|
(11) | EP 4 045 621 B1 |
| (12) | EUROPEAN PATENT SPECIFICATION |
|
|
| (54) |
DETERGENT COMPOSITION REINIGUNGSMITTELZUSAMMENSETZUNG COMPOSITION DE DÉTERGENT |
|
|
|||||||||||||||||||||||||||||||
| Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). |
TECHNICAL FIELD OF THE INVENTION
[0001] 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
[0002] Machine dishwashing compositions comprising bleaching enzymes have been described in the prior art.
[0003] WO1999/002640 discloses cleaning compositions comprising oxidoreductase (non-haem haloperoxidase) with an α/β-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. WO94/23637 A1 discloses granular machine dishwashing compositions that comprise 1.5 wt.% non-ionic surfactant, 10 wt.% glucose and 250 units/gram glucose oxidase enzyme, which form an enzymatic source of hydrogen peroxide, having a pH of 10.7. The compositions decolorise blackcurrant juice stains and require bleach catalyst. Notorious hard to remove stains include tea stains, which require substantial bleaching power to remove. There remains a need for dishwasher compositions that are free of metal bleach catalysts and 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 yet provide (tea)-stain removing power.
SUMMARY OF THE INVENTION
[0004] 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.
[0005] Accordingly, the present invention relates to a machine dishwasher composition according to claim 1.
[0006] 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.
[0007] 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. 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.
[0008] 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.
[0009] 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.
[0011] 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
[0012] 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.
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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®GO4 (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).
[0017] 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.
[0018] 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 µmol 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.
[0019] The machine dishwashing composition preferably comprises 0.01 to 0.4 wt.% active carbohydrate oxidase enzyme. More 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.
[0020] 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.
[0021] 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.
[0022] The surfactant system comprises non-ionic surfactant. Preferably the composition comprises anionic surfactants, cationic surfactants and amphoteric/zwitterionic surfactants and mixtures thereof.
[0023] 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.
[0024] 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.
[0025] 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.
[0026] 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.
[0027] The machine dishwashing composition preferably comprises 10 to 50 wt.% carbonate salts, preferably selected from Na2CO3, K2CO3, CaCO3 or a combination of both, preferably 15 to 40 wt.% carbonate salts selected from Na2CO3 and CaCO3 or a combination of both, most preferably 20 to 30 wt. % carbonate, selected from Na2CO3, CaCO3 or a combination of both. In a preferable embodiment, the carbonate salt is Na2CO3.
[0028] 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
[0029] 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) 647 653. 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
[0030] 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.
[0031] Bleach catalyst can be 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.
[0033] Bleach catalysts can be one or more of:
- [MnIII2 (µ-O)1(µ-OAc)2(TACN)2] (ClO4)2;
- [MnIIIMnIV (µ-O)2(µ-OAc)1 (TACN)2] (BPh4)2;
- [MnIV4 (µ-O)6 (TACN)4] (ClO4)4;
- [MnIII2 (µ-O), (µ-OAc)2 (Me-TACN)2] (ClO4)2 ;
- [MnIIIMnIV (µ-O)1 (µ-OAc)2 (Me-TACN)2] (PF6)2;
- [MnIV2 (µ-O)3 (Me/Me-TACN)2] (PF6)2 ;
- [MnIIImnIV(µ-O)2(µ-OAc)1 (Me-TACN)2] (BPh4)2;
- [MnIV2(µ-O)3(Me-TACN)2] (PF6)2;
- [MnIII2(µ-O)1(u-OAc)2(Me-TACN)2] (ClO4)2; and
- [MnIIIMnIV4(µ-O)1(µ-OAc)2(Me-TACN)2] (ClO4)3.
[0034] Bleach catalyst can be 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.
[0035] 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.
[0036] 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).
[0037] 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.%.
[0038] 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.
[0039] The composition may be in the form of a unit dose, wherein the unit dose is a gel, powder, liquid or combination thereof.
[0040] 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,
[0041] 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,
[0042] 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.
