EP4045621A1 - Detergent composition - Google Patents

Detergent composition

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Publication number
EP4045621A1
EP4045621A1 EP20785504.0A EP20785504A EP4045621A1 EP 4045621 A1 EP4045621 A1 EP 4045621A1 EP 20785504 A EP20785504 A EP 20785504A EP 4045621 A1 EP4045621 A1 EP 4045621A1
Authority
EP
European Patent Office
Prior art keywords
oxidase
fatty acid
composition
enzyme
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP20785504.0A
Other languages
German (de)
French (fr)
Other versions
EP4045621B1 (en
Inventor
Marina MIXTRO SERRASQUEIRO
Graham CORLETT
Dietmar Andreas LANG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4045621A1 publication Critical patent/EP4045621A1/en
Application granted granted Critical
Publication of EP4045621B1 publication Critical patent/EP4045621B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention is in the field of machine dishwashing compositions. More particularly, it relates to machine dishwashing compositions comprising carbohydrate oxidase enzymes and a surfactant system. The invention also relates to a method of washing kitchenware in a machine dishwasher with a machine dishwashing composition comprising carbohydrate oxidase enzymes and a process for making said composition.
  • Machine dishwashing compositions comprising bleaching enzymes have been described in the prior art.
  • W01 999/002640 discloses cleaning compositions comprising oxidoreductase (non haem haloperoxidase) with an a/b-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid.
  • Example 19 discloses a dishwasher composition comprising 0.002 wt.% haloperoxidase, 1.2 wt.% non-ionic surfactant, pH 8.
  • Known enzyme dishwasher compositions suffer from poor stain removing power, particularly in the absence of percarbonate and/or perborate.
  • Notorious hard to remove stains include tea stains, which require substantial bleaching power to remove.
  • dishwasher compositions that are capable of being free of bleach precursors (e.g. percarbonate and/or perborate) and more preferably have reduced amounts of, preferably being free of, bleach activators and/or have reduced amounts of, preferably being free of, metal bleach catalysts yet provide (tea)-stain removing power.
  • bleach precursors e.g. percarbonate and/or perborate
  • the present invention relates to a machine dishwasher composition comprising: a) from 0.002 to 0.5 wt.
  • % of active carbohydrate oxidase enzyme preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 1 to 40 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.5, as measured at 25 degrees Celsius and in otherwise standard conditions.
  • carbohydrate oxidase enzyme substrate b) is suitable to be acted upon by the carbohydrate oxidase enzyme a) being used in the composition according to the invention. This for the system to generate adequate amounts of H2O2.
  • a machine dish wash composition according to the invention is capable of effectively removing tea stains without the presence of bleach precursor, bleach activator and bleach catalyst at high temperatures. This is the more surprising since at such high temperature (and alkaline) conditions one may not expect the enzyme system to be able to effectively generate sufficient H2O2.
  • Typical optimal enzyme conditions are at low temperatures and or neutral to slightly acidic pH levels.
  • the optimal conditions for the used enzyme in the examples were a temperature of 35-40 degrees Celsius and a pH of 5.2. Yet in conditions of a pH of 10.5 with a temperature of 80 degrees Celsius it effectively generated H2O2 from the available glucose and provide excellent tea-stain removal.
  • a machine dish wash composition according to the invention is capable of effectively removing tea stain without the presence of bleach precursor and/or bleach activator at low-medium temperatures while using relatively small amounts of active enzyme and bleach catalyst, in particular a Manganese based catalyst.
  • the ability to employ relatively small amounts of active enzyme to provide good tea-stain removal is highly beneficial from a stability point of view, costs point of view as well as from a product stability point.
  • the invention also relates to a unit dose comprising a composition defined herein, wherein the unit dose is a gel, powder, liquid or combination thereof.
  • the invention relates to a method of cleaning kitchenware comprising the steps of contacting the composition a defined herein with kitchenware in the presence of water, preferably at a temperature in the range of 30 to 90 °C.
  • the invention relates to a use of a composition according to the invention as (tea)stain remover, preferably as a sustainable/bio-based/green tea(stain) remover wherein more preferably the stain remover is active at a temperature in the range of 40 to 90 °C, more preferably 50-80 °C.
  • the invention relates to a process of preparing compositions according to any of the preceding claims comprising the step of combining a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system.
  • carbohydrate oxidase enzyme as used herein preferably refers to an enzyme of class E.C.1.1.3 and E.C.1.1.3.4, but is otherwise use in a general sense of an enzymes capable of generating peroxide using a carbohydrate substrate.
  • the carbohydrate oxidase enzyme is selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase and mixtures thereof, more preferably glucose oxidase.
  • Suitable oxidase enzymes are those classified under enzyme classification E.C.1.1.3., namely those acting on the CH-OH group of donors with oxygen as acceptor.
  • the oxidase enzyme oxidases are selected from those under enzyme commission number E.C.1.1.3.4.
  • the carbohydrate oxidase enzyme is glucose oxidase, for example a glucose oxidase as available from Sigma Aldrich (UK) Catalog Number G7141 (CAS RN 9001-37-0), Roche (GOD), Sorachim (GLO-202A), Sekisui (HPS300 or Maxapal®G04 (DSM The Netherlands).
  • the glucose oxidase has at least 70%, preferably at least 80%, more preferably at least 90% amino acid sequence homology to the glucose oxidase with accession number P13006 (Uniprot).
  • the enzyme of the invention has its optimum temperature condition in a temperature range of from 25 to 55, more preferably from 30 to 45 and even more preferably of from 35 to 40 degrees Celsius.
