EP0162033A2 - Borsäure enthaltende flüssige Reinigungsmittel zur Stabilisierung von Enzymen - Google Patents

Borsäure enthaltende flüssige Reinigungsmittel zur Stabilisierung von Enzymen Download PDF

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Publication number
EP0162033A2
EP0162033A2 EP85870062A EP85870062A EP0162033A2 EP 0162033 A2 EP0162033 A2 EP 0162033A2 EP 85870062 A EP85870062 A EP 85870062A EP 85870062 A EP85870062 A EP 85870062A EP 0162033 A2 EP0162033 A2 EP 0162033A2
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composition according
acid
boric acid
composition
water
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EP85870062A
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French (fr)
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EP0162033B1 (de
EP0162033A3 (en
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Roland George Severson, Jr.
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from US06/609,944 external-priority patent/US4537706A/en
Priority claimed from US06/609,945 external-priority patent/US4537707A/en
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Priority to AT85870062T priority Critical patent/ATE48635T1/de
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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
    • 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

  • the present invention relates to heavy-duty liquid detergents containing anionic synthetic surfactant, fatty acid, water-soluble detergency builder, proteolytic or amylolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion.
  • Boric acid has been found to provide improved enzyme stability in the built, anionic-based compositions herein.
  • the stabilization of enzymes is particularly difficult in built, heavy-duty liquid detergents containing high levels of anionic surfactants and water.
  • Anionic surfactants especially alkyl sulfates, tend to denature enzymes and render them inactive.
  • Detergent builders can sequester the calcium ion needed for enzyme activity and/or stability.
  • the compositions can contain 10-60% surfactant, including anionics, and up to 40% builder.
  • U.S. Patent 4,404,115, Tai, issued September 13, 1983 discloses liquid cleaning compositions, preferably built liquid detergents, containing enzyme, 1-15% alkali metal pentaborate, 0-15% alkali metal sulfite, and 0-15% of a polyol having 2-6 hydroxy groups.
  • the compositions can contain 1-60% surfactant, preferably a mixture of anionic and nonionic in a weight ratio of 6:1 to 1:1, with or without soap.
  • the compositions also preferably contain 5-50% builder.
  • Japanese Patent Application J78028515 assigned to Nagase and Co., Ltd., published August 15, 1978, discloses liquid detergents containing sorbitol and borax as an enzyme-stabilizing system.
  • the compositions can contain 10-60% surfactant and up to 40% builder, although they are preferably unbuilt.
  • This invention relates to heavy-duty liquid detergent compositions comprising, by weight:
  • the liquid detergents of the present invention contain, as essential components, anionic synthetic surfactant, fatty acid, water-soluble detergency builder, proteolytic or amylolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, calcium ion, and water.
  • Boric acid provides superior enzyme stability in the built, anionic-based liquid detergents herein. While not intending to be limited by theory, it is believed that boric acid and calcium form intramolecular bonds which effectively cross-link or staple an enzyme molecule together, thereby holding it in its active spatial conformation. Surprisingly, boric acid appears to be a better enzyme stabilizer in the present compositions than in compositions which are less stressful to enzymes, such as those containing less anionic surfactant and little or no builder.
  • compositions of the present invention contain from about 10% to about 50%, preferably from about 12% to about 35%, and most preferably from about 15% to about 25%, by weight of an anionic synthetic surfactant.
  • anionic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,929,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference.
  • Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkyl- olammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • water-soluble salts particularly the alkali metal, ammonium and alkyl- olammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • alkyl is the alkyl portion of aryl groups.
  • these group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U. S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
  • anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C 8-18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
  • Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy- alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • Preferred anionic surfactants are the C 10 -C 18 alkyl sulfates and alkyl ethoxy sulfates containing an average of up to about 4 ethylene oxide units per mole of alkyl sulfate, C 11 -C 13 linear alkylbenzene sulfonates, and mixtures thereof.
  • compositions preferably contain from about 1% to about 5%, more preferably from about 2% to about 4%, by weight of unethoxylated alkyl sulfate.
  • alkyl sulfates are desired for best detergency performance, but are very denaturing to enzymes.
  • Boric acid is believed to be particularly effective at stabilizing enzymes in such stressful compositions.
  • compositions herein can optionally contain other synthetic surfactants known in the art, such as the nonionic, cationic, zwitterionic, and ampholytic surfactants described in the above-cited Barrat et al and Laughlin et al patents.
  • a preferred cosurfactant used at a level of from about 2% to about 25%, preferably from about 3% to about 15%, more preferably from about 4% to about 10%, by weight of the composition, is an ethoxylated nonionic surfactant of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 1 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 10 to about 13.
  • R 1 is a C 1 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group
  • n is from about 3 to about 9
  • said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 10 to about 13.
  • Particularly preferred are condensation products of C 12 -C 15 alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • R is an alkyl or alkyl benzyl group having from about 6 to about 16 carbon atoms in the alkyl chain; each R 3 is selected from the group consisting of -CH 2 CH 2 -, -C H 2 CH( C H 3 )-, -C H 2 CH(CH 2 0H)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, and hydrogen when y is not 0; R5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is from
  • alkyl quaternary ammonium surfactants especially the mono-long chain alkyl surfactants described in the above formula when R 5 is selected from the same groups as R 4 .
  • the most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C 8-16 alkyl trimethylammonium salts, C 8-16 alkyl di(hydroxyethyl)methylammonium salts, the C 8-16 alkyl hydroxyethyldimethylammonium salts, C 8-16 alkyloxypropyl trimethylammonium salts, and the C 8-16 alkyloxypropyl dihydroxyethylmethylammonium salts.
  • the C 10- C 14 alkyl trimethylammonium salts are preferred, e.g., decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate.
  • the C 8-10 alkyl trimethylammonium surfactants are particularly preferred since they have lower Kraft boundaries and crystallization temperatures than the longer chain quaternary ammonium surfactants.
  • Amine surfactants useful herein are of the formula: wherein the R 2 , R , R 4 , R 5 and y substituents are as defined above for the quaternary ammonium surfactants. Particularly preferred are the C 12-16 alkyl dimethyl amines.
  • Amine oxide surfactants useful herein are of the formula: wherein the R 2 , R 3 , R 4 , R 5 and y substituents are also as defined above for the quaternary ammonium surfactants. Particularly preferred are the C 12-16 alkyl dimethyl amine oxides.
  • Amine and amine oxide surfactants are preferably used at higher levels than the quaternary ammonium surfactants since they typically are only partially protonated in the present compositions.
  • preferred compositions herein can contain from about 0.5% to about 1.5% of the quaternary ammonium surfactant, or from about 1% to about 3% of the amine or amine oxide surfactants.
  • compositions of the present invention also contain from about 3% to about 30%, more preferably from about 5% to about 20%, most preferably from about 8% to about 15%, by weight of a fatty acid containing from about 10 to about 22 carbon atoms.
  • the fatty acid can also contain from about 1 to about 10 ethylene oxide units in the hydrocarbon chain.
  • Preferred are saturated fatty acids containing from about 10 to about 14 carbon atoms.
  • the weight ratio of C 10 -C 12 fatty acid to C 14 fatty acid should be at least 1, preferably at least 1.5.
  • Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., stripped palm kernel oil, stripped palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
  • suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kernel fatty acid.
  • Preferred are saturated coconut fatty acids, from about 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, mixtures of the above with minor amounts (e.g., 10%-30% of total fatty acid) of oleic acid; and stripped palm kernel fatty acid.
  • compositions herein contain from about 2% to about 15%,. preferably from about 3% to about 10%, more preferably from about 4% to about 8%, by weight of a water-soluble detergent builder material.