[0043] 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.
[0044] The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the second aspect.
[0045] The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the third aspect.
[0046] 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.
[0047] 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.
[0048] 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.
[0049] The ingredients and amounts of the ingredients described herein apply mutatis mutandis to the fourth and fifth aspects.
EXAMPLES
General methods / reagents used
[0050] Compositions 1-3, 6, 7 and A are not according to the claims and are for illustrative purposes.
Example 1
[0051] The following compositions (1-5 and comparative A) were prepared, as shown in Table 1:
Table 1
| 1 | 2 | 3 | 4 | 5 | A | |
| Sodium percarbonate (wt.%) | - | - | - | - | - | - |
| Glucose Oxidase (wt.% active enzyme)1 | 20.005 | 0.005 | 0.05 | 0.1 | 0.05 | - |
| Glucose (wt.%) | 18.9 | 18.9 | 18.9 | 18.9 | 18.9 | - |
| Macrocyclic manganese bleach catalyst (MnCat) (wt.%) | 0.02 | 0.02 | 0.02 | - | - | 0.02 |
| Tetraacetyl ethylene diamine (TAED) (wt.%) | - | - | - | 10.7 | 10.7 | |
| Sodium Carbonate (wt.%) | - | 24.99 | 24.99 | 24.99 | 24.99 | 24.99 |
| Methylglycine diacetic acid (MGDA) (wt.%) | 26.41 | 26.41 | 26.41 | 26.41 | 26.41 | 26.41 |
| Non-lonic surfactant (wt.%) | 3.00 | 3.00 | 3.00 | 3.00 | 3.00 | 3.00 |
| Minor Ingredients (wt.%) | Up to balance | Up to balance | Up to balance | Up to balance | Up to balance | Up to balance |
| 1Maxapal® GO4 (DSM, The Netherlands) 20.005 wt. % of active glucose oxidase enzyme equates to ~ 72 enzyme units per 18g of composition. |
[0052] The following compositions 6 to 8 were prepared, as shown in Table 2:
| 6 | 7 | 8 | |
| Sodium percarbonate (wt.%) | - | - | - |
| Glucose Oxidase (wt.% active enzyme)1 | 0.05 | 0.05 | 0.05 |
| Glucose (wt.%) | 12.8 | 6.4 | 12.8 |
| Macrocyclic manganese bleach catalyst (MnCat) (wt.%) | 0.02 | 0.02 | - |
| Tetraacetyl ethylene diamine (TAED) (wt.%) | - | - | - |
| Sodium Carbonate (wt.%) | - | 24.99 | 24.99 |
| Methylglycine diacetic acid (MGDA) (wt.%) | 26.41 | 26.41 | 26.41 |
| Non-lonic surfactant (wt.%) | 3.00 | 3.00 | 3.00 |
Example 2
[0053] 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
| Wash temperature and length | Stain removing power | ||
| Comparative A | 50 °C | 20 minutes | - |
| Comparative B (Finish Tablet) | 50 °C | 20 minutes | + |
| 1 | 50 °C | 20 minutes | + |
| 2 | 50 °C | 20 minutes | ++ |
| 3 | 50 °C | 20 minutes | +++ |
| 4 | 50 °C | 20 minutes | +++ |
| 5 | 50 °C | 20 minutes | +++ |
| 6 | 50 °C | 20 minutes | ++ |
| 7 | 50 °C | 20 minutes | + |
| 8 | 80 °C | 20 minutes | +++ |
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,
wherein the composition is free of metal bleach catalyst.
2. The composition according to claim 1, wherein the 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 Na2CO3, K2CO3 and CaCO3 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
is 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 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.
