EP0636170B1 - Enzym enthaltendes, flüssiges, thixotropes maschinengeschirrspülmittel - Google Patents

Enzym enthaltendes, flüssiges, thixotropes maschinengeschirrspülmittel Download PDF

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Publication number
EP0636170B1
EP0636170B1 EP93909464A EP93909464A EP0636170B1 EP 0636170 B1 EP0636170 B1 EP 0636170B1 EP 93909464 A EP93909464 A EP 93909464A EP 93909464 A EP93909464 A EP 93909464A EP 0636170 B1 EP0636170 B1 EP 0636170B1
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Prior art keywords
composition
sodium
enzyme
mixtures
group
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French (fr)
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EP0636170A1 (de
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Janet Layne Marshall
David Lee Hall
Hal Ambuter
Edward Paul Fitch
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Procter and Gamble Co
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Procter and Gamble Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to a viscoelastic, thixotropic, liquid automatic dishwashing detergent composition which is substantially free of chlorine bleach and silicate.
  • the automatic dishwashing composition contains enzyme, an enzyme stabilizing system, and detergent builder. It has a product pH between greater than 9 and 11 such that the diluted pH of 1% aqueous solution of said composition is also greater than 9.
  • liquid and/or gel automatic dishwashing detergent compositions are becoming an increasingly popular alternative to granular compositions among consumers.
  • liquid and/or gel formulations often do not deliver the same effective cleaning, spotting and filming performance as a granular composition.
  • liquid/gel and granular automatic dishwashing detergents contain chlorine bleach and have high alkalinity (i.e. silicate, carbonate and caustic). See, for example, U.S. Patents 4,116,849, Leikhim, issued September 26, 1978, 5,064,553, Dixit et al, issued November 12, 1991 and 4,917,812, Cilley, issued April 17, 1990.
  • Incorporation of chlorine bleaches requires special processing and storage steps to protect detergent composition components which are subject to deterioration upon contact with active chlorine.
  • Automatic detergent compositions have been disclosed which use enzymes in place of chlorine bleach, for example, U.S. Patents 4,162,987. Maguire et al, issued July 31, 1979, 4,101,457, Place et al, issued July 18, 1978 and 5,075,027, Dixit et al, issued December 24, 1991.
  • FR-A-2,608,168 describes a detergent composition containing an enzyme stabilising system and the use of said detergent composition in a dishwashing method.
  • EP-A-0,530,635 published on 10.03.93, describes a detergent composition of pH from 5 to 9 containing hydroxy carboxylic acid or salts thereof.
  • a viscoelastic thixotropic liquid automatic dishwashing detergent can be formed with performance equal to or better than that of comparable granular products.
  • a low alkaline product pH (between greater than 9 and 11) such that the diluted pH of a 1% aqueous solution of said composition is also greater than 9 liquid composition which is substantially free of chlorine and silicate exhibits enhanced cleaning, spotting and filming ability.
  • the cleaning benefit is achieved via the presence of enzymes and surfactant and/or builder in the composition. Removal of chlorine bleach and a lower product pH results in a composition which is safer to dishwasher articles (i.e. china, silverware, glass, and the like).
  • a viscoelastic, thixotropic, liquid automatic dishwashing detergent composition which is substantially free of chlorine bleach and silicate, and which contains enzymes and citrate, can provide performance benefits equal to or better than granular detergent compositions containing bleach, silicate and phosphate.
  • the replacement of phosphate as the builder of choice with citrate or citric acid results in additional dishwasher article safety.
  • composition of this invention is a viscoelastic, thixotropic, liquid automatic dishwashing detergent composition comprising, by weight:
  • a particularly preferred embodiment of this invention is a gel automatic dishwasning detergent composition further comprising, by weight, from 0.01% to 6% of chlorine scavenger.
  • the present invention encompasses viscoelastic, thixotropic, liquid automatic detergent compositions which exhibit enhanced cleaning performance in the absence of chlorine bleach and silicate.
  • These detergent compositions contain the following components by might of the composition:
  • a particularly preferred composition is a gel formulation.
  • thixotropic means the material exhibits a decrease in viscosity with increasing shear. In other words it exhibits high viscosity when subjected to low stress and lower viscosity when subjected to high stress.
  • a viscoelastic liquid exhibits a steady state flow behaviour after a constant stress has been applied for a sufficiently long period of time.
  • compositions of this invention contain from 0.001% to 5%, more preferably from 0.003% to 4%. most preferably from 0.005% to 3%, by weight, of active detersive enzyme.
  • the preferred detersive enzyme is selected from the group consisting of protease, amylase, lipase and mixtures thereof. Most preferred are protease or amylase or mixtures thereof.
  • the proteolytic enzyme can be of animal vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred is bacterial serine proteolytic enzyme obtained from Bacillus , Bacillus subtilis and/or Bacillus licheniformis .
  • Suitable proteolytic enzymes include Alcalase®, Esperase®, Savinase® (preferred); Maxatase®, Maxacal® (preferred), and Maxapem® 15 (protein engineered Maxacal); and subtilisin BPN and BPN' (preferred); which are commercially available.
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application 251,446, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to modified bacterial serine proteolytic enzyme which is called "Protease A” herein.