  • the enzyme of the invention has its optimal pH condition in the range of from 4.5 to 8.0, more preferably of from 4.6 to 7.0 even more preferably of from 4.8 to 6.0 and still even more preferably of from 5.0 to 5.5.
  • the amount of carbohydrate oxidase enzyme will depend on its specific activity, but preferably the machine dishwash composition of the invention comprises from 10 to 5000, preferably from 60 to 2000, more preferably from 100 to 1500 and even more preferably from 200 to 1000 units of carbohydrate oxidase enzyme per 18g of the composition.
  • a unit of enzyme activity is defined as the quantity required to convert 1 pmol of its substrate per minute under standard conditions.
  • the range of 200 to 1000 units of carbohydrate oxidase enzyme was found to be optimal in view of providing good tea-stain cleaning and minimizing the amounts of ingredients actives used. In fact, it was interestingly observed that very high levels of carbohydrate oxidase enzyme did not per se lead to better tea stain removal.
  • the machine dishwashing composition comprises 0.01 to 0.4 wt.% active carbohydrate oxidase enzyme.
  • the machine dishwashing composition comprises 0.02 to 0.3 wt.% of active carbohydrate oxidase enzyme, even more preferably 0.04 to 0.2 wt.%, and still even more preferably of from 0.045 to 0.08 wt. % of active carbohydrate oxidase enzyme.
  • the later range was likewise found to provide an optimal balance between good tea stain cleaning and minimizing the amounts of detergent actives required.
  • the amount of active enzyme can generally be equated to the amount of pure enzyme.
  • the carbohydrate oxidase enzyme substrate is selected from the group consisting of allose, altrose, glucose, mannose, gulose, idose, galactose, talos, sorbose and mixtures thereof, preferably the carbohydrate oxidase enzyme substrate is selected from the group consisting of D-(+)-Allose, D-(+)-Altrose, D-(+)-Glucose, D-(+)-Mannose, D-(-)-Gulose, D-(+)-ldose, D-(+)-Galactose, D-(+)-Talose and mixtures thereof.
  • the carbohydrate oxidase enzyme substrate is selected from the group consisting of glucose, galactose, sorbose and mixtures thereof.
  • the carbohydrate oxidase enzyme substrate is selected from the group consisting of The D-glucose 2-deoxy-D-glucose, 4-O-methyl-D-glucose, 6-deoxy-D- glucose, 4-deoxy-D-glucose, 3-deoxy-D-glucose, 3-O-methyl-D-glucose and mixtures thereof.
  • the composition of the invention preferably comprises from 2 to 35 wt. %, more preferably from 5 to 33 wt. %, even more preferably from 10 to 30 wt.% and still more preferably from 11 to 25 wt.% of the carbohydrate substrate. Such levels of carbohydrate substrate were found to be more optimal for the removal of tea-stains especially at low- medium temperatures.
  • the surfactant system comprises non-ionic surfactant.
  • the composition comprises anionic surfactants, cationic surfactants and amphoteric/zwitterionic surfactants and mixtures thereof.
  • the non-ionic and or anioninc surfactants of the Surfactant System may be chosen from the surfactants described in “Surface Active Agents' Vol.
  • Suitable non-ionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Non-ionic detergent compounds are C-C alkyl phenol ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs-Cs primary or Secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
  • the machine dishwashing composition comprises a non-ionic surfactant system selected from a C10-20 fatty acid, an alkoxylated fatty alcohol, an alkoxylated fatty acid, alkylphenol alkoxylates, alkoxylated amines, alkoxylated fatty acid amides, terminally blocked alkoxylates, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine-oxides, sulphoxides, phosphine oxides, more preferably selected from a C10-20 fatty acid, an ethoxylated fatty alcohol, an ethoxylated fatty acid, alkylphenol ethoxylates, ethoxylated amines, ethoxylated fatty acid amides, terminally blocked ethoxylates, fatty acid esters of glycerol, fatty acid esters
  • the machine dishwashing composition comprises from 0.1 to 15 wt.% non ionic surfactant, preferably 1.0 to 12.0 wt.% non-ionic surfactant, more preferably 2.0 to 8 wt.% non-ionic surfactant, most preferably 2.5 to 5 wt.% non-ionic surfactant.
  • the machine dishwashing composition comprises at most 5.0 wt. %, more preferably at most 4.0 wt. %, even more preferably at most 3.0 wt. %, still even more preferably at most 2.0 wt. % and still even more preferably at most 1.0 wt. % of anionic surfactant.
  • the machine dishwashing composition preferably comprises 10 to 50 wt.% carbonate salts, preferably selected from Na 2 CC> 3 , K 2 CO 3 , CaCCh or a combination of both, preferably 15 to 40 wt.% carbonate salts selected from Na2CC>3 and CaCCh or a combination of both, most preferably 20 to 30 wt. % carbonate, selected from Na2CC>3, CaCCh or a combination of both.
  • the carbonate salt is Na 2 C0 3 .
  • builder refers to a material that is capable of removing calcium and/or magnesium ion from aqueous solution by ion exchange, complexation, sequestration and/or precipitation.
  • the builder or sequestrant material is preferably fully soluble in water so as to eliminate the possibility of unwanted and unsightly residues on substrates. For that reason alkali metal aluminosilicates are not favoured.
  • Typical examples of phosphorus containing inorganic builders, when present, include the water- soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates.
  • inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
  • suitable non-phosphorus water-soluble detergency builders when present, include carbonate, citrate, zeolite, silicate and aminopolycarboxylic compounds, such as glutamate diacetic acid (GLDA), methylglycine diacetic acid (MGDA), and Trisodium Citrate.
  • non-phosphorus water-soluble detergency builders may include inorganic builders as alkali metal carbonate, bicarbonates, sesquicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates, and organic builders as polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
  • Bleach activator alkali metal carbonate, bicarbonates, sesquicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates
  • organic builders as polycarboxylate polymers, such as polyacrylates, acrylic/maleic copoly
  • bleach activator refers to compounds employed in cleaning compositions to activate the bleaching agent, or bleach component, especially at lower temperatures.
  • bleach activators suitable for use in the cleaning compositions of this invention include one or more activators such as peroxyacid bleach precursors.
  • Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC).
  • the detergent composition of the invention may comprise from 0.01 to 15 wt. % of bleach activator, more preferably from 0.2 to 10 wt. % and even more preferably from 1.0 to 6 wt. %, but more preferably comprises no bleach activator.
  • Bleach catalyst 0.01 to 15 wt. % of bleach activator, more preferably from 0.2 to 10 wt. % and even more preferably from 1.0 to 6 wt. %, but more preferably comprises no bleach activator.
  • Bleach catalysts function by oxidizing typically via peroxide or a peracid to form a bleaching species. They require the presence of an oxidizable soil so that they can be reduced back to the starting bleach activator state.
  • the preferred bleach catalyst according used in the invention is a manganese complex of formula (A):
  • Such bleach catalysts are described in EP0458397A2.
  • the preferred features of the manganese-based bleach catalyst described therein are preferred as well for the purposes of this invention and explicitly belong to the description of this invention.
  • the preferred features referred to are described on pages 3 to 8 of EP0458397A2 insofar as relating to manganese-based bleach catalysts.
  • the bleach catalysts of the invention are more preferably one or more of:
  • the still even more preferred bleach catalyst is Mn lv 2 (p-0) 3 (Me-TACN) 2 ] (PFe) 2 .
  • the preferred amount of the bleach catalyst is from 0.001 to 2 wt. %, more preferably from 0.005 to 1 wt. %, even more preferably from 0.008 to 0.5 wt. % and still more preferably from 0.01 to 0.1 wt. %, as based on actives levels.
  • the preferred form of adding the bleach catalyst is as of part of a bleach catalyst granule comprising less than 5 wt. % of active bleach catalyst. The use of such granules improves the accurate dosing of the bleach catalyst.
  • the detergent composition is preferably a powder, a tablet, an aqueous or non-aqueous liquid, a loose flowing powder, a paste, a capsule or a gel.
  • the composition is in the form a gel, a capsule or a tablet, more preferably a capsule.
  • the carbohydrate oxidase enzyme used in the present invention can usefully be added to the detergent composition in any suitable form, i.e. the form of a granular composition, a liquid or a slurry of the enzyme, or with carrier material.
  • adding the enzyme to a liquid detergent product is in the form of a slurry containing 0.5 to 50% by weight of the enzyme in an ethoxylated alcohol nonionic surfactant, such as described in EP-A-450702 (Unilever).
  • the machine dishwashing composition is a solid or flowing powder
  • the machine dishwashing composition preferably has a water content of less than 5 wt.%.
  • machine dishwashing composition is tablet with a water content of less than 5 wt.%.
  • a 1 wt. % solution of the detergent composition in deionised water has a pH in the range of 8.5 - 11.0, more preferably 9.0 - 10.75 and most preferably 9.5 - 10.5. The pH being measured at 25 °C, in otherwise standard conditions.
  • the composition may be in the form of a unit dose, wherein the unit dose is a gel, powder, liquid or combination thereof.
  • a preferred machine dishwash composition comprises: a) from 0.02 to 0.3 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 30 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.0, as measured at 25 degrees Celsius and in otherwise standard conditions.
  • active carbohydrate oxidase enzyme preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase
  • a more preferred machine dishwash composition comprises, especially for use at a wash temperature of below 65 degrees Celsius: a) from 0.04 to 0.2 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 25 wt.
  • active carbohydrate oxidase enzyme preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase
  • the composition further comprises from 0.01 to 1 wt. % bleach catalyst, wherein the bleach catalyst preferably comprises manganese complex of formula (A): [L n Mn m X p ] z Yq
  • an even more preferred machine dishwash composition according to the invention for use at a wash temperature above 65 degrees Celsius comprises: a) from 0.04 to 0.2 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 25 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.0, as measured at 25 degrees Celsius and in otherwise standard conditions; wherein little or no bleach activator and/or bleach catalyst is present.
  • active carbohydrate oxidase enzyme
  • the machine dish wash compositions of the invention preferably comprise no bleach precursor, although the presence of such does not negatively affect the tea-stain cleaning.
  • a method of cleaning kitchenware comprising the steps of contacting a detergent composition as defined herein with kitchenware in the presence of water.
  • the method is carried out at a temperature in the range of 30 to 90 °C, more preferably 40 to 85 °C, even more preferably 50 to 80 °C.
  • a high temperature wash conditions is defined as using a temperature of above 65 degrees Celsius; low-medium temperature wash conditions as a temperature of at most 65 degrees Celsius.
  • the stain remover is active at a temperature in the range of 40 to 90 °C, more preferably 40 to 85 °C, even more preferably 50 to 80 °C.
  • a process of preparing compositions as described herein comprising the step of combining a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system.