1. Zusammensetzung für Maschinengeschirrspüler, umfassend:
a) 0,002 bis 0,5 Gew.-% aktives Kohlenhydratoxidase-Enzym, vorzugsweise ausgewählt aus der Gruppe, bestehend aus Alkoholoxidase, Glucoseoxidase, Galactoseoxidase, Sorboseoxidase, Hexoseoxidase, Aldoseoxidase und Mischungen davon, besonders bevorzugt Glucoseoxidase;
b) 1 bis 40 Gew.-% des Kohlenhydratoxidase-Enzymsubstrats und
c) ein Tensidsystem, umfassend nicht-ionisches Tensid,
wobei der pH-Wert einer 1-gew.-%igen Lösung der Zusammensetzung in entionisiertem Wasser in dem Bereich von 8,5 bis 11,5 liegt, gemessen bei 25 Grad Celsius und bei sonst üblichen Bedingungen,
wobei die Zusammensetzung frei von Metallbleichkatalysator ist.
2. Zusammensetzung nach Anspruch 1, wobei die Zusammensetzung 0,01 bis 0,4 Gew.-% aktives
Kohlenhydratoxidase-Enzym, vorzugsweise 0,02 bis 0,3 Gew.-% Kohlenhydratoxidase-Enzym,
bevorzugter 0,04 bis 0,2 Gew.-% und noch bevorzugter 0,045 bis 0,08 Gew.-% aktives
Kohlenhydratoxidase-Enzym umfasst.
3. Zusammensetzung nach Anspruch 1 oder 2, wobei das Kohlenhydratoxidase-Enzym eine Aspergillus
niger-Glucoseoxidase ist.
4. Zusammensetzung nach Anspruch 3, wobei das Kohlenhydratoxidase-Enzymsubstrat Glucose
ist.
5. Zusammensetzung nach einem der vorhergehenden Ansprüche, umfassend 2 bis 35 Gew.-%,
vorzugsweise 5 bis 33 Gew.-%, bevorzugter 10 bis 30 Gew.-% Kohlenhydratquelle und
noch bevorzugter 11 bis 25 Gew.-% Kohlenhydratquelle.
6. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei das Tensidsystem 1,0
bis 15,0 Gew.-%, bevorzugter 2,0 bis 10 Gew.-%, höchst bevorzugt 2,5 bis 5 Gew.-%
nicht-ionisches Tensid umfasst.
7. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung
umfasst ein nicht-ionisches Tensidsystem, ausgewählt unter einer C10-C20-Fettsäure,
einem alkoxylierten Fettalkohol, einer alkoxylierten Fettsäure, Alkylphenolalkoxylaten,
alkoxylierten Aminen, alkoxylierten Fettsäureamiden, endständig blockierten Alkoxylaten,
Fettsäureestern von Glycerin, Fettsäureestern von Sorbit, Fettsäureestern von Saccharose,
Alkylpolyglucosiden, Aminoxiden, Sulfoxiden, Phosphinoxiden, bevorzugter ausgewählt
unter einer C10-C20-Fettsäure, einem ethoxylierten Fettalkohol, einer ethoxylierten
Fettsäure, Alkylphenolethoxylaten, ethoxylierten Aminen, ethoxylierten Fettsäureamiden,
endständig blockierten Ethoxylaten, Fettsäureestern von Glycerin, Fettsäureestern
von Sorbit, Fettsäureestern von Saccharose, Alkylpolyglucosiden, Aminoxiden, Sulfoxiden,
Phosphinoxiden.
8. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung
10 bis 50 Gew.-% wasserlösliches Alkalimetallcarbonat umfasst, wobei das wasserlösliche
Alkalimetallcarbonat vorzugsweise unter Na2CO3, K2CO3 und CaCO3 und Kombinationen davon ausgewählt ist.
9. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei eine 1-gew.-%ige Lösung
der Zusammensetzung in entionisiertem Wasser einen pH-Wert in dem Bereich von 8,5
- 11,0, vorzugsweise 9,0 - 10,75 und bevorzugter 9,5 - 10,5, gemessen bei 25 Grad
Celsius, aufweist.
10. Zusammensetzung nach einem der vorhergehenden Ansprüche, wobei die Zusammensetzung
in Form eines Gels, eines Pulvers, einer wässrigen oder nichtwässrigen Flüssigkeit
vorliegt.