  • Preferred proteolytic enzymes are selected from the group consisting of Savinase®, Esperase®, Maxacal®, BPN Protease A and Protease B, and mixtures thereof. Esperase® is most preferred.
  • Suitable lipases for use herein include those of bacterial, animal, and fungal origin, including those from chemically or genetically modified mutants.
  • Suitable bacterial lipases include those produced by Pseduomonas , such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372.034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced the the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978.
  • Lipas P Lipas P
  • Such lipases should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Oucheterlon (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • Oucheterlon Acta. Med. Scan., 133, pages 76-79 (1950)
  • These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987.
  • Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum var. lipolyticum NRRlb 3673, and further Chromobacter viscousm lipases, and lipases ex Pseudomonas gladioli .
  • Other lipases of interest are Amano AKG and Bacillis Sp lipase (e.g. Solvay enzymes).
  • lipases which are of interest where they are compatible with the composition are those described in EP A 0 339 681, published November 28, 1990, EP A 0 385 401, published September 5, 1990, EP A 0 218 272, published April 15, 1987, and WO-A-89/04361, published May 18, 1989.
  • Suitable fungal lipases include those produced by Humicola lanuginosa and Thermomyces lanuginosus . Most preferred is lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European Patent Application 0 258 068, commercially available under the trade name Lipolase® from Novo-Nordisk.
  • Amylases include for example, ⁇ -amylases obtained from a special strain of B. licheniforms , described in more detail in British Patent Specification No. 1,296,839.
  • Amylolytic enzymes include, for example, RapidaseTM, MaxamylTM, TermamylTM and BANTM.
  • active amylase in a preferred embodiment, from 0.001% to 5%, preferably 0.005% to 3%, by weight of active amylase can be used. Preferably from 0.005% to 3% by weight of active protease can be used.
  • amylase is MaxamylTM and/or TermamylTM and the protease is Esperase® and/or Savinase®.
  • the viscoelastic, thixotropic thickening agent in the compositions of the present invention is from 0.1% to 10%, preferably from 0.25% to 5%, most preferably from 0.5% to 3%, by weight of the detergent composition.
  • the viscoelastic, thixotropic thickening agent is free of any enzymatically reactive species. Without being bound by theory, it is believed that the enzyme(s) present in the automatic detergent composition could degrade the thickening agent which contains such species, resulting in a rheologically unstable product.
  • the thickening agent is a polymer with a molecular weight from 500.000 to 10,000,000, more preferably from 750,000 to 4,000,000.
  • the preferred cross-linkedpolycarboxylate polymer is preferably a carboxyvinyl polymer.
  • carboxyvinyl polymer Such compounds are disclosed in U.S. Patent 2,798,053, issued on July 2, 1951, to Brown. Methods for making carboxyvinyl polymers are also disclosed in Brown. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
  • Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccarides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol; most preferred is sucrose or pentaerythritol. It is preferred that the hydroxyl groups of the modified poiyol be etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether of the polyol comprise from 0.1% to 4% of the total monomers, more preferably from 0.2% to 2.5%.
  • Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, polymerizable. alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure where R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
  • Carbopol® Various carboxyvinyl polymers, homopolymers and copolymers are commercially available from B.F. Goodrich Company, New York, N.Y., under the trade name Carbopol®. These polymers are also known as carbomers or polyacrylic acids.
  • Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of 750,000. Carbopol 941 having a molecular weight of 1,250,000, and Carbopols 934 and 940 having molecular weights of 3,000,000 and 4,000.000, respectively. More preferred are the series of Carbopols which use ethyl acetate and cyclohexane in the manufacturing process, Carbopol 981, 2984, 980, and 1382.
  • Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with polyalkenyl polyether and having a molecular weight of from 750.000 to 4,000,000.
  • polycarboxylate polymers for use in the present invention are Sokalan PHC.25®, a polyacrylic acid available from BASF Corporation, the Carbopol 600 series resins available from B.F. Goodrich. and more preferred is Polygel DK available from 3-V Chemical Corporation. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention.
  • the polycarboxylate polymer thickening agent is preferably utilized with essentially no clay thickening agents since the presence of clay usually results in a less desirable product having phase instability.
  • the polycarboxylate polymer is preferably used instead of clay as a thickening agent in the present compositions, although clay can be used if so desired.
  • the preferred clay thickening agent can be either naturally occurring or synthetic.
  • a preferred synthetic clay is the one disclosed in U.S. Patent 3,843,598.
  • Naturally occurring clays include some smectite and attapulgite clays as disclosed in U.S. Patent 4,824,590.
  • the ceilulosic type thickeners: hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCEL® available from Dow Chemical) can also be used.
  • the polycarboxylate polymer thickening agent provides an apparent viscosity at high shear of greater than 250 centipoise and an apparent yield value of from 40 to 800, and most preferably from 60 to 600, dynes/cm 2 to the composition.
  • Viscosity is a measure of the internal resistance to flow exhibited by a fluid in terms of the ratio of the shear stress to the shear rate.
  • the yield value is an indication of the shear stress at which the gel strength is exceed and flow is initiated. Yield value can be measured herein with a Brookfield RVT model viscometer with a T-bar B spindle at about 77°F (25°C) utilizing a Helipath drive during associated readings.
