EP0703974B1 - Konzentriertes phosphatfreies flüssiges enzymhaltiges maschinengeschirrspülmittel - Google Patents

Konzentriertes phosphatfreies flüssiges enzymhaltiges maschinengeschirrspülmittel Download PDF

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Publication number
EP0703974B1
EP0703974B1 EP94919327A EP94919327A EP0703974B1 EP 0703974 B1 EP0703974 B1 EP 0703974B1 EP 94919327 A EP94919327 A EP 94919327A EP 94919327 A EP94919327 A EP 94919327A EP 0703974 B1 EP0703974 B1 EP 0703974B1
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Prior art keywords
sodium
composition
mixtures
enzyme
weight
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EP0703974A1 (de
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Hal Ambuter
Todd Stephen Alwart
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • C11D3/38—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

Definitions

  • This invention is in the field of liquid automatic dishwashing compositions. More specifically, the invention relates to concentrated compositions containing non-phosphate builders, enzymes, and a potassium/sodium weight ratio of at least 0.01.
  • liquid and/or gel automatic dishwashing detergent compositions are a popular alternative to granular compositions among consumers.
  • liquid and/or gel formulations often do not deliver the same effective cleaning, sporting and filming performance as a granular composition.
  • a viscoelastic, thixotropic liquid automatic dishwashing detergent can be formed which has superior performance to conventional liquid/gel products and comparable performance to granular products.
  • a low alkaline product pH (between 7 and 11) 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 also results in a composition which is safer to dishwasher articles (i.e. china, silverware, glass).
  • a concentrated liquid automatic dishwashing detergent composition containing enzymes and non-phosphate builder(s) requires a potassium/sodium weight ratio of at least 0.01, preferably, between 0.01 and 10, in order to maintain long term product stability.
  • composition of this invention is a concentrated viscoelastic, thixotropic, liquid automatic dishwashing detergent composition comprising, by weight:
  • a particularly preferred embodiment of this invention is a gel automatic dishwashing detergent composition further comprising an organic dispersant, a detergent surfactant and/or a chlorine scavenger.
  • the present invention encompasses viscoelastic, thixotropic, liquid automatic detergent compositions which exhibit enhanced performance in the absence of chlorine bleach, silicate, and phosphate.
  • These detergent compositions contain the following components by weight of the composition:
  • Various other optional ingredients such as fatty acids, oxygen bleaches, perfumes, dyes, suds control agents, and organic dispersants, can be added to provide additional performance, product stability, and aesthetic benefits.
  • a particularly preferred composition is a gel formulation.
  • thixotropic means the material exhibits a decrease in viscosity with increasing shear stress. In other words, it exhibits high viscosity when subjected to low shear stress and lower viscosity when subjected to higher shear stress.
  • a viscoelastic liquid exhibits a steady state flow behavior after a constant shear stress has been applied for a sufficiently long period of time.
  • compositions of the present invention comprises less than 0.5% form of phosphorous, and less than 0.2% silicate. No level of chlorine bleach species is acceptable; however, if present chlorine scavengers discussed herein can be added to the composition.
  • the detergency builders used can be any of the non-phosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium carbonates, bicarbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates (e.g. citrates), and polycarboxylates.
  • the alkali metal especially sodium and potassium, salts of the above and mixtures thereof.
  • the amount of builder is from 5% to 50%, preferably from 8% to 40%, most preferably from 10% to 30% by weight of the automatic dishwashing detergent composition.
  • non-phosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, and sesquicarbonate.
  • Water-soluble, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates (e.g. citrates), polycarboxylates and polyhydroxysulfonates.
  • polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxy methyloxysuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
  • Preferred detergency builders have the ability to remove metal ions other than alkali metal ions from washing solutions by sequestration, which as defined herein includes chelation, or by precipitation reactions. Some of the above-described detergency builders additionally serve as buffering agents (pH adjusting), and/or chlorine scavengers.
