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EP0118933B1 - Stabilized aqueous enzyme composition - Google Patents

Stabilized aqueous enzyme composition Download PDF

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Publication number
EP0118933B1
EP0118933B1 EP84200157A EP84200157A EP0118933B1 EP 0118933 B1 EP0118933 B1 EP 0118933B1 EP 84200157 A EP84200157 A EP 84200157A EP 84200157 A EP84200157 A EP 84200157A EP 0118933 B1 EP0118933 B1 EP 0118933B1
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EP
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Prior art keywords
composition
calcium
enzyme
sequestering agent
compositions
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Expired
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EP84200157A
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German (de)
English (en)
French (fr)
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EP0118933A1 (en
Inventor
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 to AT84200157T priority Critical patent/ATE34767T1/de
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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
    • 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 stabilized aqueous enzyme compositions which contain detergent components.
  • the stabilized aqueous enzyme compositions of this invention comprise: (a) from 1 % to 75% of a non-soap detergent surfactant; (b) from 0.01 % to 5% of a preparation, having an activity of 120 KNU/g, of an a-amylolytic enzyme derived from Bacillus licheniformis; (c) from 3% to 30% of a sequestering agent; (d) a calcium-containing component to provide at least 1 x 10- 4.5 millimoles of enzyme-accessible calcium ion per liter of said composition; and (e) from 10% to 80% water.
  • detergency builder components The use of calcium to stabilize enzymes in aqueous media is well known, but this method of stabilization is in conflict with the incorporation of detergency builder components into liquid detergent compositions.
  • a major function of effective detergency builder components is to remove metal ions other than alkali metal ions from washing solutions by sequestration or precipitation. These undesirable metal ions, calcium and magnesium ions in particular, are generally designated water hardness.
  • the incorporation of such detergency builder components in a liquid detergent composition clearly complicates enzyme stability considerations.
  • an a-amylase can be stabilized in liquid detergent compositions containing calcium sequestering agents when said a-amylase is derived from Bacillus licheniformis (B. licheniformis) and a very low mimimum level of "enzyme-accessible" calcium ion, as hereinafter defined, is provided by incorporation of a calcium-containing component in accordance with a mathematical formula involving the equilibrium constants of complexation of said calcium sequestering agents.
  • the non-soap detergent surfactant can be selected from nonionic, anionic, cationic, zwitterionic, amphoteric and semi-polar nonionic surfactants and mixtures thereof.
  • the surfactants preferably comprise from 10% to 65%, more preferably from 20% to 50% of the formula by weight.
  • nonioic surfactant is produced by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, e.g., a hydroxyl, carboxyl, amino, or amido group, in the presence of an acidic or basic catalyst.
  • Such nonionic surfactants have the general formula RA(CH 2 CH 2 0),,H wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom and n represents the average number of ethylene oxide moieties.
  • R typically contains from 8 to 22 carbon atoms, but can also be formed by the condensation of propylene oxide with a lower molecular weight compound.
  • n can vary from 2 to 24 depending on the desired physical and detergency properties.
  • the hydrophobic moiety of the nonionic compound is preferably a primary or secondary, straight or slightly branched, aliphatic alcohol having from 8 to 24, preferably from 12 to 20 carbon atoms.
  • Alkyl amine oxides and other semi-polar nonionic surfactants are hereinafter described.
  • Another class of useful nonionic surfactants are alkylpolysaccharides having a hydrophobic group containing from about 8 to about 20 carbon atoms and a polysaccharide hydrophilic group containing from 1.5 to 10 saccharide units.
  • Synthetic anionic surfactants can be represented by the general formula R 1 S0 3 M wherein R 1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 8 to 24 carbon atoms and alkyl phenyl radicals containing from 9 to 15 carbon atoms in the alkyl group.
  • M is a salt forming cation which typically is selected from the group consisting of sodium, potassium, ammonium, monoalkanolammonium, dialkanolammonium, trialkanolammonium, and magnesium cations and mixtures thereof.
  • Preferred synthetic anionic surfactants include the water-soluble salts of alkylbenzene sulfonic acid containing from 9 to 15 carbon atoms in the alkyl group and water-soluble alkyl sulfates containing from 10 to 18 carbon atoms.