  • the system is set to 0.5 rpm and a torque reading is taken for the composition to be tested after 30 seconds or after the system is stable.
  • the system is stopped and the rpm is reset to 1.0 rpm.
  • a torque reading is taken for the same composition after 30 seconds or after the system is stable.
  • a preferred method herein for measuring viscosity and yield value is with Contraves Rheomat 115 viscometer which utilizes a Rheoscan 100 controller, a DINI 45 spindle and cup at 25°C.
  • the shear rate is increased from 0 to 150 sec-1 over 30 second time period.
  • the viscosity, measured in centipoise, is taken at a shear rate of 150 sec-1.
  • the shear rate for yield value measurements is increased linearly from 0 to 0.4 sec-1 over period of 500 seconds after an initial 5 minute rest period.
  • compositions herein comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight, of an enzyme stabilizing system.
  • the enzyme stabilizing system is selected from the group consisting of calcium ion, boric acid, propylene glycol, short chain carboxylic acid. boronic acid, polyhydroxyl compounds and mixtures thereof.
  • the level of calcium ion should be selected so that there is always some minimum level available for the enzyme. after allowing for complexation with builders, etc., in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, and calcium acetate.
  • a small amount of calcium ion is often also present in the composition due to calcium in the enzyme and formula water.
  • calcium ions are used with a suitable salt of boric acid, described herein below, they can associate to form calcium borate which is insoluble in cold water and under certain product conditions can be insoluble above pH 9. This precipitate can lead to phase instability, decrease in effective enzyme stabilization and undesired product aesthetics.
  • a sufficient amount of calcium ion and boric acid or the salt of boric acid should be used to achieve enzyme stability without affecting phase stability, enzyme stability, or aesthetics. From 0.03% to 0.6%, more preferably from 0.05% to 0.45% of calcium formate is preferred.
  • Suitable enzyme stabilizing systems comprise polyols containing only carbon, hydrogen and oxygen atoms. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2-propanediol, which is preferred), 1,2-butanediol, ethylene glycol, glycerol, sorbitol, mannitol, and glucose.
  • the polyol generally represents from 0.5% to 10%, preferably from 1.5% to 8%, by weight of the composition.
  • the weight ratio of polyol to a boric acid added is at least 1, most preferably at least 1.3.
  • compositions can also contain the water-soluble short chain carboxylates described in U.S. Patent 4,318.818. Letton et al., issued March 9, 1982.
  • the formates are preferred and can be used at levels from 0.05% to 5%, preferably from 0.075% to 2.5%, most preferably from 0.1% to 1.5%, by weight.
  • Sodium formate is preferred.
  • Another stabilizing system comprises from 0.05% to 7%, preferably from 0.1% to 5%, by weight of boric acid.
  • the boric acid may be, but is preferably not, formed by a compound capable of forming boric acid in the composition.
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium orthometa- and pyroborate, and sodium pentaborate) are suitable.
  • Still another enzyme stabilizing system includes polyhydroxyl compounds, such as sugar alcohols, monosaccharides and disaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-soluble sodium or potassium salts and water-soluble hydroxy alcohols, as disclosed in U.S. Published Patent Application B-458,819, Weber, published April 13, 1976; diamines and polyamines, as disclosed in German Pat. No. 2,058,826; amino acids, as disclosed in German Pat. No. 2,060,485; and reducing agents, as disclosed in Japanese Pat. No. 72-20235.
  • polyhydroxyl compounds such as sugar alcohols, monosaccharides and disaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-soluble sodium or potassium salts and water-soluble hydroxy alcohols, as disclosed in U.S. Published Patent Application B-458,819, Weber, published April 13, 1976
  • diamines and polyamines as disclosed in German Pat. No. 2,058,826
  • amino acids as disclosed in German Pat.
  • the enzyme mixture may be incorporated into the detergent composition in a coated, encapsulated, agglomerated, prilled, or noodled form in accordance with, e.g., U.S. Patent 4,162,987, Maguire et al. issued July 31, 1979.
  • Substituted boric acids can also be used in place of boric acid.
  • a particularly preferred boronic acid is an aryl boronic acid of the structure: where x is selected from C 1 -C 6 alkyl, substituted C 1 C 6 alkyl, aryl, substituted aryl, hydroxyl, hydroxyl derivative, amine C 1 -C 6 alkylated amine, amine derivative, halogen, nitro, thiol, thio derivative, aldehyde, acid, acid salt, ester, sulfonate or phosphonate; each Y is independently selected from hydrogen, C 1 -C 6 alkyl, substituted C 1 C 6 alkyl, aryl, substituted aryl, hydroxyl, hydroxyl derivative, halogen, amine, alkylated amine, amine derivative, nitro, thiol
  • chlorine bleach scavengers can be added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate or iodide, antioxidants like carbamate or ascorbate, organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate or iodide
  • antioxidants like carbamate or ascorbate
  • organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof and monoethanolamine (MEA), and mixtures thereof.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • the preferred ammonium salts can be simply admixed with the detergent composition, they are prone to adsorb water and/or give off ammonia gas. Accordingly, it is better if they are protected in a particle like that described in U.S. Patent 4,652,392, Baginski et al.