  • a process of preparing a unit dose comprising the step of: i. providing a carbohydrate oxidase enzyme, substrate for said enzyme and a non ionic surfactant system to provide a mixture, ii. forming the mixture of step (i) into a unit dose.
  • the ingredients and amounts of the ingredients described herein apply mutatis mutandis to the fourth and fifth aspects.
  • compositions 6 to 8 were prepared, as shown in Table 2:
  • Stained tiles (DM-14 Dark Tea on Melamine; Supplier: Center For Test materials B.V.) were placed in a 5L solution made from dosing 18g according to formulations listed in Table 1 in water. Each solution was placed in a beaker under agitation and temperature controlled for 20min. The temperate was as indicated in Table 3. Scale: (-) poor to (+++) best) stain removing power:

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Abstract

The present invention is in the field of machine dishwashing compositions. More particularly, it relates to machine dishwashing compositions comprising a carbohydrate oxidizing enzyme. The invention also relates to a method of washing kitchenware in a machine dishwasher with a machine dishwashing composition comprising a carbohydrate oxidizing enzyme and a process for making said composition.

Description

DETERGENT COMPOSITION
TECHNICAL FIELD OF THE INVENTION
The present invention is in the field of machine dishwashing compositions. More particularly, it relates to machine dishwashing compositions comprising carbohydrate oxidase enzymes and a surfactant system. The invention also relates to a method of washing kitchenware in a machine dishwasher with a machine dishwashing composition comprising carbohydrate oxidase enzymes and a process for making said composition.
BACKGROUND OF THE INVENTION
Machine dishwashing compositions comprising bleaching enzymes have been described in the prior art.
W01 999/002640 discloses cleaning compositions comprising oxidoreductase (non haem haloperoxidase) with an a/b-hydrolase fold and a catalytic triad consisting of the amino acid residues serine, histidine and aspartic acid. Example 19 discloses a dishwasher composition comprising 0.002 wt.% haloperoxidase, 1.2 wt.% non-ionic surfactant, pH 8. Known enzyme dishwasher compositions suffer from poor stain removing power, particularly in the absence of percarbonate and/or perborate.
Notorious hard to remove stains include tea stains, which require substantial bleaching power to remove. There remains a need for dishwasher compositions that are capable of being free of bleach precursors (e.g. percarbonate and/or perborate) and more preferably have reduced amounts of, preferably being free of, bleach activators and/or have reduced amounts of, preferably being free of, metal bleach catalysts yet provide (tea)-stain removing power.
SUMMARY OF THE INVENTION
The inventors have developed a machine dishwasher composition that has excellent (tea)stain removing powder, in particular in the absence of percarbonate and/or perborate, and in some conditions even show very good tea stain bleaching when free from bleach activator and bleach catalyst. Accordingly, the present invention relates to a machine dishwasher composition comprising: a) from 0.002 to 0.5 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 1 to 40 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.5, as measured at 25 degrees Celsius and in otherwise standard conditions.
It will be appreciated that the carbohydrate oxidase enzyme substrate b) is suitable to be acted upon by the carbohydrate oxidase enzyme a) being used in the composition according to the invention. This for the system to generate adequate amounts of H2O2.
It was surprisingly found that a machine dish wash composition according to the invention is capable of effectively removing tea stains without the presence of bleach precursor, bleach activator and bleach catalyst at high temperatures. This is the more surprising since at such high temperature (and alkaline) conditions one may not expect the enzyme system to be able to effectively generate sufficient H2O2. Typical optimal enzyme conditions are at low temperatures and or neutral to slightly acidic pH levels. In fact, the optimal conditions for the used enzyme in the examples were a temperature of 35-40 degrees Celsius and a pH of 5.2. Yet in conditions of a pH of 10.5 with a temperature of 80 degrees Celsius it effectively generated H2O2 from the available glucose and provide excellent tea-stain removal.
It was further surprisingly found that a machine dish wash composition according to the invention is capable of effectively removing tea stain without the presence of bleach precursor and/or bleach activator at low-medium temperatures while using relatively small amounts of active enzyme and bleach catalyst, in particular a Manganese based catalyst. The ability to employ relatively small amounts of active enzyme to provide good tea-stain removal is highly beneficial from a stability point of view, costs point of view as well as from a product stability point. In a second aspect, the invention also relates to a unit dose comprising a composition defined herein, wherein the unit dose is a gel, powder, liquid or combination thereof. In a third aspect, the invention relates to a method of cleaning kitchenware comprising the steps of contacting the composition a defined herein with kitchenware in the presence of water, preferably at a temperature in the range of 30 to 90 °C.
In a fourth aspect, the invention relates to a use of a composition according to the invention as (tea)stain remover, preferably as a sustainable/bio-based/green tea(stain) remover wherein more preferably the stain remover is active at a temperature in the range of 40 to 90 °C, more preferably 50-80 °C.
In a fifth aspect, the invention relates to a process of preparing compositions according to any of the preceding claims comprising the step of combining a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system.
DETAILED DESCRIPTION OF THE INVENTION
The term “carbohydrate oxidase enzyme” as used herein preferably refers to an enzyme of class E.C.1.1.3 and E.C.1.1.3.4, but is otherwise use in a general sense of an enzymes capable of generating peroxide using a carbohydrate substrate.
The word ‘comprising’ as used herein is intended to mean ‘including’ but not necessarily ‘consisting of or ‘composed of. In other words, the listed steps or options need not be exhaustive.