  • Another preferred synthetic anionic surfactant is a water-soluble salt of an alkyl polyethoxylate ether sulfate wherein the alkyl group contains from 8 to 24, preferably from 10 to 18 carbon atoms and there are from 1 to 20, preferably from 1 to 12 ethoxy groups.
  • alkyl group contains from 8 to 24, preferably from 10 to 18 carbon atoms and there are from 1 to 20, preferably from 1 to 12 ethoxy groups.
  • Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
  • Suitable cationic surfactants have the general formula wherein each R 2 is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to four structures selected from the group consisting of and mixtures thereof, each R 2 containing from 8 to 22 carbon atoms, and which may additionally contain up to 12 ethylene oxide groups, m is a number from 1 to 3, each R 3 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R 3 in a molecule being benzyl, x is a number from 0 to 11, the remainder of any carbon atoms positions being filled by hydrogens, Y is selected from the group consisting of: wherein p is from 1 to 12, and (9) mixtures thereof and Z is an anion such as halide, methyl sulfate or hydroxide.
  • One R 3 can also be a proton.
  • the resultant tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5.
  • a type of cationic surfactant generally compatible with anionic surfactants is a Cg-is alkyl tri C j - 3 alkyl ammonium chloride or methyl sulfate.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and one contains an anionic water- solubilizing group.
  • Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patents 3,925,262, Laughlin et al, issued December 9, 1975 and 3,929,678, Laughlin et al, issued December 30, 1975.
  • Ampholytic surfactants include derivatives of aliphatic heterocyclic secondary and ternary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent contains an anionic water- solubilizing group.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to 3 carbon atoms which can optionally be joined into ring structures; water-soluble phosphine oxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 and 2 moieties selected from the group consisting of alkyl groups and hydroxy alkyl groups, containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing 1 alkyl or hydroxy alkyl moiety of from 8 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxy alkyl moieties of from 1 to 3 carbon atoms.
  • compositions of the invention contain from 0.01 % to 5% by weight on a standard enzyme basis of an a-amylolytic enzyme (a-amylase) derived from B. licheniformis, preferably from 0.05% to about 2% by weight and most preferably from 0.1% to 1.0% by weight.
  • a-amylase a-amylolytic enzyme
  • Commercial enzyme preparations particularly those prepared for use in detergent compositions, are rarely pure enzyme and are, in any case, generally mixed with various inert materials.
  • Commercial enzyme preparations will typically have a low calcium metal content complexed with the enzyme and as part of the inert portion of the preparation. As described hereinafter, this calcium content must be recognized for stability considerations.
  • Standard enzyme basis is defined as an enzyme preparation having an activity measured in Kilo Novo a-amylase Units (KNU) of 120 KNU/gram.
  • KNU Kilo Novo a-amylase Units
  • One Kilo Novo a-amylase Unit (1 KNU) is the amount of enzyme which breaks down 5.26 grams of starch (Merck, Amylum Solubile Erg. B. 6, Batch 9947275) per hour at Novo's standard method for determination of a-amylase based upon the following standard conditions:
  • the Novo method Novo Industri A/S, Bagsvaerd, Denmark
  • the SKB method is described in Cereal Chemistry, 16, 712 (1939).
  • a-Amylases derived from B. licheniformis have been characterized as carbohydrases and more particularly 1,4-a-D-Glucan Glucanohydrolase.
  • a-Amylases for use in detergent compositions, granule detergent compositions in particular have been generally derived from Bacillus subtilis, but a-amylase derived from B. licheniformis suitable for use in the compositions of the present invention is available from a number of sources.
  • Termamyl® 120L Novo Industri A/S, Bagsvaerd, Denmark; Taka-Therm® L-340, Miles Laboratories, Elkhart, Indiana; Rohalase At * , Rohm & Haas, West Philadelphia, PA; Maxamyl HT®, Gist Brocades, Delft, The Netherlands, are a-amylases derived from B. licheniformis and suitable for use in the compositions of the present invention.
  • Reported deposit numbers for Bacillus licheniformis capable of producing a-amylase are NCIB 8061, NCIB 8059, ATCC, 6634, ATCC 6598, ATCC 11945, ATCC 8480, and ATCC 9945a.
  • British Patent Specification 1,296,839 published November 22, 1972, discloses methods of making a-amylases derived from B. licheniformis.
  • compositions of the invention contain from 3% to 30% and preferably from 5% to 25% of a calcium ion sequestering agent.