11. Einheitsdosis, umfassend eine Zusammensetzung nach einem der vorhergehenden Ansprüche,
wobei die Einheitsdosis ein Gel, ein Pulver, eine Flüssigkeit oder eine Kombination
davon ist.
12. Verfahren zum Reinigen von Küchengeschirr, umfassend die Schritte des Kontaktierens
der Zusammensetzung nach einem der Ansprüche 1-10 oder der Einheitsdosis nach Anspruch
11 mit Küchengeschirr in Gegenwart von Wasser, vorzugsweise bei einer Temperatur in
dem Bereich von 30 bis 90°C.
13. Verwendung einer Zusammensetzung nach einem der Ansprüche 1-10 oder einer Einheitsdosis
nach Anspruch 11 als Teefleckenentferner, vorzugsweise als nachhaltiger/bio-basierter/Grüntee-Fleckenentferner,
wobei der Fleckenentferner besonders bevorzugt bei einer Temperatur in dem Bereich
von 30 bis 90°C, bevorzugter von 40 bis 90°C und sogar bevorzugter von 50-80°C aktiv
ist.
14. Verfahren zur Herstellung von Zusammensetzungen nach einem der Ansprüche 1 bis 10,
umfassend den Schritt des Kombinierens eines Kohlenhydratoxidase-Enzyms, eines Substrats
für das Enzym und eines nicht-ionischen Tensidsystems.
15. Verfahren zur Herstellung einer Einheitsdosis nach Anspruch 11:
i. Bereitstellen eines Kohlenhydratoxidase-Enzyms, eines Substrats für das Enzym und eines nicht-ionischen Tensidsystems, um eine Mischung bereitzustellen,
ii. Formen der Mischung von Schritt (i) zu einer Einheitsdosis.
1. Composition pour lave-vaisselle comprenant :
a) de 0,002 à 0,5 % en masse d'enzyme de carbohydrate oxydase active, de préférence choisie dans le groupe consistant en alcool oxydase, glucose oxydase, galactose oxydase, sorbose oxydase, hexose oxydase, aldose oxydase, et des mélanges de celles-ci, encore mieux glucose oxydase ;
b) de 1 à 40 % en masse de l'enzyme de carbohydrate oxydase d'un substrat et
c) un système de tensioactif comprenant un tensioactif non-ionique,
dans laquelle le pH d'une solution à 1 % en masse de la composition dans de l'eau désionisée se trouve dans l'intervalle de 8,5 à 11,5, comme mesuré à 25 degrés Celsius et dans des conditions par ailleurs standard,
dans laquelle la composition est exempte de catalyseur de blanchiment à base de métal.
2. Composition selon la revendication 1, dans laquelle la composition comprend 0,01 à
0,4 % en masse d'enzyme de carbohydrate oxydase active, de préférence 0,02 à 0,3 %
en masse d'enzyme de carbohydrate oxydase, encore mieux 0,04 à 0,2 % en masse et bien
mieux encore 0,045 à 0,08 % en masse d'enzyme de carbohydrate oxydase active.
3. Composition selon la revendication 1 ou 2, dans laquelle l'enzyme de carbohydrate
oxydase est une glucose oxydase d'Aspergillus niger.
4. Composition selon la revendication 3, dans laquelle le substrat d'enzyme de carbohydrate
oxydase est le glucose.
5. Composition selon l'une quelconque des revendications précédentes, comprenant de 2
à 35 % en masse, de préférence de 5 à 33 % en masse encore mieux de 10 à 30 % en masse
de source de carbohydrate et bien mieux encore de 11 à 25 % en masse de la source
de carbohydrate.
6. Composition selon l'une quelconque des revendications précédentes, dans laquelle le
système de tensioactif comprend de 1,0 à 15,0 % en masse de tensioactif non-ionique,
encore mieux de 2,0 à 10 % en masse, bien mieux encore de 2,5 à 5 % en masse.