Unless specified otherwise, numerical ranges expressed in the format ‘from x to y’ or ‘x- y’ are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format ‘from x to y’ or ‘x-y’, it is understood that all ranges combining the different endpoints are also contemplated. For the purpose of the invention ambient temperature is defined as a temperature of about 20°C. Unless indicated otherwise, weight percentages (wt.%) are based on the total weight of the composition. The enzyme, selected from the group of carbohydrate oxidases is capable of generating a hydrogen peroxide. Preferably, the carbohydrate oxidase enzyme is selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase and mixtures thereof, more preferably glucose oxidase. Suitable oxidase enzymes are those classified under enzyme classification E.C.1.1.3., namely those acting on the CH-OH group of donors with oxygen as acceptor. Preferably, the oxidase enzyme oxidases are selected from those under enzyme commission number E.C.1.1.3.4. In a preferable embodiment the carbohydrate oxidase enzyme is glucose oxidase, for example a glucose oxidase as available from Sigma Aldrich (UK) Catalog Number G7141 (CAS RN 9001-37-0), Roche (GOD), Sorachim (GLO-202A), Sekisui (HPS300 or Maxapal®G04 (DSM The Netherlands). Preferably, the glucose oxidase has at least 70%, preferably at least 80%, more preferably at least 90% amino acid sequence homology to the glucose oxidase with accession number P13006 (Uniprot).
Preferably the enzyme of the invention has its optimum temperature condition in a temperature range of from 25 to 55, more preferably from 30 to 45 and even more preferably of from 35 to 40 degrees Celsius. Advantageously the enzyme of the invention has its optimal pH condition in the range of from 4.5 to 8.0, more preferably of from 4.6 to 7.0 even more preferably of from 4.8 to 6.0 and still even more preferably of from 5.0 to 5.5. Surprisingly, it was found that an enzyme capable of generating peroxide and having temperature and pH optimums in these ranges was able to provide good tea-stain bleaching in MDW wash conditions, even in very alkaline conditions at high temperatures. Such conditions are quite far removed from the general enzyme optimal conditions, yet good carbohydrate oxidase-based tea-stain bleaching was observed.
The amount of carbohydrate oxidase enzyme will depend on its specific activity, but preferably the machine dishwash composition of the invention comprises from 10 to 5000, preferably from 60 to 2000, more preferably from 100 to 1500 and even more preferably from 200 to 1000 units of carbohydrate oxidase enzyme per 18g of the composition. A unit of enzyme activity is defined as the quantity required to convert 1 pmol of its substrate per minute under standard conditions. The range of 200 to 1000 units of carbohydrate oxidase enzyme was found to be optimal in view of providing good tea-stain cleaning and minimizing the amounts of ingredients actives used. In fact, it was interestingly observed that very high levels of carbohydrate oxidase enzyme did not per se lead to better tea stain removal.
The machine dishwashing composition comprises 0.01 to 0.4 wt.% active carbohydrate oxidase enzyme. Preferably the machine dishwashing composition comprises 0.02 to 0.3 wt.% of active carbohydrate oxidase enzyme, even more preferably 0.04 to 0.2 wt.%, and still even more preferably of from 0.045 to 0.08 wt. % of active carbohydrate oxidase enzyme. The later range was likewise found to provide an optimal balance between good tea stain cleaning and minimizing the amounts of detergent actives required. The amount of active enzyme can generally be equated to the amount of pure enzyme.
Preferably, the carbohydrate oxidase enzyme substrate is selected from the group consisting of allose, altrose, glucose, mannose, gulose, idose, galactose, talos, sorbose and mixtures thereof, preferably the carbohydrate oxidase enzyme substrate is selected from the group consisting of D-(+)-Allose, D-(+)-Altrose, D-(+)-Glucose, D-(+)-Mannose, D-(-)-Gulose, D-(+)-ldose, D-(+)-Galactose, D-(+)-Talose and mixtures thereof. More preferably the carbohydrate oxidase enzyme substrate is selected from the group consisting of glucose, galactose, sorbose and mixtures thereof. In certain preferred embodiments, the carbohydrate oxidase enzyme substrate is selected from the group consisting of The D-glucose 2-deoxy-D-glucose, 4-O-methyl-D-glucose, 6-deoxy-D- glucose, 4-deoxy-D-glucose, 3-deoxy-D-glucose, 3-O-methyl-D-glucose and mixtures thereof.
The composition of the invention preferably comprises from 2 to 35 wt. %, more preferably from 5 to 33 wt. %, even more preferably from 10 to 30 wt.% and still more preferably from 11 to 25 wt.% of the carbohydrate substrate. Such levels of carbohydrate substrate were found to be more optimal for the removal of tea-stains especially at low- medium temperatures. The surfactant system comprises non-ionic surfactant. Preferably the composition comprises anionic surfactants, cationic surfactants and amphoteric/zwitterionic surfactants and mixtures thereof. In general, the non-ionic and or anioninc surfactants of the Surfactant System may be chosen from the surfactants described in “Surface Active Agents' Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, InterScience 1958, in the current edition of “McCutcheon's Emulsifiers and Detergents' published by Manufacturing Confectioners Company or in “Tenside-Taschenbuch”, H. Stache, 2nd Edn., Carl Hauser Veriag, 1981. Suitable non-ionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific non-ionic detergent compounds are C-C alkyl phenol ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs-Cs primary or Secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.