  • sequestering agents act as detergency builders to improve cleaning, particularly when the washing solution will contain metal ions other than alkali metal ions. Sequestration involves the formation of a coordination complex of the sequestering agent and metallic ions in solution to reduce the interactions of calcium with other materials in the wash solution.
  • sequestering agent includes multidentate ligands which can act as chelating agents and can include some ion exchange materials, but not those detergency builder materials which remove calcium ions from solutions only by precipitation reactions.
  • the sequestering agents used in the compositions of this invention include polyphosphates, polyphosphonates and polycarboxylates in soluble salt or acid form.
  • Polyphosphates which can sequester calcium ions are characterized by the general formula: and comprise the acid form and alkali metal, ammonium and substituted ammonium salts of pyrophosphoric acid and tripolyphosphoric acid and the water soluble polymetaphosphates.
  • pyrophosphoric acid and its salts are preferred because of their stability.
  • Water solutions of tripolyphosphates and polymetaphosphates tend to degrade to a mixture of pyrophosphate and orthophosphate, the latter having the ability to precipitate but not sequester calcium.
  • Polyphosphonates comprise a large range of organic compounds having two or more wherein M is a hydrogen or a salt-forming radical.
  • Suitable phosphonates include ethane-1-hydroxy-1,1- diphosphonates, ethanehydroxy-1,1,2-triphosphonates and their oligomeric ester chain condensates.
  • Particularly suitable polyphosphonates for use in the compositions of the invention are nitrogen-containing polyphosphonates such as ethylenediaminetetramethylene phosphonic acid and diethylenetriaminepenta- methylene phosphonic acid and alkali metal, ammonium and substituted ammonium salts thereof.
  • Suitable polycarboxylates include the acid form and alkali metal, ammonium and substituted ammonium salts of citric, ascorbic, phytic, mellitic, benzene, pentacarboxylic, oxydiacetic, carboxy- methyloxysuccinic, carboxymethyloxymalonic, cis-cyclohexanehexacarboxylic, cis-cyclopentanetetracarboxylic and oxydisuccinic acids. Also suitable are the polycarboxylate materials described in U.S. Patent 3,364,103 and polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
  • Particularly suitable polycarboxylates are those containing nitrogen such as ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid and nitrilotriacetic acid and alkali metal, ammonium and substituted ammonium salts thereof.
  • combinations of sequestering agents with different degrees of calcium ion sequestering power are particularly useful in the practice of this invention.
  • the combinations of citric acid and a nitrogen-containing sequestering agent selected from the group consisting of ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenephosphonic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid or mixtures and suitable salts thereof are particularly preferred.
  • Citric acid has a relatively lower equilibrium constant of complexation with calcium than the nitrogen-containing sequestering agents recited above.
  • Preferred ratios of citric acid to the nitrogen-containing sequestering agent are from about 50:1 to about 1:2 by weight and, more preferably, from about 30:1 to about 2:1 by weight.
  • the stabilized aqueous enzyme compositions of this invention comprise a calcium-containing component to provide at least 1 x 10 -4.5 millimoles of enzyme-accessible calcium, as hereinafter defined, per liter of said composition.
  • a calcium-containing component to provide at least 1 x 10 -4.5 millimoles of enzyme-accessible calcium, as hereinafter defined, per liter of said composition.
  • sufficient calcium-containing component is incorporated to provide at least 1 x 10 -4 millimoles of enzyme-accessible calcium and more preferably at least 1 x 10- 3 millimoles.
  • the compositions contain at least 1 x 10- 2 millimoles of enzyme-accessible calcium per liter of said composition.
  • the calcium-containing component can be or can be part of other essential or optional components, for example, an anionic surfactant in the form of a calcium salt or a calcium-sequestering agent complex. More typically, water-soluble or solubilizable calcium salts such as calcium chloride are employed. In the aqueous liquid detergent compositions of the present invention, calcium in different forms, insoluble, sequestered and enzyme-accessible, will reach an equilibrium as a function of the composition components and pH without regard to the initial nature of the calcium-containing component.
  • a upper limit of enzyme-accessible calcium in compositions of the invention can be set by practical considerations not related to enzyme stability. There is little improvement in the stability of alpha-amylase derived from B. licheniformis in compositions of the invention at enzyme-accessible calcium levels above 1 x 10- 2 millimoles per liter. In the preferred compositions of the invention this level of enzyme-accessible calcium is provided by total calcium levels of no more than from 0.1% to 0.3% of the composition by weight.