  • the preferred ammonium salts or other salts of the specific chlorine scavenger anions can either replace the suds controlling agent or be added in addition to the suds controlling agent.
  • one or more buffering agents can be included which are capable of maintaining the pH of the compositions within the desired alkaline range.
  • the pH of the undiluted composition (“as is") is determined at room temperature (about 20°C) with a pH meter. It is in the low alkaline pH range that optimum performance and stability of the enzyme are realized. and it is also within this pH range wherein optimum compositional chemical and physical stability are achieved. Maintenance of the composition pH between greater than 9 and 11 such that the diluted pH of a 1% aqueous solution of said composition is also greater than 9 minimizes undesirable degradation of the active enzymes. Maintenance of this particular pH range also maximizes the soil and stain removal properties and prevents spotting and filming during utilization of the present compositions.
  • the pH adjusting agents are generally present in a level from 0.001% to 25%, preferably 0.5% to 20% by weight of the detergent composition.
  • any compatible material or mixture of materials which has the effect of maintaining the composition pH within the pH range of greater than 9 to 11 such that the diluted pH of a 1% aqueous solution of said composition is also greater than 9 can be utilized as the pH adjusting agent in the instant invention.
  • Such agents can include, for example, various water-soluble, inorganics salts such as the carbonates, bicarbonates, sesquicarbonates, pyrophosphates, phosphates, tetraborates, and mixtures thereof. Silicates are not included because of their high alkaline buffering properties.
  • Examples of preferred materials which can be used either alone or in combination as the pH adjusting agent herein include sodium carbonate, sodium bicarbonate, potassium carbonate, sodium sequicarbonate, sodium pyrophosphate, tetrapotassium pyrophosphate, tripotassium phosphate, trisodium phosphate, organic amines and their salts such as monoethanol amine (MEA), anhydrous sodium tetraborate, sodium tetraborate pentahydrate, potassium hydroxide, sodium hydroxide, and sodium tetraborate decahydrate. Combinations of these pH adjusting agents, which include both the sodium and potassium salts, may be used.
  • compositions of this invention can contain from 0.01% to 40%, preferably from 0.1% to 30% of a detergent surfactant which preferably results in a low foaming detergent composition.
  • a detergent surfactant which preferably results in a low foaming detergent composition.
  • the detergent surfactant is low foaling or which in combination with other components (i.e. suds suppressors) is low foaming.
  • the surfactant is a low foaming surfactant.
  • the surfactant employed is preferably enzyme stable (enzyme compatible) and free of enzymatically reactive species.
  • the surfactant should be free of peptide or glycosidic bonds.
  • Desirable detergent surfactants include nonionic, anionic, amphoteric and zwitterionic detergent surfactants, and mixtures thereof.
  • nonionic surfactants examples include:
  • Useful surfactants in detergent compositions are those having the formula RO-(C 2 H 4 O) x R 1 wherein R is an alkyl or alkylene group containing from 17 to 19 carbon atoms, x is a number from 6 to 15, preferably from 7 to 12, and R 1 is selected from the group consisting of: preferably, hydrogen, C 1-5 alkyl groups, C 2-5 acyl groups and groups having the formula -(C y H 2y O) n H wherein y is 3 or 4 and n is a number from one to about 4.
  • Particularly suitable surfactants are the low-sudsing compounds of (4), the other compounds of (5), and the C 17- C 19 materials of (1) which have a narrow ethoxy distribution.
  • Certain of the block co-polymer surfactant compounds designated PLURONIC, PLURAFAC® and TETRONIC® by the BASF Corp., Parsippany, N.J. are suitable as the surfactant for use herein.
  • a particularly preferred embodiment contains from 40% to 70% of a polyoxypropylene, polyoxethylene block polymer blend comprising 15%, by weight of the blend, of a reverse block co-polymer of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 mole of propylene oxide; and 25%, by weight of the blend, of a block co-polymer of polyoxyethylene and polyoxypropylene, initiated with tri-methylol propane, containing 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylol propane.
  • nonionic type surfactants which may be employed have melting points at or above ambient temperatures, such as octyldimethylamine N-oxide dihydrate, decyldimethylamine N-oxide dihydrate or C8-C12 N-methyl-glucamides.
  • Such surfactants may advantageously be blended in the instant compositions with short-chain anionic surfactants, such as sodium octyl sulfate and similar alkyl sulfates, though short-chain sulfonates such as sodium cumene sulfonate could also be used.
  • Anionic surfactants which are suitable for the compositions of the present invention include, but are not limited to, water soluble-alkyl sulfates and/or sulfonates, containing from 8 to 18 carbon atoms.
  • Natural fatty alcohols include those produced by reducing the glycerides of naturally occurring fats and oils. Fatty alcohols can be produced synthetically, for example, by the Oxo process. Examples of suitable alcohols which can be employed in alkyl sulfate manufacture include decyl, lauryl, myristyl, palmityl and stearyl alcohols and the mixtures of fatty alcohols derived by reducing the glycerides of tallow and coconut oil.
  • alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alkyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, magnesium coconut alkyl sulfate, calcium coconut alkyl sulfate, potassium coconut alkyl sulfate and mixtures thereof.
  • a preferred sulfonated anionic surfactant is the alkali metal salt of secondary alkane sulfonates, an example of which is the Hostapur® SAS from Hoechst Celanese.
  • Another class of surfactants operable in the present invention are the water-soluble betaine surfactants. These materials have the general formula: wherein R 1 is an alkyl group containing from 8 to 22 carbon atoms; R 2 and R 3 are each lower alkyl groups containing from about 1 to 5 carbon atoms, and R 4 is an alkylene group selected from the group consisting of methylene, propylene, butylene and pentylene. (Propionate betaines decompose in aqueous solution and hence are not included in the instant compositions).
  • betaine compounds of this type include dodecyldimethylananonium acetate, tetradecyldimethylammonium acetate, hexadecyldimethylananonium acetate, alkyldimethylammonium acetate wherein the alkyl group averages about 14.8 carbon atoms in length, dodecyldimethylammonium butanoate, tetradecyldimethylammonium butanoate, hexadecyldimethylammonium butanoate, dodecyldimethylammonium hexanoate, hexadecyldimethylammonium hexanoate, tetradecyldiethylammonium pentanoate and tetradecyldipropylammonium pentanoate.
  • Especially preferred betaine surfactants include dodecyldimethylammonium acetate, dodecyldimethylammonium hexanoate, hexadecyldimethylammonium acetate, and hexadecyldimethylammonium hexanoate.
  • surfactants include amine oxides, phosphine oxides, and sulfoxides. However, such surfactants are usually high sudsing.
  • a disclosure of surfactants can be found in published British Patent Application 2,116,199A; U.S. Patent 4,005,027, Hartman; U.S. Patent 4,116,851, Rupe et al; U.S. Patent 3,985,668, Hartman; U.S. Patent 4,271,030, Brierley et al; and U.S. Patent 4,116,849, Leikhim.
  • alkyl phosphonates taught in U.S. Patent 4,105,573 to Jacobsen issued August 8, 1978.
  • Still other preferred anionic surfactants include the linear or branched alkali metal mono- and/or di-(C 8-14 ) alkyl diphenyl oxide nomo- and/or disulfonates, commercially available under the trade names DOWFAX® 3B-2 (sodium n-decyl diphenyloxide disulfonate) and DOWFAX® 2A-1. These and similar surfactants are disclosed in published U.K. Patent Applications 2,163,447A; 2,163,448A; and 2,164,350A.
  • Detergency builder is added to the present invention in levels from 3% to 40%, preferably from 3% to 30%, most preferably from 3% to 25% by weight of the composition.
  • the builders reduce the free calcium and/or magnesium ion concentration in a surfactant-containing aqueous solution, enhancing stain removal and providing additional cleaning benefits.
  • the builder is citric acid or an alkali metal citrate such as sodium citrate in levels preferably from 3% to 20% by weight of the composition.
  • compositions can contain organic dispersant which overcomes the problem of unsightly films which form on china and especially on glassware due to calcium- or magnesium-hardness-induced precipitation of pH-adjusting agents, especially carbonates, used herein.
  • the organic dispersants herein can be used at levels of 0 to 20%, typically from 0.5% to 17%, most preferably from 1% to 15% of the automatic dishwashing composition. Such organic dispersants are preferably water-soluble sodium polycarboxylates.
  • Polycarboxylate dispersants herein generally contain truly polymeric numbers of carboxylate groups, e.g., 8 or more, as distinct from carboxylate builders, sometimes called “polycarboxylates" in the art when, in fact, they have relatively low numbers of carboxylate groups such as four per molecule.
  • the organic dispersants are known for their ability to disperse or suspend calcium and magnesium "hardness", e.g., carbonate salts. Crystal growth inhibition.
  • organic dispersants are polyacrylates or acrylate-containing copolymers.
  • SOKALAN Polymeric Dispersing Agents. SOKALAN
  • These polyanionic materials are, as noted. usually available as viscous aqueous solutions, often having dispersant concentrations of 30-50%.
  • the organic dispersant is most commonly fully neutralized; e.g., as the sodium salt form.
  • Suitable polymers are generally at least partially neutralized in the form of their alkali metal, ammonium or other conventional cation salts.
  • the alkali metal, especially sodium salts are most preferred.
  • the molecular weight of such dispersants can vary over a wide range, it preferably is from 1,000 to 500,000, more preferably is from 2,000 to 250,000, and most preferably is from 3,000 to 100,000. Nonlimiting examples of such materials are as follows.
  • suitable organic dispersants include those disclosed in U.S. Patent 3,308,067 issued March 7, 1967, to Diehl.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence of monomeric segments containing no carboxylate radicals such as vinylmethyl ether, styrene or ethylene is suitable, preferably when such segments do not constitute more than 40% by weight of the polymer.
  • Suitable organic dispersants for use herein are copolymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, preferably from 4,000 to 20,000, and an acrylamide content of less than 50%, preferably less than 20%, by weight of the polymer. Most preferably, the polymer has a molecular weight of from 4,000 to 10,000 and an acrylamide content of from 1% to 15%, by weight of the polymer.