  • Particularly preferred automatic dishwashing detergent compositions of the invention contain, by weight of the automatic dishwashing detergent composition, from 5% to 50%, preferably from 8% to 30%, most preferably from 10% to 30%, of carbonate, citrate, and mixtures thereof.
  • compositions of this invention must include sufficient amounts of potassium and sodium ions to provide a finished product K/Na weight ratio of at least 0.01, preferably between 0.01 and 10, more preferably between 0.1 and 1.0, even more preferably between 0.1 and 0.8, most preferably between 0.1 and 0.5.
  • the potassium and sodium ions can be incorporated into the composition from the alkali metal cation of the detergent builder salt(s), or alkali metal hydroxide(s), or as the alkali metal cation of any other component of the composition. In determining the total finished product K/Na weight ratio, all of these sources should be taken into consideration.
  • the finished product K/Na weight ratio is directly proportional to the weight percent of detergent components/salts incorporated in the composition.
  • a higher weight percent of detergent components in the composition requires a higher finished product K/Na weight ratio to achieve acceptable finished product stability.
  • the K/Na ratio should be between 0.01 and 0.20 for builder levels between 5% and 10%; between 0.05 and 1.50 for builder levels between 10% and 30%; and between 0.6 and 10.0 for builder levels between 30% and 50%.
  • compositions of this invention can contain from 0.0001% to 5%, more preferably from 0.001% to 1%, most preferably from 0.005% to 0.5%, by weight, of active detersive enzyme.
  • Weight percent of "active detersive enzyme” is defined by the weight percent of the enzyme present in the composition - it does not include the weight percent of other materials commonly included in commercial enzyme feedstocks (e.g. solvents, stabilizers, residuals).
  • 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 AlcalseR, EsperaseR, DurazyrmR, SavinaseR (preferred); MaxataseR MaxacalR (preferred), and MaxapemR 15 (protein engineered Maxacal), PurafectR (preferred) and subtilisin BPN and BPN'; which are commercially available.
  • Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called “Protease A” herein and in PCT Application Number WO 91/02792, Wilson et al, published March 7, 1991 which is called "BLAP" herein.
  • Preferred proteolytic enzymes are selected from the group consisting of SavinaseR, AlcalaseR, EsperaseR, MaxacalR, PurafectR, BPN', Protease A and Protease B, and mixtures thereof. SavinaseR or "Protease B" 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 from 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.
  • Lipase P Lipase P
  • Mano-P Lipase 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 Oucheterion (Acta. Med. Scan., 133, pages 76-79 (1950)).
  • Oucheterion 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 viscosum lipases, and lipases ex Pseudomonas gladioli .
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes , which is described in Granted European Patent, EP-B-0218272.
  • 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, EO A 0 218 272, published April 15, 1987, and PCT/DK 88/00177, published May 18, 1989.
  • Suitable funzal 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 LipolaseR from Novo-Nordisk.
  • Amylases include for example, a-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.
  • the preferred compositions herein comprise from 0.001% to 20%, preferably from 0.01% to 15%, most preferably from 0.5% to 12%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme of the present invention.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid having a chain length of one carbon atom boronic acid, Polyhydroxyl compounds, peptide aldehydes, 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 can be used with boric acid or a suitable salt of boric acid, described herein below, in a composition with a product pH between 7 and 9.
  • boric acid or a suitable salt of boric acid, described herein below
  • calcium ions and the salt of boric acid can associate to form calcium borate which is insoluble in cold water and under certain product conditions can be insoluble above about 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% to 1%, 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 0.001% to 20%, 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 about 1.3.
  • compositions can also contain the water-soluble short chain carboxylates having a chain length of one carbon atom 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% to 5%, preferably from 0.075% to 2.5%, most 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 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 ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Still another enzyme stabilizing system includes polyhydoxyl compounds, such as sugar alcohols, monosaccharides and discaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-solule 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.