  • Detergent builders useful herein include the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981, incorporated herein by reference. Polycarboxylate builders are preferred.
  • Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates.
  • polycarboxylate builders are sodium and potassium ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; the water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S. Patent 1,739,942, Eckey, issued March 27, 1956, incorporated herein by reference; the polycarboxylate materials described in U.S. Patent 3,364,103, incorporated herein by reference; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference.
  • Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (3) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms: (d) the site of attachment of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical.
  • Specific examples of such builders are the polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid.
  • Suitable polycarboxylate builders include the water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxy- methyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
  • water-soluble salts especially the sodium and potassium salts
  • polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,146,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference.
  • Polyphosphonate builders useful herein are disclosed in U.S. Patent 3,213,030, Diehl, issued October 19, 1965, U.S. Patent 3,433,021, Roy, issued January 14, 1968, U.S. Patent 3,292,121, Gedge, issued January 9, 1969 and U.S. Patent 2,599,807, Bersworth, issued June 10, 1952, all incorporated herein by reference.
  • Preferred polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, ethane 1-hydroxy-1,1-diphosphonic acid, and ethane-1,1,2-triphosphonic acid.
  • Preferred aminopolyphosphonate builders are the sodium and potassium salts of diethylenetriaminepenta- methylenephosphonic acid, hexamethylenediaminetetra- methylenephosphonic acid, diethylenediaminetetramethyl- enephosphonic acid, and nitrilotrimethylenephosphonic acid.
  • Polyphosphates useful herein include the water-soluble tripolyphosphates, pyrophosphates, and the polymeric metaphosphates having a degree of polymerization of from about 6 to 21.
  • the tripolyphosphates and metaphosphates tend to hydrolyze to a mixture of orthophosphate and pyrophosphate with prolonged storage in aqueous solutions.
  • the pyrophosphates are the preferred polyphosphates for use in the present invention.
  • Particularly preferred is potassium pyrophosphate since sodium pyrophosphate has a tendency to precipitate from concentrated solutions at low storage temperatures.
  • Citrates are highly preferred builder materials.
  • the compositions also preferably contain from about 0.1% to about 1%, preferably from about 0.2% to about 0.6%, by weight of water-soluble salts of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenephosphonic acid, ethylenediamine tetraacetic acid, or diethylenetriamine pentaacetic acid to enhance cleaning performance when pretreating fabrics.
  • compositions of the present invention contain from about 0.01% to about 5%, preferably from about 0.05% to about 2%, by weight of the composition of a proteolytic or amylolytic enzyme.
  • Proteolytic enzymes are preferably included in an amount sufficient to provide an activity of from about 0.005 to about 0.1, more preferably from about 0.01 to about 0.07, most preferably from about 0.012 to about 0.04, Anson units per gram of composition.
  • Suitable proteolytic enzymes include the many species known to be adapted for use in detergent compositions. Commercial enzyme preparations such as “Alcalase” sold by Novo Industries, and “Maxatase” sold by Gist-Brocades, Delft, The Netherlands, are suitable. Other preferred enzyme compositions include those commercially available under the tradenames SP-72 (“Esperase”) manufactured and sold by Novo Industries, A/S, Copenhagen, Denmark and "AZ-Protease” manufactured and sold by Gist-Brocades, Delft, The Netherlands.
  • proteases herein are preferably purified, prior to incorporation in the finished composition, so that they have no detectable odor at a concentration of less than about 0.002 Anson units per gram in one liter of distilled water. They preferably have no detectable odor at a concentration of less than about 0.0025, more preferably less than about 0.003, Anson units per gram per liter of distilled water.
  • Proteases herein can be odor purified by any method known in the art. Examples include the solvent precipitation methods described in Precipitation of the Enzymes and Their Stability in High Alcohol Concentrations by Bauer et al in the Israel J. Chem. 5(3), pages 117-20 (1967) and Enzyme Preparations by Sugiura et al and Yakusaigaku 1967, Volume 27(2), pages 135-9.