In a preferred embodiment, the machine dishwashing composition comprises a non-ionic surfactant system selected from a C10-20 fatty acid, an alkoxylated fatty alcohol, an alkoxylated fatty acid, alkylphenol alkoxylates, alkoxylated amines, alkoxylated fatty acid amides, terminally blocked alkoxylates, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine-oxides, sulphoxides, phosphine oxides, more preferably selected from a C10-20 fatty acid, an ethoxylated fatty alcohol, an ethoxylated fatty acid, alkylphenol ethoxylates, ethoxylated amines, ethoxylated fatty acid amides, terminally blocked ethoxylates, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine-oxides, sulphoxides, phosphine oxides. Preferably, the machine dishwashing composition comprises from 0.1 to 15 wt.% non ionic surfactant, preferably 1.0 to 12.0 wt.% non-ionic surfactant, more preferably 2.0 to 8 wt.% non-ionic surfactant, most preferably 2.5 to 5 wt.% non-ionic surfactant. Preferably, the machine dishwashing composition comprises at most 5.0 wt. %, more preferably at most 4.0 wt. %, even more preferably at most 3.0 wt. %, still even more preferably at most 2.0 wt. % and still even more preferably at most 1.0 wt. % of anionic surfactant.
The machine dishwashing composition preferably comprises 10 to 50 wt.% carbonate salts, preferably selected from Na2CC>3, K2CO3, CaCCh or a combination of both, preferably 15 to 40 wt.% carbonate salts selected from Na2CC>3 and CaCCh or a combination of both, most preferably 20 to 30 wt. % carbonate, selected from Na2CC>3, CaCCh or a combination of both. In a preferable embodiment, the carbonate salt is Na2C03.
The term "builder" as used herein refers to a material that is capable of removing calcium and/or magnesium ion from aqueous solution by ion exchange, complexation, sequestration and/or precipitation. The builder or sequestrant material is preferably fully soluble in water so as to eliminate the possibility of unwanted and unsightly residues on substrates. For that reason alkali metal aluminosilicates are not favoured. Typical examples of phosphorus containing inorganic builders, when present, include the water- soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates. Examples of suitable non-phosphorus water-soluble detergency builders, when present, include carbonate, citrate, zeolite, silicate and aminopolycarboxylic compounds, such as glutamate diacetic acid (GLDA), methylglycine diacetic acid (MGDA), and Trisodium Citrate. Other non-phosphorus water-soluble detergency builders may include inorganic builders as alkali metal carbonate, bicarbonates, sesquicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates, and organic builders as polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates. Bleach activator
The term "bleach activator" as used herein refers to compounds employed in cleaning compositions to activate the bleaching agent, or bleach component, especially at lower temperatures. Examples of bleach activators suitable for use in the cleaning compositions of this invention include one or more activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC). These and other related compounds are described in fuller detail by Grime and Clauss in-Chemistry & Industry (Oct. 15, 1990) 647653. The detergent composition of the invention may comprise from 0.01 to 15 wt. % of bleach activator, more preferably from 0.2 to 10 wt. % and even more preferably from 1.0 to 6 wt. %, but more preferably comprises no bleach activator. Bleach catalyst
Bleach catalysts function by oxidizing typically via peroxide or a peracid to form a bleaching species. They require the presence of an oxidizable soil so that they can be reduced back to the starting bleach activator state. The preferred bleach catalyst according used in the invention is a manganese complex of formula (A):
[LnMnmXp]zYq
.wherein Mn is manganese, which can be in the II, III, IV or V oxidation state or mixtures thereof; n and m are independent integers from 1-4; X represents a co-ordination or bridging species; p is an integer from 0-12; Y is a counter-ion, the type of which is dependent on the charge z of the complex which can be positive, zero or negative; q = z/[charge Y]; and L is a ligand being a macrocyclic organic molecule of the general formula: wherein R1 and R2 can each be zero, H, alkyl or aryl optionally substituted; t and t’ are each independent integers from 2-3; each D can independently be N, NR, PR, O or S, where R is H, alkyl or aryl, optionally substituted; and s is an integer from 2-5.
Such bleach catalysts are described in EP0458397A2. The preferred features of the manganese-based bleach catalyst described therein are preferred as well for the purposes of this invention and explicitly belong to the description of this invention. The preferred features referred to are described on pages 3 to 8 of EP0458397A2 insofar as relating to manganese-based bleach catalysts.
The bleach catalysts of the invention are more preferably one or more of:
• [Mnm2 (p-OMp-OAc)2(TACN)2] (CI04)2 ;
• [MnmMnlv (m-0)2(m-OAo)i (TACN)2] (BPh4)2 ;
• [Mhin 4 (m-0)6 (TACN)4] (CI04)4 ;
• [Mnm 2 (m-0)i (m-OAo)2 (Me-TACN)2] (CI04)2 ;
• [MnmMnlv (m-O)i (m-OA (Me-TACN)2] (PF6)2 ;
• [Mnlv 2 (m-0)3 (Me/Me-TACN)2] (PF6)2 ;
• [MhINMhin(m-0)2(m-OAo)i (Me-TACN)2] (BPh4)2 ;
• [Mnlv 2(p-0)3(Me-TACN)2] (PF6)2 ;
• [Mnm 2(p-0)i(u-0Ac)2(Me-TACN)2] (CI04)2 ; and
• [MhINMhin 4(m-0)i(m-OAo)2 (Me-TACN)2] (CI04)3. wherein 1 ,4,7-trimethy-1 ,4,7-triazacyclononane is coded as Me-TACN; 1 ,4,7- triazacyclononane is coded as TACN; 1,5,9-trimethyl-1 ,5,9-triazacyclododecane is coded as Me-TACD; 2-methyl-1 ,4,7-trimethyl-1,4,7-triazacyclononane is coded as Me/Me-TACN; and 2-methyl-1 ,4,7-triazacyclononane is coded as Me/TACN.