  • polyhydoxyl compounds such as sugar alcohols, monosaccharides and discaccharides as disclosed in the specification of German Pat. No. 2,038,103, water-solule 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
  • the enzyme mixture may be incorporated into the detergent composition in a coated, encapsulated, agglomerated, prilled, or noodled from in accordance with, e.g., U.S. Patent 4,162,987, Maguire et al, issed 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,
  • peptide aldehyde comprising from 2 to 50 amino acids, or mixtures thereof.
  • peptide aldehydes refers to compounds comprising a peptidic chain wherein the C-terminal end of said chain is converted from a carboxylic group to an aldehyde group.
  • Peptide aldehydes are known per se and have been described as well as processes for their manufacture, for instance in US 5,015,627, EP 185 930 and DE 32 00 812.
  • Preferred peptide aldehydes for use herein comprise from 2 to 6 amino acids, most preferably 3 to 4.
  • the viscoelastic, thixotropic thickening agent in the compositions of the present invention is from 0.1% to 10%, preferably from 0.25% to 8%, most preferably from 0.5% to 5%, 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 at least 500,000, preferably from 500,000 to 10,000,000.
  • the polymeric thickening agent can be, but is not limited to, a cross-linked polycarboxylate polymer.
  • the preferred cross-linked polycarboxylate polymer is preferably a carboxyvinyl polymer.
  • carboxyvinyl polymer Such compounds are disclosed in U.S. Patent 2,798,053, issued on July 2, 1957, 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, a pentaerythritol; most preferred is sucrose or pentaerythritol. It is preferred that the hydroxyl groups of the modified polyol 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 about 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; for example, acrylic acid.
  • Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 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, for example, Carbopol 981, 2984, 980, and 1382.
  • Preferred polycarboxylate polymers of the invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and having a molecular weight of at least 750,000, preferably from 750,000 to 4,000,000.
  • polycarboxylate polymers for use in the present invention are Sokalan PHC-25R, a polyacrylic acid available from BASF Corporation, the Carbopol series resins available from B.F. Goodrich, and the Polygel series available from 3-V Chemical Corporation. Mixtures of polycarboxylate polymers as herein described may also be used.
  • the polycarboxylate polymer thickening agent can be used alone or with inorganic clays (e.g. aluminum silicate, bentonite, fumed silica).
  • 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.
  • Semi-synthetic thickeners such as the cellulosic type thickeners: hydroxyethyl and hydroxymethyl cellulose (ETHOCEL and METHOCELR available from Dow Chemical) can also be used.
  • Mixtures of polymeric thickening agents, semi- synthetic, and natural thickeners herein described may 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 a Contraves Rheomat 115 viscometer which utilizes a Rheoscan 100 controller, a DIN 145 spindle and cup at 25°C.
  • the shear rate is increased from 0 to 150 sec -1 over a 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 a period of 500 seconds after an initial 5 minute rest period.
  • 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 (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.
  • composition pH between 7 and 11, preferably between 8 and 10.5, 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% to 50%, preferably from 8% to 40% 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 7 to 11, preferably 8 to 10.5, most prefably 9 to 10.5, 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, tetraborates, hydroxides, 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 sesquicarbonate, 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. As set forth herein, the compositions of the present invention comprise sufficient amount of both potassium and sodium ions.
  • the pH adjusting can be a source for these ions.
  • compositions of this invention can contain from 0% to 20%, preferably from 0.1% to 15%, more from 1% to 10% of a detergent surfactant which preferably results in a low foaming detergent composition.
  • a detergent surfactant is low foaming or which in combination with other components (i.e. suds suppressors) is low foaming.
  • the surfactant is a low foaming nonionic surfactant.
  • the surfactant is chlorine bleach free, there is no requirement that the surfactant be chlorine bleach stable.
  • 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.
  • the composition is phosphate free, compounds containing phosphorous should be avoided.
  • 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, PLURAFACR and TETRONICR by the BASF Corp., Parsippany, N.J. are suitable as the surfactant for use herein.