  • a calcium-sequestering agent complex is nevertheless capable of sequestering heavy metal ions such as iron, manganese and copper which are associated with certain staining problems. This is a result of higher complexation and formation constants of said sequestering agents with heavy metal ions relative to the constants with calcium.
  • Enzyme-accessible calcium is analogous to free or ionic calcium in aqueous solutions of less complexity than the compositions of the invention.
  • enzyme-accessible calcium is determined by the method described in the following publication:
  • compositions of the invention by use of the following assumptions:
  • alkaline earth metals other than calcium are substantially less effective for stabilizing the compositions of the invention.
  • compositions of this invention contain from 10% to 80% water, preferably from 15% to 60% water, by weight.
  • Preferred compositions have a pH of from about 6.5 to about 9.0.
  • compositions of this invention can contain components other than those disclosed as essential.
  • compositions of this invention can contain enzymes other than a-amylase derived from B. licheniformis, proteolytic enzymes in particular.
  • suitable proteolytic enzymes include many enzyme preparations adapted for use in detergent compositions and, in fact, used in detergent compositions.
  • Sources of the enzymes include commercial enzyme preparations such as Alcalase@ sold by Novo Industries, A/S, Copenhagen, Denmark and Maxatase @ sold by Gist-Brocades, Delft, The Netherlands.
  • Other preferred enzyme compositions include those commercially available under the tradenames Esperase @ , manufactured and sold by Novo Industries, A/S, Copenhagen, Denmark and "Az-Protease” manufactured and sold by Gist-Brocades, Delft, The Netherlands.
  • levels of enzyme accessible calcium above about 1 x 10- 2 millimoles per liter provide excellent stability to proteolytic enzymes (proteases) incorporated in the compositions of the invention and the inclusion of a proteolytic enzyme is a preferred embodiment. There is, however, no dramatic increase in proteolytic enzyme stability over any narrow range of enzyme-accessible calcium levels as is seen with a-amylase (derived from B. licheniformis) between 1 x 10- S and 1 x 10- 4.
  • compositions of this invention can contain solvents other than water.
  • Low molecular weight primary or secondary alcohol exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing the surfactant but polyols containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups can be used and can provide improved enzyme stability.
  • polyols include propylene glycol, ethylene glycol, glycerine and 1,2-propanediol.
  • Ethanol is a particularly preferred alcohol.
  • the compositions contain from 0% to 30%, preferably from about 1% to 15%, of alcohols.
  • a short chain carboxylic acid salt can be used to stabilize enzymes, particularly proteolytic enzymes, as disclosed in U.S. Patent 4,318,818, issued March 9, 1982.
  • the short chain carboxylic acid salt preferably is a formate, e.g., formic acid and its salts.
  • the formates are surprisingly much more effective than other short chain carboxylic salts such as the acetates and the propionates.
  • the short chain carboxylic acid salt is used at a level from 0.1% to 10%, preferably from 0.3% to 3%, more preferably from 0.5% to 2.0% when the product pH is below about 8.5 and from 3% to 10%, preferably from 4% to 8%, when the product pH is from 8.5 to 10.
  • a fatty acid component is incorporated in an amount of from 3% to 25% by weight, preferably from 5% to 20% by weight.
  • the fatty acids have from 10 to 22, preferably from 12 to 18 carbon atoms in the alkyl chain.
  • Compositions containing fatty acids will have a pH of from 6.5 to 9.0.
  • compositions of the invention can contain such materials as fabric whiteners and brighteners, sudsing control agents, hydrotropes such as sodium toluene or xylene sulfonate, perfumes, colorants, opacifiers, anti-redeposition agents and alkalinity control or buffering agents such as monoethanolamine and triethanolamine.
  • materials such as fabric whiteners and brighteners, sudsing control agents, hydrotropes such as sodium toluene or xylene sulfonate, perfumes, colorants, opacifiers, anti-redeposition agents and alkalinity control or buffering agents such as monoethanolamine and triethanolamine.
  • the use of these materials is well known in the detergent art.
  • Materials or anions that tend to precipitate calcium should preferably be restricted to minimum levels. Examples are carbonates, sulfates, and orthophosphates.