  • Still other useful organic dispersants include acrylate/ maleate or acrylate/fumarate copolymers with an average molecular weight in acid form of from 2,000 to 80,000 and a ratio of acrylate to maleate or fumarate segments of from 30:1 to 2:1.
  • Other such suitable copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published December 15, 1982.
  • Yet other organic dispersants are useful herein, as illustrated by water-soluble oxidized carbohydrates, e.g., oxidized starches prepared by art-disclosed methods.
  • compositions of the present invention may optionally comprise certain esters of phosphoric acid (phosphate ester).
  • Phosphate esters are any materials of the general formula: wherein R and R' are C 6 -C 20 alkyl or ethoxylated alkyl groups.
  • R and R' are of the general formula: alkyl-(OCH 2 CH 2 ) Y wherein the alkyl substituent is C 12 -C 18 and Y is between 0 and about 4.
  • the alkyl substituent of that formula is C 12 -C 18 and Y is between 2 and 4.
  • Such compounds are prepared by known methods from phosphorus pentoxide, phosphoric acid, or phosphorus oxy halide and alcohols or ethoxylated alcohols.
  • phosphate esters will generally comprise mixtures of the mono- and di-esters, together with some proportion of tri-ester.
  • Typical commercial esters are available under the trademarks "Phospholan” PDB3 (Diamond Shamrock), “Servoxyl” VPAZ (Servo), PCUK-PAE (BASF-Wyandotte), SAPC (Hooker).
  • Preferred for use in the present invention are KN340N and KL340N (Hoechst) and monostearyl acid phosphate (Occidental Chemical Corp.). Most preferred for use in the present invention is Hostophat®-TP-2253 (Hoechst).
  • the phosphate esters useful herein provide protection of silver and silver-plated utensil surfaces.
  • the phosphate ester component also acts as a suds suppressor in the anionic surfactant-containing detergent compositions disclosed herein.
  • a phosphate ester component is used in the compositions of the present invention, it is generally present from 0.1% to 5%, preferably from 0.15% to 1.0% by weight of the composition.
  • long chain fatty acids and/or long chain hydroxy fatty acids have been found to be useful in automatic dishwashing detergent compositions to inhibit tarnishing caused by repeated exposure of sterling or silver-plate flatware to bleach-containing automatic dishwashing detergent compositions (U.S. Patent 4,859,358, Gabriel et al).
  • long chain is meant the higher aliphatic fatty acids or hydroxy fatty acids having from 6 to 24 carbon atoms, preferably from 8 to 22 carbon atoms, and most preferably from 10 to 20 carbon atoms and most preferably from 12 to 18, inclusive of the carbon atom of carboxyl group of the fatty acid, e.g., stearic acid, and hydroxy stearic acid.
  • metal salts of the long chain fatty acids and/or hydroxy fatty acids is meant both monovalent and polyvalent metal salts, particularly the sodium, potassium, lithium, aluminum, and zinc salts, e.g., lithium salts of the fatty acids.
  • this material are aluminum, potassium, sodium, calcium and lithium stearate or hydroxy stearate, particularly preferred is aluminum tristearate.
  • this component generally comprises from 0.01% to 2%, preferably from 0.05% to 0.2% by weight of the composition.
  • An alkali metal salt of an amphoteric metal salt of an amphoteric metal anion (metalate), such as aluminate, can be added to provide additional structuring to the polycarboxylate polymer thickening agent. See U. S. Patent 4,941,988, Wise, issued July 17, 1990.
  • Suitable nonchlorine bleaches in the present compositions are solid, water-soluble peroxygen compounds in levels from 0 to 15%, preferably from 0.2% to 12% by weight of the composition.
  • Preferred compounds include perborates, persulfates, peroxydisulfates, perphosphates and the crystalline peroxyhydrates, 2,124,526, U.S. Patent 3,933,672, Bartolotta et al., and U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.
  • compositions hereof will generally comprise from 0% to 5% of suds suppressor.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • compositions hereof A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, draining promoting agents, processing aids, corrosion inhibitors, perfumes, dyes or pigments, oxygen bleaches or bleach activators.
  • the above-described other optional materials generally are enzyme compatible and comprise no more than 10% by weight of the total composition and are dissolved, suspended, or emulsified in the present compositions.
  • Preferred viscoeleastic, thixotropic, liquid automatic dishwashing detergent compositions hereof will preferably be formulated such that during use in aqueous operations, the wash water will have a pH of between 7 and 11, preferably between 8 and 10.5.
  • This invention further provides a method for cleaning dishware (i.e. glass, china, flatware, silverware and the like) by contacting the dishware with a liquid detergent composition comprising detersive enzyme, detersive surfactant, viscoelastic thixotropic thickening agent, enzyme stabilizing system, and buffering agent. Agitation is preferably provided for enhanced cleaning.
  • dishware i.e. glass, china, flatware, silverware and the like
  • a liquid detergent composition comprising detersive enzyme, detersive surfactant, viscoelastic thixotropic thickening agent, enzyme stabilizing system, and buffering agent. Agitation is preferably provided for enhanced cleaning.
  • gel and/or paste automatic dishwashing detergent compositions are gel and/or paste automatic dishwashing detergent compositions, more preferably gel automatic dishwashing detergent compositions.