  • a particularly preferred embodiment contains a polyoxypropylene, polyoxethylene block polymer blend comprising 75%, 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, C8-C12 N-methyl-glucamides and the like.
  • 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 compostions of the present invention include, but are not limited to, water soluble secondary alcohol sulfates, and alkyl sulfates and/or sulfonates, containing from 6 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.
  • suitable alcohols which can be employed in alkyl sulfate manufacture include nonyl, undecyl, decyl, lauryl, tridecyl, myristyl, pentadecyl, 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 about 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 dodecyldimethylammonium acetate, tetradecyldimethylammonium acetate, hexadecyldimethylammonium acetate, alkyldimethylammonium acetate wherein the alkyl group averages 14.8 carbon atoms in length, dodecyldimethylammonium butanoate, tetradecyldimethyl- ammonium butanoate, hexadecyldimethylammonium butanoate, dodecyl- dimethylammonium hexanoate, hexadecyldimethylammonium hexanoate, tetradecyldiethylammonium pentanoate and tetradecyldipropyl- ammonium pentanoate.
  • Especially preferred betaine surfactants include dodecyldimethylammonium acetate, dodecyldimethylammonium hexanoate, hexadecyldimethylammonium acetate, and hexadecyldi- methylammonium hexanoate.
  • surfactants include amine oxides and sulfoxides. However, such surfactants are usually high sudsing.
  • a disclosure of surfactants can be fbund 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.
  • 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 name DOWFAXR 3B-2 (sodium n-decyl diphenyloxide disulfonate) and DOWFAXR 2A-1. These and similar surfactants are disclosed in published U.K. Patent Applications 2,163,447A; 2,163,448A; and 2,164,350A.
  • chlorine bleach scavengers can be added to prevent chlorine bleach species present in many water supplies from attacking and deactivating 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 for compositions of the present invention with a pH less than 8 are salts containing ammonium cations. These can be selected from the group consisting of reducing materials like sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc., antioxidants like carbamate, ascorbate.
  • compositions can contain an organic dispersant which overcomes the problem of unsightly films and spots which form on china and especially on glassware due to calcium or magnesium hardness induced precipitation of the builders and/or pH adjusting agents (e.g. especially carbonate).
  • an organic dispersant which overcomes the problem of unsightly films and spots which form on china and especially on glassware due to calcium or magnesium hardness induced precipitation of the builders and/or pH adjusting agents (e.g. especially carbonate).
  • the organic dispersants herein can be used at levels of 0 to 40% typically from 0.5% to 30%, most preferably from 1% to 20% of the automatic dishwashing composition. Such organic dispersants are preferably water-soluble sodium polycarboxylates.
  • Polycarboxylate dispersant 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.
  • Organic dispersants are polyacrylates or acrylate-containing copolymers.
  • SOKALAN Polymeric Dispersing Agents
  • a printed publication of BASF Aktiengesellschaft, D-6700 Ludwigshaven, Germany describes organic dispersants useful herein.
  • Preferred dispersants herein described include, but are not limited to sodium polyacrylate having a nominal molecular weight of 4500, obtainable from Rohm & Haas under the tradename ACUSOLR (e.g. ACUSOLR 445N), or acrylate/maleate copolymers such as are available under the tradename SOKALANR, from BASF Corp.
  • ACUSOLR e.g. ACUSOLR 445N
  • SOKALANR acrylate/maleate copolymers
  • Suitable polymers are generally low molecular weight and 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, ethylene, etc. 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 about 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 popolymers 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.
  • a particularly preferred embodiment of the present invention can contain from 0% to 40%, preferably from 1% to 30%, most preferably from 1% to 20%, by weight of the automatic dishwashing detergent composition, of low molecular weight modified polyacrylate copolymers.
  • modified polyacrylate is defined as a copolymer which contains as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula: wherein at least one of the substituents R 1 , R 2 or R 3 , preferably R 1 or R 2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R 1 or R 2 can be a hydrogen and R 3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R 1 is methyl, R 2 is hydrogen and R 3 is sodium.