  • Solvent initiated precipitation of a crude commercial enzyme solution results in most of the enzymatic activity being precipitated from solution and most of the odor and color impurities remaining in the supernatant liquid. Decantation or centrifugation of the supernatant liquid from the precipitated enzyme results in an enzyme fraction with enriched enzymatic activity/gram and improved odor and color.
  • solvents or solvent pair combinations can be used to effect the desired precipitation.
  • methanol, ethanol, acetone, other organic solvents, and combinations of organic solvents with and without water can be used.
  • a highly preferred solvent is a combination of water and 30-70% by weight ethanol. This appears to be optimal to prevent enzyme deactivation and maximum recovery of activity.
  • Purification of protease enzymes also provide benefits in the area of product color stability.
  • Amylases useful herein include “Rapidase” sold by Gist-Brocades and “Termamyl” sold by Novo Industries. Purifying amylases, using methods described above for purifying proteases, can also provide some finished product odor and/or color benefits. However, amylases are inherently less odorous and are typically used at much lower levels than the proteases, so malodors are generally not as severe.
  • compositions herein contain from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or a compound capable of forming boric acid in the composition (calculated on the basis of the boric acid).
  • 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.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • the composition also contains from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12 millimoles of calcium ion per liter.
  • 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, fatty acid, 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 generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • compositions herein contain from about 20% to about 80%, preferably from about 30% to about 60%, more preferably from about 35% to about 50%, by weight of water.
  • compositions of the present invention can also contain other materials known in the art to enhance enzyme stability.
  • Particularly preferred are 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 propane diol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose.
  • the polyol generally represents from about 1% to about 15%, preferably from about 1.5% to about 10%, most preferably from about 2% to about 7%, by weight of the composition.
  • the weight ratio of polyol to boric acid is at least 1, more preferably at least about 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, incorporated herein by reference.
  • the formates are preferred and can be used at levels of from about 0.05% to about 5%, preferably from about 0.2% to about 2%, most preferably from about 0.4% to about 1.5%, by weight of the composition.
  • Formates have been found to further enhance protease stability, although amylase stability appears to be slightly less than that obtained using boric acid alone.
  • compositions herein have an initial pH of from about 6.5 to about 10, preferably from about 7 to about 9, most preferably from about 7.5 to about 8.8, at a concentration of 10% by weight in water at 68°F (20°C).
  • Preferred pH buffers include monoethanolamine and triethanolamine.
  • Monoethanolamine and triethanolamine also further enhance enzyme stability, and preferably are included at levels of from about 0.5% to about 10%, preferably from about 1% to about 4%, by weight of the composition.
  • optional components for use in the liquid detergents herein include soil removal agents, antiredeposition agents, suds regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art.
  • Such optional components generally represent less than about 15%, preferably from about 1% to about 10%, by weight of the composition.
  • Enzyme stability in Composition A was as follows.
  • Enzyme stability in Composition A was as follows.
  • Enzyme stability in Composition B was as follows.
  • Enzyme stability in Composition C was as follows.
  • Enzyme stability in Compositions D and E was as follows. (NC means no significant change in stability after six weeks.)
  • boric acid is a much better enzyme stabilizer than sodium formate in Compositions A-E of the invention.
  • the combination of boric acid and formate provides even greater protease stability, but slightly less amylase stability, than that obtained using boric acid alone.
  • boric acid to stabilize enzymes in Compositions A-E in place of sodium formate also allows for a reduction in the level of sodium and calcium ions, which enhances the stability of the compositions against precipitation when stored at low temperatures or under freeze-thaw conditions.
  • Enzyme stability in Compositions A and B was as follows.