7. Composition selon l'une quelconque des revendications précédentes, dans laquelle la
composition comprend un système de tensioactif non-ionique choisi parmi un acide gras
en C10-20, un alcool gras alcoxylé, un acide gras alcoxylé, des alcoxylates d'alkylphénol,
amines alcoxylées, amides d'acides gras alcoxylés, alcoxylates bloqués en terminaison,
esters d'acides gras de glycérol, esters d'acides gras de sorbitol, esters d'acides
gras de saccharose, alkyl polyglucosides, amine-oxydes, sulfoxydes, oxydes de phosphine,
encore mieux choisis parmi un acide gras en C10-20, un alcool gras éthoxylé, un acide
gras éthoxylé, des éthoxylates d'alkylphénol, amines éthoxylées, amides d'acides gras
éthoxylés, éthoxylates bloqués en terminaison, esters d'acides gras de glycérol, esters
d'acides gras de sorbitol, esters d'acides gras de saccharose, alkyl polyglucosides,
amine-oxydes, sulfoxydes, oxydes de phosphine.
8. Composition selon l'une quelconque des revendications précédentes, qui comprend de
10 à 50 % en masse de carbonate de métal alcalin soluble dans l'eau, le carbonate
de métal alcalin soluble dans l'eau est de préférence choisi parmi Na2CO3, K2CO3 et CaCO3 et des combinaisons de ceux-ci.
9. Composition selon l'une quelconque des revendications précédentes, dans laquelle une
solution à 1 % en masse de la composition dans de l'eau désionisée présente un pH
dans l'intervalle de 8,5 - 11,0, de préférence 9,0 - 10,75 et encore mieux 9,5 - 10,5,
comme mesuré à 25 degrés Celsius.
10. Composition selon l'une quelconque des revendications précédentes, dans laquelle la
composition est dans la forme d'un gel, d'une poudre, d'un liquide aqueux ou non aqueux.
11. Dose unitaire comprenant une composition selon l'une quelconque des revendications
précédentes, dans laquelle la dose unitaire est un gel, une poudre, un liquide ou
une combinaison de ceux-ci.
12. Procédé de lavage de vaisselle comprenant les étapes de mise en contact de la composition
selon l'une quelconque des revendications 1-10 ou d'une dose unitaire selon la revendication
11 avec de la vaisselle en présence d'eau, de préférence à une température dans l'intervalle
de 30 à 90°C.
13. Utilisation d'une composition selon l'une quelconque des revendications 1-10 ou d'une
dose unitaire selon la revendication 11 comme agent d'élimination de tache de thé,
de préférence comme un agent d'élimination de tache de thé vert/de base bio/durable,
dans laquelle l'agent d'élimination de tache est encore mieux actif à une température
dans l'intervalle de 30 à 90°C, encore mieux 40 à 90°C et bien mieux encore 50-80°C.
14. Procédé de préparation de compositions selon l'une quelconque des revendications 1-10,
comprenant l'étape de combinaison d'une enzyme de carbohydrate oxydase, d'un substrat
pour ladite enzyme et d'un système de tensioactif non-ionique.
15. Procédé de préparation d'une dose unitaire selon la revendication 11 :
i. en fournissant une enzyme de carbohydrate oxydase, un substrat pour ladite enzyme et un système de tensioactif non-ionique pour fournir un mélange,
ii. en façonnant le mélange de l'étape (i) en une dose unitaire.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.
Patent documents cited in the description
Non-patent literature cited in the description
- CHEMICAL ABSTRACTS, 9001-37-0 [0016]
- SCHWARTZPERRYSurface Active AgentsInterscience19490000vol. 1, [0023]
- SCHWARTZPERRYBERCHSurface Active AgentsInterScience19580000vol. 2, [0023]
- McCutcheon's Emulsifiers and DetergentsManufacturing Confectioners Company [0023]
- H. STACHETenside-TaschenbuchCarl Hauser Veriag19810000 [0023]
- GRIMECLAUSSChemistry & Industry, 1990, 647-653 [0029]