  • the low molecular weight modified polyacrylate preferably has a molecular weight of less than 15,000, preferably from 500 to 10,000, most preferably from 1,000 to 5,000.
  • the most preferred polyacrylate copolymer has a molecular weight of 3500 and is 70% by weight acrylic acid and 30% by weight methyl acrylic acid.
  • Suitable modified polyacrylate copolymers include the low molecular weight copolymers of unsaturated aliphatic carboxylic acids as disclosed in U.S. Patent 4,530,766, and 5,084,535.
  • 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% 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.
  • compositions hereof will generally comprise from 0% to 5% of suds suppressor.
  • Suitable suds suppressors are described in Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979), U.S. Patent 2,954,347, issued September 27, 1960 to St. John, U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., and European Patent Application No. 89307851.9, published February 7, 1990, U.S. Patent 3,455,839, German Patent Application DOS 2,124,526, U.S. Patent 3,933,672, Bartolatta et al and U.S. Patent 4,652,392, Baginski.
  • a commercially acceptable suds suppressor is LPKN, from Knapsack.
  • 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.
  • the peroxygen compound can be a preformed peroxyacid, an inorganic persalt or a combination of an inorganic per salt and an inorganic precursor (i.e. bleach activator).
  • compositions of the invention contain peroxygen compounds such as perborates, persulfates, percarbonates, peroxydisulfates, crystalline peroxyhydrates and mixtures thereof.
  • Liquid detergent compositions can contain water and other solvents as carriers. These solvents include, but are not limited to, low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol. 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.
  • solvents include, but are not limited to, low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol. 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, gly
  • solvents include the higher glycols, polyoxides, glycol ethers, propylene glycol ehters and tripropylene glycol ethers. Any water used in the composition should preferably be softened or deionized.
  • 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, etc.
  • the above-described other optional materials generally are enzyme compatible 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 and silverware) 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 and silverware
  • 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.
  • concentrated gel and/or paste automatic dishwashing detergent compositions are preferably gel automatic dishwashing detergent compositions.
  • concentrate or “compact” is meant that these compositions will deliver to the wash the same amount of active detersive ingredients at a lower dosage while achieving equal or improved performance.
  • dishwasher machines range in total dispenser cup capacity (many dishwashers have several dispenser cups) from 80 cc to 150 cc of product, depending on the machine manufacturer.
  • Most current automatic dishwashing products are formulated to deliver the desired performance based on this dispensing volume.
  • Compact products allow the reduction in the amount of product used to between 40% and 60%, but can range from 1% to 99%.
  • a preferred method for preparing a final product of the present invention comprises:
  • step (d) adding surfactant and other suitable agents
  • the thickener 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 should be 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.