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  • Wood Science & Technology (AREA)
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EP85870062A 1984-05-14 1985-05-06 Borsäure enthaltende flüssige Reinigungsmittel zur Stabilisierung von Enzymen Expired EP0162033B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85870062T ATE48635T1 (de) 1984-05-14 1985-05-06 Borsaeure enthaltende fluessige reinigungsmittel zur stabilisierung von enzymen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/609,944 US4537706A (en) 1984-05-14 1984-05-14 Liquid detergents containing boric acid to stabilize enzymes
US06/609,945 US4537707A (en) 1984-05-14 1984-05-14 Liquid detergents containing boric acid and formate to stabilize enzymes
US609945 1984-05-14
US609944 1984-05-14

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EP0162033A2 true EP0162033A2 (de) 1985-11-21
EP0162033A3 EP0162033A3 (en) 1986-03-26
EP0162033B1 EP0162033B1 (de) 1989-12-13

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0181041A2 (de) * 1984-11-09 1986-05-14 The Procter & Gamble Company Äthanolfreie flüssige Wäschereinigungsmittel
EP0199405A2 (de) * 1985-04-15 1986-10-29 The Procter & Gamble Company Flüssige Reinigungsmittel mit einer oberflächenaktiven Verbindung, einem proteolytischen Enzym und Borsäure
FR2585363A1 (fr) * 1985-07-26 1987-01-30 Colgate Palmolive Co Composition detergente liquide renforcee stabilisee contenant des enzymes, et procede de lavage la mettant en oeuvre
FR2585361A1 (fr) * 1985-07-26 1987-01-30 Colgate Palmolive Co Composition detergente liquide renforcee stabilisee contenant des enzymes et assouplissant les tissus, et procede pour sa mise en oeuvre
EP0348183A2 (de) * 1988-06-23 1989-12-27 Unilever Plc Enzymhaltige, flüssige Waschmittel
WO1992007930A1 (de) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Enzymatisches flüssigwaschmittel
US5990066A (en) * 1995-12-29 1999-11-23 The Procter & Gamble Company Liquid hard surface cleaning compositions based on carboxylate-containing polymer and divalent counterion, and processes of using same
WO2009140481A1 (en) * 2008-05-14 2009-11-19 Novozymes A/S Liquid detergent compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2369338A1 (fr) * 1976-11-01 1978-05-26 Unilever Nv Composition detergente liquide enymatique a longue conservation
US4261868A (en) * 1979-08-08 1981-04-14 Lever Brothers Company Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound
EP0028865A1 (de) * 1979-11-09 1981-05-20 THE PROCTER & GAMBLE COMPANY Homogene, Enzym enthaltende, flüssige Reinigungsmittelzusammensetzungen, die gesättigte Fettsäuren enthalten
DE3330323A1 (de) * 1982-08-30 1984-03-01 Colgate-Palmolive Co., 10022 New York, N.Y. Stabilisiertes enzymhaltiges fluessiges reinigungsmittel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2369338A1 (fr) * 1976-11-01 1978-05-26 Unilever Nv Composition detergente liquide enymatique a longue conservation
US4261868A (en) * 1979-08-08 1981-04-14 Lever Brothers Company Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound
EP0028865A1 (de) * 1979-11-09 1981-05-20 THE PROCTER & GAMBLE COMPANY Homogene, Enzym enthaltende, flüssige Reinigungsmittelzusammensetzungen, die gesättigte Fettsäuren enthalten
DE3330323A1 (de) * 1982-08-30 1984-03-01 Colgate-Palmolive Co., 10022 New York, N.Y. Stabilisiertes enzymhaltiges fluessiges reinigungsmittel

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0181041A3 (en) * 1984-11-09 1988-01-27 The Procter & Gamble Company Ethanol-free liquid laundry detergent compositions
EP0181041A2 (de) * 1984-11-09 1986-05-14 The Procter & Gamble Company Äthanolfreie flüssige Wäschereinigungsmittel
EP0199405A2 (de) * 1985-04-15 1986-10-29 The Procter & Gamble Company Flüssige Reinigungsmittel mit einer oberflächenaktiven Verbindung, einem proteolytischen Enzym und Borsäure
EP0199405A3 (en) * 1985-04-15 1988-08-31 The Procter & Gamble Company Liquid detergents containing surfactant, proteolytic enzyme and boric acid
AT397810B (de) * 1985-07-26 1994-07-25 Colgate Palmolive Co Stabilisiertes, textilweichmachendes, flüssiges waschmittel
FR2585363A1 (fr) * 1985-07-26 1987-01-30 Colgate Palmolive Co Composition detergente liquide renforcee stabilisee contenant des enzymes, et procede de lavage la mettant en oeuvre
FR2585361A1 (fr) * 1985-07-26 1987-01-30 Colgate Palmolive Co Composition detergente liquide renforcee stabilisee contenant des enzymes et assouplissant les tissus, et procede pour sa mise en oeuvre
NL8601926A (nl) * 1985-07-26 1987-02-16 Colgate Palmolive Co Gestabiliseerd, samengesteld, enzymbevattend vloeibaar wasmiddel.
NL8601927A (nl) * 1985-07-26 1987-02-16 Colgate Palmolive Co Gestabiliseerde weefselverzachtende, enzym-bevattende, samengestelde, vloeibare wasmiddelen, alsmede werkwijze voor het toepassen daarvan.
EP0348183A2 (de) * 1988-06-23 1989-12-27 Unilever Plc Enzymhaltige, flüssige Waschmittel
EP0348183A3 (de) * 1988-06-23 1991-05-29 Unilever Plc Enzymhaltige, flüssige Waschmittel
USH1776H (en) * 1988-06-23 1999-01-05 Linard; Jack E. Enzyme-containing heavy duty liquid detergent
WO1992007930A1 (de) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Enzymatisches flüssigwaschmittel
US5990066A (en) * 1995-12-29 1999-11-23 The Procter & Gamble Company Liquid hard surface cleaning compositions based on carboxylate-containing polymer and divalent counterion, and processes of using same
WO2009140481A1 (en) * 2008-05-14 2009-11-19 Novozymes A/S Liquid detergent compositions
US8691743B2 (en) 2008-05-14 2014-04-08 Novozymes A/S Liquid detergent compositions

Also Published As

Publication number Publication date
DE3574729D1 (de) 1990-01-18
IE58048B1 (en) 1993-06-16
IE851185L (en) 1985-11-14
EP0162033B1 (de) 1989-12-13
EP0162033A3 (en) 1986-03-26

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