Of these the following are the even more preferred:
• [Mnlv 2(p-0)3(Me-TACN)2] (PF6)2 ;
• [Mnm 2(p-0)i(u-0Ac)2(Me-TACN)2] (CI04)2 ;
• [Mnlv 4(p-0)6(TACN)4] (CI04)4 ; and
• [MhINMhin 4(m-0)i(m-OAo)2 (Me-TACN)2] (CI04)3.
The still even more preferred bleach catalyst is Mnlv 2(p-0)3(Me-TACN)2] (PFe)2. The preferred amount of the bleach catalyst is from 0.001 to 2 wt. %, more preferably from 0.005 to 1 wt. %, even more preferably from 0.008 to 0.5 wt. % and still more preferably from 0.01 to 0.1 wt. %, as based on actives levels. The preferred form of adding the bleach catalyst is as of part of a bleach catalyst granule comprising less than 5 wt. % of active bleach catalyst. The use of such granules improves the accurate dosing of the bleach catalyst.
The detergent composition is preferably a powder, a tablet, an aqueous or non-aqueous liquid, a loose flowing powder, a paste, a capsule or a gel. Preferably, the composition is in the form a gel, a capsule or a tablet, more preferably a capsule.
The carbohydrate oxidase enzyme used in the present invention can usefully be added to the detergent composition in any suitable form, i.e. the form of a granular composition, a liquid or a slurry of the enzyme, or with carrier material. For example, adding the enzyme to a liquid detergent product is in the form of a slurry containing 0.5 to 50% by weight of the enzyme in an ethoxylated alcohol nonionic surfactant, such as described in EP-A-450702 (Unilever). In a preferred embodiment in which the machine dishwashing composition is a solid or flowing powder, the machine dishwashing composition preferably has a water content of less than 5 wt.%. An even more preferred embodiment is that in which the machine dishwashing composition is tablet with a water content of less than 5 wt.%. Preferably a 1 wt. % solution of the detergent composition in deionised water has a pH in the range of 8.5 - 11.0, more preferably 9.0 - 10.75 and most preferably 9.5 - 10.5. The pH being measured at 25 °C, in otherwise standard conditions.
The composition may be in the form of a unit dose, wherein the unit dose is a gel, powder, liquid or combination thereof.
Given the above, a preferred machine dishwash composition according to the invention comprises: a) from 0.02 to 0.3 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 30 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.0, as measured at 25 degrees Celsius and in otherwise standard conditions.
Given the above a more preferred machine dishwash composition according to the invention comprises, especially for use at a wash temperature of below 65 degrees Celsius: a) from 0.04 to 0.2 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 25 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.0, as measured at 25 degrees Celsius and in otherwise standard conditions; and wherein the composition further comprises from 0.01 to 1 wt. % bleach catalyst, wherein the bleach catalyst preferably comprises manganese complex of formula (A): [LnMnmXp]zYq
.wherein Mn is manganese, which can be in the II, III, IV or V oxidation state or mixtures thereof; n and m are independent integers from 1-4; X represents a co-ordination or bridging species; p is an integer from 0-12; Y is a counter-ion, the type of which is dependent on the charge z of the complex which can be positive, zero or negative; q = z/[charge Y]; and L is a ligand being a macrocyclic organic molecule of the general formula: wherein R1 and R2 can each be zero, H, alkyl or aryl optionally substituted; t and t’ are each independent integers from 2-3; each D can independently be N, NR, PR, O or S, where R is H, alkyl or aryl, optionally substituted; and s is an integer from 2-5.
Given the above an even more preferred machine dishwash composition according to the invention for use at a wash temperature above 65 degrees Celsius comprises: a) from 0.04 to 0.2 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 10 to 25 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.0, as measured at 25 degrees Celsius and in otherwise standard conditions; wherein little or no bleach activator and/or bleach catalyst is present.
The machine dish wash compositions of the invention preferably comprise no bleach precursor, although the presence of such does not negatively affect the tea-stain cleaning.
In a second aspect, there is provided a method of cleaning kitchenware comprising the steps of contacting a detergent composition as defined herein with kitchenware in the presence of water. Preferably, the method is carried out at a temperature in the range of 30 to 90 °C, more preferably 40 to 85 °C, even more preferably 50 to 80 °C. A high temperature wash conditions is defined as using a temperature of above 65 degrees Celsius; low-medium temperature wash conditions as a temperature of at most 65 degrees Celsius. The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the second aspect.
The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the third aspect.
Preferably the stain remover is active at a temperature in the range of 40 to 90 °C, more preferably 40 to 85 °C, even more preferably 50 to 80 °C. In a fourth aspect, there is provided a process of preparing compositions as described herein comprising the step of combining a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system.
In fifth aspect there is provided a process of preparing a unit dose according to any of the preceding claims comprising the step of: i. providing a carbohydrate oxidase enzyme, substrate for said enzyme and a non ionic surfactant system to provide a mixture, ii. forming the mixture of step (i) into a unit dose. The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the fourth and fifth aspects.
EXAMPLES General methods / reagents used
Example 1
The following compositions (1-5 and comparative A) were prepared, as shown in Table 1 : Table 1
1Maxapal® G04 (DSM, The Netherlands)
20.005 wt. % of active glucose oxidase enzyme equates to ~ 72 enzyme units per 18g of composition.