  • Concentrated gel automatic dishwashing detergent compositions of the present invention prepared according to the above described process are as follows: % by weight Ingredients A B C D E F G Potassium carbonate 2.00 4.00 0.00 9.73 3.50 0.00 0.25 Sodium carbonate 13.47 5.43 0.00 12.42 3.74 0.00 5.00 Sodium citrate dihydrate 0.00 15.00 25.00 0.00 0.00 0.00 0.00 0.00 Potassium hydroxide (45%) 0.00 0.00 4.98 0.00 8.44 17.78 0.67 Sodium hydroxide (50%) 0.00 0.00 0.00 0.00 0.00 3.00 7.72 0.00 Citric Acid (50%) 0.00 0.00 0.00 0.00 0.00 19.70 34.58 1.10 Monoethanolamine 1.91 1.91 1.91 1.91 1.91 1.91 1.91 Polyacrylate thickener 2.00 2.00 2.00 1.75 2.00 2.00 2.00 Perfume 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Dye 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.002 0.00

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Claims (12)

  1. Konzentrierte, viskoelastische, thixotrope, flüssige Reinigerzusammensetzung zum maschinellen Geschirrspülen, umfassend, bezogen auf Gewicht:
    (a) 5 bis 50 % eines Nichtphosphat-Waschmittelbuilders, gewählt aus der wasserlösliche Alkalimetall-, Ammonium- oder substituierte Ammoniumcarbonate, Bicarbonate, Borate, Polyhydroxysulfonate, Polyacetate, Carboxylate, Polycarboxylate und Mischungen hiervon umfassenden Gruppe;
    (b) 0,0001 bis 5 % aktives Waschenzym, vorzugsweise gewählt aus der Protease, Lipase, Amylase und Mischungen hiervon umfassenden Gruppe;
    (c) 0,1 bis 10 % eines viskoelastischen, thixotropen Verdickungsmittels. vorzugsweise gewählt aus der vernetzte Polycarboxylatpolymere mit einem Molekulargewicht von mindestens 500.000, natürliche Gummen, Tone, Polymere vom Cellulosetyp und Mischungen hiervon umfassenden Gruppe;
    (d) ausreichend pH-Einstellungsmittel, um die Zusammensetzung mit einem Produkt-pH zwischen 7 und 11 zu versehen; und
    (e) 0,001 bis 20 % eines Enzymstabilisierungssystems, gewählt aus der Calciumionen, Propylenglykol, kurzkettige Carbonsäure mit einer Kettenlänge von einem Kohlenstoffatom, Polyhydroxylverbindungen, Borsäure, Boronsäure, Peptidaldehyde und Mischungen hiervon umfassenden Gruppe; und
    (f) Wasser, wobei die wäßrige Phase sowohl Kalium als auch Natriumionen in einem K/Na-Gewichtsverhältnis von mindestens 0,01, vorzugsweise zwischen 0,01 und 10, beinhaltet:
    wobei die Zusammensetzung im wesentlichen frei an Chlorbleichmittel, Silicat und Phosphat ist.
  2. Zusammensetzung nach Anspruch 1, umfassend weiterhin 0,1 bis 20 % eines Waschtensids, gewählt aus der Gruppe, bestehend aus gekapptem Propylenoxid, Ethylenoxid-Blockcopolymeren; Kondensationsprodukten aus Ethylenoxid und Propylenoxid mit einer Mono-, Di- oder Polyhydroxylverbindung, wobei die restlichen Hydroxylgruppen gekappt sind; Alkalimetallsalzen von Mono- und/oder Di-(C8-14)-alkyldiphenyloxidmono- und/oder -disulfonaten; C8-18-Alkylsulfaten; C8-18-Alkylsulfonaten; und Mischungen hiervon.
  3. Zusammensetzung nach Anspruch 1 oder 2, umfassend 8 bis 40 % des Wachmittelbuilders und 0,001 bis 1 % des aktiven Waschenzyms.
  4. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche. umfassend weiterhin 0,5 bis 30 % eines organischen Dispergiermittels, vorzugsweise ein niedermolekulargewichtiges wasserlösliches Natriumpolyacrylat mit einem Molekulargewicht von 1.000 bis 500.000, und 0,01 bis 6 % eines Chlorfängers, vorzugsweise Monoethanolamin.
  5. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei der Produkt-pH zwischen 8 und 10,5 liegt, und wobei das pH-Einstellungsmittel aus der Gruppe gewählt ist, bestehend aus Natriumcarbonat, Natriumbicarbonat, Kaliumcarbonat, Natriumsesquicarbonat, wasserfreies Natriumtetraborat, Natriumtetraboratpentahydrat, Kaliumhydroxid, Natriumhydroxid, einem Natriumtetraboratdecahydrat, Monoethanolamin, Triethanolamin und Mischungen hiervon.
  6. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend weiterhin 0,1 bis 15 % wasserlöslicher Persauerstoffverbindungen.