  • This invention also allows for concentrated gel automatic dishwashing detergent compositions.
  • concentrated is meant that these compositions will deliver to the wash the same amount of active detersive ingredients at a lower dosage.
  • Concentrated gel automatic detergent compositions herein contain 10 to 100 weight % more active detersive ingredients than regular gel automatic dishwashing detergent compositions.
  • a preferred method for preparing a final product of the present invention comprises:
  • step (d) adding surfactant and other suitable agents
  • the polymer may be added as either a powder or slurry.
  • the enzyme stabilizing system should be added prior to the addition of builder. Without being bound by theory, it is believed the enzyme stabilizing system added after the builder will associate with the builder and lose its effectiveness; whereas, if added prior to the builder it will form an effective compound which will not associate with the builder.
  • enzymes are added last to minimize degradation due to temperature and pH changes resulting during the process.
  • compositions prepared as above described exhibit a viscoelastic, thixotropic nature, and have good phase stability.
  • Viscoelastic, thixotropic liquid automatic dishwashing detergent compositions are as follows:
  • Compositions 1-4 demonstrate the use of various enzyme stabilizing systems, i.e. boric acid (composition 1), boric acid and 1,2-propanediol (composition 4), and calcium/sodium formate (compositions 2 and 3). All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40°F (4.4°C) to about 120°F (48.9°C).
  • various enzyme stabilizing systems i.e. boric acid (composition 1), boric acid and 1,2-propanediol (composition 4), and calcium/sodium formate (compositions 2 and 3). All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40°F (4.4°C) to about 120°F (48.9°C).
  • Viscoelastic, thixotropic liquid automatic dishwashing detergent compositions are shown below containing chlorine scavengers.
  • Compositions 5-12 demonstrate the use of chlorine scavengers in viscoelastic, thixotropic liquid automatic diswashing detergent compositions. All exhibit enhanced cleaning, spotting and filming performance and phase stability when stored up to about ten (10) weeks at from about 40°F (4.4°C) to about 120°F (48.9°C).
  • a concentrated, viscoelastic, thixotropic liquid automatic dishwashing detergent composition is as follows:
  • Concentrated gel automatic dishwashing detergent compositions with chlorine scavengers are shown below.
  • Viscoelastic, thixotropic liquid automatic dishwashing detergent compositions are as follows: Table 5 % Weight Ingredients 13 14 Sodium citrate 9.00 9.00 Sodium hydroxide (50%) 1.90 1.90 Sodium carbonate 0.00 8.00 Aluminum tristearate 0.10 0.00 Polyacrylate thickener (1) 2.00 2.50 Dye 0.0002 0.002 Perfume 0.05 0.05 Sodium cumene sulfonate 0.00 0.85 Sodium polyacrylate (2) 2.40 2.40 Sodium n-decydiphenyloxide disulfonate (3) 0.00 0.00 Boric acid 0.00 2.00 1,2-propanediol 0.00 4.70 Calcium formate 0.20 0.00 Sodium formate 0.45 0.00 Protease enzyme (4) 0.02 0.02 Amylase enzyme (5) 0.01 0.01 Water and minors ------------------------------------ (1) Polygel® DK, 3-V Chemical Corporation (2) Molecular weight about 4500 (3) DOWFAX® 3B2 (4) Esperase® 8.0L, Novo

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Claims (8)

  1. Viskoelastische, thixotrope, flüssige Reinigerzusammensetzung zum maschinellen Geschirrspülen, umfassend, bezogen auf Gewicht,
    a) 0,001 bis 5 % eines aktiven Waschenzyms oder -enzyme, die vorzugsweise aus der Protease, Lipase, Amylase und Mischungen hiervon umfassenden Gruppe gewählt sind;
    b) 0,1 bis 10% eines viskoelastsichen, thixotropen Verdickungsmittels, das vorzugsweise aus der vernetzte Polycarboxylatpolymere mit einem Molekulargewicht von 750.000 bis 4.000.000, natürliche Gummen, Polymere vom Zellulosetyp und Mischungen hiervon umfassenden Gruppe gewählt ist; am meisten bevorzugt ein Polycarboxylatpolymer-Verdickungsmittel mit einem Molekulargewicht von 750.000 bis 4.000.000;
    c) 0,001 bis 10 % eines Enzym-stabilisierenden Systems, gewählt aus der Calciumionen. Propylenglykol, kurzkettige Carbonsäure, Polyhydroxylverbindungen, Borsäure, Boronsäure und Mischungen hiervon umfassenden Gruppe, vorzugsweise gewählt aus der Borsäure, 1.2-Propandiol, Calciumformiat, Natriumformiat und Mischungen hiervon umfassenden Gruppe;
    d) 3 bis 40 % eines Waschmittelbuilders; und
    e) ein pH-Einstellungsmittel in ausreichender Menge, das am meisten bevorzugt aus der Natriumcarbonat, Natriumbicarbonat, Kaliumcarbonat, Natriumsequicarbonat, Natriumpyrophosphat, Tetrakaliumpyrophosphat, Trikaliumphosphat, Trinatriumphosphat, wasserfreies Natriumtetraborat, Natriumtetraboratpentahydrat, Kaliumhydroxid, Natriumhydroxid, Natriumtetraboratdecahydrat, Monoethanolamin, Triethanolamin und Mischungen hiervon umfassenden Gruppe gewählt ist, um die Zusammensetzung mit einem Produkt-pH zwischen größer als 9 und 1 1 zu versehen, so daß der verdünnte pH einer 1 %-igen wäßrigen Lösung der Zusammensetzung ebenfalls größer als 9 ist, wobei die Zusammensetzung frei von Chlor-Bleichmitteln und Silikat ist, und wobei der Builder aus der Citronensäure, Alkalimetallcitrat und Mischungen hiervon umfassenden Gruppe gewählt ist.