The following compositions 6 to 8 were prepared, as shown in Table 2:
Example 2
Stained tiles (DM-14 Dark Tea on Melamine; Supplier: Center For Test materials B.V.) were placed in a 5L solution made from dosing 18g according to formulations listed in Table 1 in water. Each solution was placed in a beaker under agitation and temperature controlled for 20min. The temperate was as indicated in Table 3. Scale: (-) poor to (+++) best) stain removing power:
Table 3

Claims

Claims
1. A machine dishwasher composition comprising: a) from 0.002 to 0.5 wt. % of active carbohydrate oxidase enzyme, preferably selected from the group consisting of alcohol oxidase, glucose oxidase, galactose oxidase, sorbose oxidase, hexose oxidase, aldose oxidase, and mixtures thereof, more preferably glucose oxidase; b) from 1 to 40 wt. % of the carbohydrate oxidase enzyme substrate and c) a surfactant system comprising non-ionic surfactant, wherein the pH of a 1 wt. % solution of the composition in deionized water is in the range of from 8.5 to 11.5, as measured at 25 degrees Celsius and in otherwise standard conditions.
2. The composition according to claim 1, composition comprises 0.01 to 0.4 wt.% active carbohydrate oxidase enzyme, preferably 0.02 to 0.3 wt.% carbohydrate oxidase enzyme, more preferably 0.04 to 0.2 wt.% and even more preferably from 0.045 to 0.08 wt. % of active carbohydrate oxidase enzyme.
3. The composition according to claims 1 or 2, wherein the carbohydrate oxidase enzyme is an Aspergillus niger glucose oxidase.
4. The composition according to claim 3, wherein the carbohydrate oxidase enzyme substrate is glucose.
5. The composition according to any of the preceding claims, comprising from 2 to 35 wt. %, preferably from 5 to 33 wt. % more preferably from 10 to 30 wt.% carbohydrate source and even more preferably from 11 to 25 wt.% of the carbohydrate source.
6. The composition according to claims any of the preceding claims, wherein the surfactant system comprises 1.0 to 15.0 wt.% non-ionic surfactant, more preferably 2.0 to 10 wt.%, most preferably 2.5 to 5 wt.%.
7. The composition according to claims any of the preceding claims, wherein the composition comprises a non-ionic surfactant system selected from a C10-20 fatty acid, an alkoxylated fatty alcohol, an alkoxylated fatty acid, alkylphenol alkoxylates, alkoxylated amines, alkoxylated fatty acid amides, terminally blocked alkoxylates, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine-oxides, sulphoxides, phosphine oxides, more preferably selected from a C10-20 fatty acid, an ethoxylated fatty alcohol, an ethoxylated fatty acid, alkylphenol ethoxylates, ethoxylated amines, ethoxylated fatty acid amides, terminally blocked ethoxylates, fatty acid esters of glycerol, fatty acid esters of sorbitol, fatty acid esters of sucrose, alkyl polyglucosides, amine- oxides, sulphoxides, phosphine oxides.
8. The composition according to any of the preceding claims, composition comprises 10 to 50 wt.% of water soluble alkali metal carbonate, preferably the water soluble alkali metal carbonate is selected from Na2CC>3 K2CO3 and CaCCh and combinations thereof.
9. The composition according to any of the preceding claims, wherein a 1 wt. % solution of the composition in deionised water has pH in the range of 8.5 - 11.0 preferably 9.0 - 10.75 and more preferably 9.5 - 10.5, as measured at 25 degrees Celsius.
10. The composition according to any of the preceding claims, wherein the composition in the form of a gel, a powder, an aqueous or non-aqueous liquid.
11. Unit dose comprising a composition according to any of the preceding claims, wherein the unit dose is a gel, powder, liquid or combination thereof.
12. Method of cleaning kitchenware comprising the steps of contacting the composition according to any of claims 1-10 or unit dose according to claim 11 with kitchenware in the presence of water, preferably at a temperature in the range of 30 to 90 °C.
13. Use of a composition according to any of claims 1-10 or unit dose according to claim 11 as (tea)stain remover, preferably as a sustainable/bio-based/green tea(stain) remover, wherein more preferably the stain remover is active at a temperature in the range of 30 to 90 °C, more preferably 40 to 90 °C and even more preferably 50-80 °C.
14. A process of preparing compositions according to any of the claims 1-10, comprising the step of combining a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system.
15. A process of preparing a unit dose according to any claim 11 : i. providing a carbohydrate oxidase enzyme, substrate for said enzyme and a non-ionic surfactant system to provide a mixture, ii. forming the mixture of step (i) into a unit dose.
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EP0450702A3 (en) 1990-04-06 1993-06-02 Unilever N.V. Process for preparing liquid enzymatic detergent compositions
DE69125309T2 (en) 1990-05-21 1997-07-03 Unilever Nv Bleach activation
EP0692947A4 (en) * 1993-04-09 1996-03-13 Procter & Gamble DISHWASHER WASHING METHOD USING AN ORGANOMETALLIC CATALYST AND AN ENZYME FOR PRODUCING HYDROGEN PEROXIDE
EP1002041B1 (en) 1997-07-09 2003-03-05 The Procter & Gamble Company Cleaning compositions comprising an oxidoreductase
DE102010039814A1 (en) * 2010-08-26 2012-03-01 Henkel Ag & Co. Kgaa Enzyme-containing machine dishwashing detergent
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