  7. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche. umfassend 0,25 bis 5 % des Polycarboxylatpolymer-Verdickungsmittels, und wobei das viskoelastische, thixotrope Verdickungsmittel ein Polycarboxylatpolymer-Verdickungsmittel mit einem Molekulargewicht von 750.000 bis 4.000.000 ist.
  8. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei der Waschmittelbuilder das Alkalimetall von Citrat oder Carbonat oder Mischungen hiervon ist, vorzugsweise 10 bis 30 % Carbonat.
  9. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, umfassend 0,01 bis 15 % des Enzymstabilisierungssystems, wobei das Enzymstabilisierungssystem aus der Gruppe gewählt ist, bestehend aus Borsäure, 1,2-Propandiol, Calciumformiat, Natriumformiat, Peptidaldehyd und Mischungen hiervon.
  10. Zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei das aktive Waschenzym eine Protease oder Amylase oder Mischung hiervon ist, und das K/Na-Verhältnis zwischen 0,05 und 1,5 liegt.
  11. Zusammensetzung nach mindestens einem der Ansprüche 4-10, wobei das Polyacrylatcopolymer mit einem Molekulargewicht von 1,000 bis 500,000 ein modifiziertes Polyacrylat ist, das definiert ist als ein Copolymer. welches als Monomereinheiten a) 90 bis 10 Gew.-%, vorzugsweise 80 bis 20 Gew.-%, Acrylsäure oder deren Salze, und b) 10 bis 90 Gew.-%. vorzugsweise 20 bis 80 Gew.-% eines substituierten Acrylmonomeren oder dessen Salze der allgemeinen Formel:
    Figure 00290001
    enthält, worin mindestens einer der Substituenten R1, R2 oder R3, vorzugsweise R1 oder R2 eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 Kohlenstoffatomen ist, R1 oder R2 ein Wasserstoffatom sein kann, und R3 ein Wasserstoffatom oder Alkalimetallsalz sein kann; wobei am meisten bevorzugt ein substituiertes Acrylmonomer ist, worin R1 Methyl ist, R2 Wasserstoff ist und R3 Natrium ist.
  12. Konzentrierte, gelförmige Reinigerzusammensetzung zum maschinellen Geschirrspülen, umfassend, bezogen auf Gewicht:
    (a) 5,0 bis 40 % eines Nichtphosphat-Waschmittelbuilders;
    (b) 0,0001 bis 5 % eines aktiven Waschenzyms:
    (c) 0,1 bis 10 % eines viskoelastischen, thixotropen Verdickungsmittels:
    (d) 0,001 bis 10 % eines Enzymstabilisierungssystems, gewählt aus der Gruppe, bestehend aus Calciumionen, Propylenglykol, kurzkettiger Carbonsäure mit einer Kettenlänge von einem Kohlenstoffatom, Borsäure, Boronsäure und Mischungen hiervon;
    (e) 0,1 bis 30 % eines Waschtensids;
    (f) 0,01 bis 6 % eines Chlorfängers;
    (g) ausreichend Puffermittel, um die Zusammensetzung mit einem Produkt-pH zwischen 7 und 11 zu versehen;
    (h) 0.5 bis 30 % eines niedermolekulargewichtigen Polyacrylatpolymeren; und
    (i) Wasser, wobei die wäßrige Phase sowohl Kalium- und Natriumionen bei einem K:Na-Gewichtsverhältnis von 0,01 bis 10 beinhaltet;
    wobei die Zusammensetzung im wesentlichen frei ist an Chlorbleichmittel, Silicat und Phosphat.
EP94919327A 1993-06-14 1994-06-03 Konzentriertes phosphatfreies flüssiges enzymhaltiges maschinengeschirrspülmittel Expired - Lifetime EP0703974B1 (de)

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EP3074494B1 (de) 2013-11-27 2018-04-04 Henkel AG & Co. KGaA Lipasestabilisierung in geschirrspülmitteln

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EP3074494B1 (de) 2013-11-27 2018-04-04 Henkel AG & Co. KGaA Lipasestabilisierung in geschirrspülmitteln

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