  2. Zusammensetzung nach Anspruch 1, wobei das Enzym-stabilisierende System weiterhin 0,01 bis 6 % eines Chlor-Fängers umfaßt, bei dem es sich um ein Ammoniumkation enthaltendes Salz handelt.
  3. Zusammensetzung nach Anspruch 1 oder 2, umfassend 0,1 bis 30 % eines Waschtensids, 0,003 bis 4 % des aktiven Waschenzyms, 0,25 bis 5 % des viskoelastischen Verdickungsmittels, 0,005 bis 8 % des Enzym-stabilisierenden Systems, wobei der Produkt-pH zwischen mehr als 9 und 10,5 liegt.
  4. Zusammensetzung nach Anspruch 3, wobei das aktive Waschenzym eine Protease oder Amylase oder eine Mischung hiervon ist, und wobei das Waschtensid frei von enzymatisch reaktiven Spezies ist.
  5. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend weiterhin einen organischen Dispergator und 0,1 bis 15 % wasserlösliche Persauerstoffverbindungen.
  6. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung ein Gel ist.
  7. Gelförmige Reinigerzusammensetzung zum maschinellen Geschirrspülen nach Anspruch 1, umfassend weiterhin
    0,1 bis 30% eines Waschmitteltensids; und
    0,01 bis 6 % eines Chlor-Fängers.
  8. Zusammensetzung nach Anspruch 7, wobei die Zusammensetzung ein konzentriertes Gel ist, umfassend
    5 bis 20 % des Waschmittelbuilders; und
    2 bis 15 % des Waschtensids.
EP93909464A 1992-04-13 1993-03-31 Enzym enthaltendes, flüssiges, thixotropes maschinengeschirrspülmittel Expired - Lifetime EP0636170B1 (de)

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JP7134474B2 (ja) * 2018-08-01 2022-09-12 シーバイエス株式会社 硬表面自動洗浄機用洗浄剤組成物
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US7153818B2 (en) 2000-07-28 2006-12-26 Henkel Kgaa Amylolytic enzyme extracted from bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
US7803604B2 (en) 2000-07-28 2010-09-28 Henkel Ag & Co. Kgaa Amylolytic enzyme extracted from Bacillus sp. A 7-7 (DSM 12368) and washing and cleaning agents containing this novel amylolytic enzyme
DE102009000879A1 (de) 2009-02-16 2010-08-19 Henkel Ag & Co. Kgaa Reinigungsmittel
WO2010092066A1 (de) 2009-02-16 2010-08-19 Henkel Ag & Co. Kgaa Reinigungsmittel
EP3260524A1 (de) 2009-06-24 2017-12-27 Henkel AG & Co. KGaA Maschinelles geschirrspülmittel
US10005987B2 (en) 2012-01-24 2018-06-26 Henkel Ag & Co. Kgaa Enzyme-containing washing or cleaning composition comprising calcium nitrate
DE102012203475A1 (de) 2012-03-06 2013-09-12 Henkel Ag & Co. Kgaa Enzymhaltiges Handgeschirrspülmittel
WO2013131941A1 (de) 2012-03-06 2013-09-12 Henkel Ag & Co. Kgaa Enzymhaltiges handgeschirrspülmittel
WO2015078742A1 (de) 2013-11-27 2015-06-04 Henkel Ag & Co. Kgaa Lipasestabilisierung in geschirrspülmitteln
DE102015217594A1 (de) 2015-09-15 2017-03-16 Henkel Ag & Co. Kgaa Stabilisierung von Enzymen in Wasch- oder Reinigungsmitteln
WO2017046020A1 (de) 2015-09-15 2017-03-23 Henkel Ag & Co. Kgaa Stabilisierung von enzymen in wasch- oder reinigungsmitteln
EP4065678A2 (de) * 2019-11-28 2022-10-05 Aspen Pumps Limited Reinigungszusammensetzungen
US12590271B2 (en) 2019-11-28 2026-03-31 Aspen Pumps Limited Cleaning compositions

Also Published As

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WO1993021299A1 (en) 1993-10-28
JPH07505669A (ja) 1995-06-22
DE69312924D1 (de) 1997-09-11
ATE156515T1 (de) 1997-08-15
BR9306243A (pt) 1998-06-23
AU4024993A (en) 1993-11-18
CA2133446A1 (en) 1993-10-28
EP0636170A1 (de) 1995-02-01
KR950700986A (ko) 1995-02-20

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