040] The detergent may comprise one or more polymers. Examples are carboxymethyl- cellulose, poly(vinylpyrrolidone), poly (ethylene glycol), polyvinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as poly- acrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
[0041] The enzyme(s) of the detergent composition of the invention may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.
[0042] The detergent may also contain other conventional detergent ingredients such as e.g. fabric conditioners including clays, foam boosters, suds suppressors, anti-corrosion agents, soil-suspending agents, anti-soil redeposition agents, dyes, bactericides, optical brighteners, hydrotropes, tarnish inhibitors, or perfumes.
[0043] It is at present contemplated that in the detergent compositions any enzyme, and the carbohydrate oxidase of the method and composition of invention, may be added in an amount corresponding to 0.01-100 mg of enzyme protein per liter of wash liqour, preferably 0.05-10 mg of enzyme protein per liter of wash liqour, more preferably 0.1-5 mg of enzyme protein per liter of wash liqour, and most preferably 0.1-1 mg of enzyme protein per liter of wash liqour.
[0044] The pH of an aqueous solution of the detergent composition is in the range of from pH 6 to 11, preferably in the range of from pH 6.5 to 10.5, more preferably in the range of from pH 7 to 10.5, most preferably in the range of from pH 7 to 10.
Methods and Uses
[0045] The present invention provides an enzymatic method for simultaneous formation of a builder and a bleach system in a detergent solution, which includes combining a bleach activator, lactose and a carbohydrate oxidase in an aqueous solution comprising a surfactant. [0046] In the context of the present invention the term "formation of a builder and a bleach system" is intended to mean that at least 2%, preferably at least 5%, more preferably at least 10%, even more preferably at least 20%, most preferably at least 50% of the lactose is converted to lactobionic acid, or a salt thereof, and hydrogen peroxide by the carbohydrate oxidase. [0047] Lactobionic acid and salts thereof, have calcium binding (builder) capabilities, as shown in
US 5069808 (KALI CHEMIE AG). 1991-12-03.
; and hydrogen peroxide combines with the bleach activator to become a bleaching system.
[0048] In an embodiment, the formed lactobionic acid, or a salt thereof, is used as a co- builder in conjunction with another builder, such as a zeolite or a phosphate.
Preferably, the detergent solution does not contain any other hydrogen peroxide sources, such as perborates or percarbonates. [0049] The surfactant of the method of the invention is described above in "detergent composition". [0050] The method of the invention is preferably carried out during a washing process, such as a laundry washing process or a dish washing process. [0051] The method of the invention may be carried out at a temperature between 0 and 90 degrees Celsius, preferably between 5 and 80 degrees Celsius, more preferably between 10 and 70 degrees Celsius, and most preferably between 20 and 60 degrees
Celsius. [0052] The present invention is further described by the following examples which should not be construed as limiting the scope of the invention.
Examples
[0053] Chemicals used as buffers and substrates were commercial products of at least reagent grade.
Example 1
[0054] Enzymatic formation of lactobionic acid and hydrogen peroxide in a detergent solution
[0055] A model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate. It further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
)•
[0056] A Launder-O-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/ sebum, Wfk20LI redwine, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend and dirty motor oil, Ragu, Grass, Tomato puree, Asda chocolate ice cream, Cocoa, artificial menstrual fluid, Coffee, and Beta carotene from Equest were included for 800 mL wash liquor. Wash performance was measured as remission at 460 nm.
[0057] The tests showed that by adding the carbohydrate oxidase containing enzyme cocktail, performance is increased on both the builder sensitive clay stain and the bleach sensitive redwine stain.
[0058]
Table 1
Figure imgf000009_0001
[0059]
Example 2
[0060] Enzymatic formation of peracids as bleaching agents in a detergent solution [0061] A model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate. It further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 99/31990).
[0062] A Tergo-To-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/ sebum, Wfk20LI redwine, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend and dirty motor oil, Ragu, Grass, Tomato puree, Asda chocolate ice cream, Cocoa, artificial menstrual fluid, Coffee, and Beta carotene from Equest were included for 800 mL wash liquor.
[0063] Peracid levels were measured as described in
BINDER, WH. Assay of peracid in the presence of excess hydrogen peroxide. Analytical Letters, 2000 vol. 33, no. 3, p. 479-488.
. The tests showed that by adding the carbohydrate containing enzyme cocktail, 0.031 mM peracid was detected at the end of the wash. The presence of peracid shows that an activated bleaching system is present.
Example 3
[0064] Enzymatic formation of hydrogen peroxide and peracids in a detergent solution [0065] A model laundry detergent was prepared. It comprised 18.8% surfactant of which 12.2% was C9-15, EO3 alkyl ethoxy sulfate (AEOS) and 6.2% was a C12-15, 3EO alcohol ethoxylate (AEO), 61.1% Lactose, 10.2% bleach activator tetraacetylethylenediamine (TAED) and 10.2% carbonate. It further comprised 0.06% protease protein derived from Bacillus clausii, 0.04% lipase protein derived from Thermomyces lanuginosus, 0.006% amylase protein derived from Bacillus subtilus, 0.004% cellulase protein derived from Bacillus subtilus, 0.002% cellulase protein derived from Humicola insolens, 0.004% pectate lyase protein derived from Bacillus subtilis, 0.004% mannase protein derived from Alkalophilic Bacillus, and 0.02% carbohydrate oxidase protein derived from Microdochium nivale (see WO 9931990 (NOVO NORDISK AIS). 1999-07-01.
)•
[0066] A Tergo-To-Meter wash was performed for 40 minutes at 25°C, pH 8.5, 14°dH, Ca:Mg 3:1. 4Og of fabric comprising WfklOTE Clay, WfklOppm veg.oil/milk, Wfk20LS lipstick, Wfk20MU Make up, WfklOD pigment/sebum, Wfk20D pigment/s ebum, Wfk20LI redwine, WfklOK coffee, Wfk20M motor oil, EMPAl 11 blood, Empa 112 milk/cocoa, EMPA160 Chocolate pudding, CS-IO butterfat, Wfk80A cotton, Wfk30A polyester, a cotton/polyester blend, and Ragu, Grass, and Tomato puree from Equest were included for 800 mL wash liquor.
[0067] Hydrogen peroxide and peracid levels were measured as described in BINDER, WH. Assay of peracid in the presence of excess hydrogen peroxide. Analytical Letters, 2000 vol. 33, no. 3, p. 479-488.
. The tests showed that by adding the carbohydrate containing enzyme cocktail, 0.044 mM peracid and 0.074 mM hydrogen peroxide was present at the end of the wash.

Claims

Claims
[0001] A detergent composition comprising a surfactant, a bleach activator, lactose and a carbohydrate oxidase. [0002] The composition of claim 1, wherein the carbohydrate oxidase is capable of converting lactose to lactobionic acid and hydrogen peroxide. [0003] An enzymatic method for simultaneous formation of a builder and a bleach system in a detergent solution, which includes combining a bleach activator, lactose and a carbohydrate oxidase in an aqueous solution comprising a surfactant. [0004] The method of claim 3, wherein the carbohydrate oxidase is capable of converting lactose to lactobionic acid and hydrogen peroxide.
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US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
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US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
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WO2007106293A1 (en) * 2006-03-02 2007-09-20 Genencor International, Inc. Surface active bleach and dynamic ph
EP2159278A1 (en) * 2008-08-27 2010-03-03 The Procter & Gamble Company A detergent composition comprising carbohydrate: acceptor oxidoreductase
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US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants

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