  • the fatty acids of preferred compositions act to precipitate calcium in a washing solution, they have no such effect in the undiluted compositions of the invention if calcium levels are controlled carefully.
  • the fatty acid content of the compositions of the invention at least at pH values below 8.5, does not substantially effect the enzyme-accessible calcium level of said compositions and can be neglected when calculating the enzyme-accessible calcium level as disclosed hereinbefore.
  • Liquid detergent compositions were prepared by mixing the components listed hereinafter in the stated proportions.
  • Composition A was prepared in thirteen variations with CaC1 2 and sodium diethylenetriaminepentaacetate (DTPA) levels as indicated. The variations were stored in airtight containers for 1 week at 100°F. (37.8°C) a-amylase activity was then measured by Technicon Industrial Method #500-77P dated September 12, 1977, as revised September 1979, (Technicon Industrial Systems, Tarrytown, N.Y. 10591), but any suitable method such as the one described in U.S. Patent 4,284,722 issued August 18, 1981, to Tamuri et al, will give equivalent results. a-amylase activity at the end of the storage period was divided by activity directly after composition preparation to calculate percent retained activity.
  • DTPA sodium diethylenetriaminepentaacetate
  • Composition B was prepared in seven variations with CaCl 2 ⁇ levels as indicated. The variations were stored for 1 month at 90°F (32.2°C) and at 70°F (21°C) and evaluated for a-amylase stability in the same manner as the variations of Composition A. Footnotes to Composition B
  • results show the dramatic improvement in a-amylase (derived from B. licheniformis) stability in an aqueous liquid detergent composition when a calcium-containing component is incorporated that provides at least 1 x 10 -4.5 millimoles of enzyme-accessible calcium.
  • the results also point out the advantage of mixtures of sequestering agents.
  • a sequestering agent with high equilibrium constant of complexation e.g., the nitrogen-containing sequestering agents disclosed hereinbefore, will tend to sequester all available calcium to the point of theoretical capacity, but can release such calcium in washing solutions to in turn sequester heavy metal ions such as copper, iron and manganese.
  • a sequestering agent with a lower equilibrium constant of complexation such as alkali metal citrates or citric acid can be incorporated in the compositions of the invention without addition of calcium-containing components at a level to satify theoretical capacity.
  • sequestering agents are available to act as detergency builders effective in the presence of alkaline earth metal ions in washing solutions.
  • a-amylase derived from B. licheniformis has, in effect, an equilibrium constant of complexation with calcium somewhat greater than citrate, or more precisely, an equilibrium constant that can hold sufficient calcium for stabilization in an aqueous solution containing at least 1 x 10 -4.5 millimoles of enzyme accessible calcium.
  • a-amylases derived by B. subtilis, Ban@ from Novo Industri and Rapidase @ from Gist Brocade are incorporated in the compositions of Example I replacing the Termamyl R120L. It is not possible to add a sufficient amount of a calcium-containing component to stabilize said a-amylases derived from B. subtilis without precipitation of calcium citrate in the aqueous liquid detergent compositions.
  • composition is prepared by mixing the ingredients listed.
  • the incorporation of 0.02% calcium chloride in the composition provides an enzyme accessible calcium level of at least 1 x 10- 4.5 millimoles per liter.
  • Potassium pyrophosphate, potassium carboxymethyloxymalonate and potassium carboxymethyloxysuccinate are each substituted for citric acid in Examples I, II and IV.
  • Composition pH is adjusted to 8.0.
  • a calcium chloride level of 0.3% by weight is sufficient to provide an enzyme-accessible calcium level greater than 1 x 10- 4.5 millimoles and stabilize the a-amylase derived from B. licheniformis incorporated in said compositions.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Enzymes And Modification Thereof (AREA)
EP84200157A 1983-02-14 1984-02-06 Stabilized aqueous enzyme composition Expired EP0118933B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84200157T ATE34767T1 (de) 1983-02-14 1984-02-06 Stabilisierte waessrige enzymzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46624383A 1983-02-14 1983-02-14
US466243 1983-02-14

Publications (2)

Publication Number Publication Date
EP0118933A1 EP0118933A1 (en) 1984-09-19
EP0118933B1 true EP0118933B1 (en) 1988-06-01

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EP (1) EP0118933B1 (es)
JP (1) JPS59206497A (es)
AT (1) ATE34767T1 (es)
AU (1) AU575313B2 (es)
CA (1) CA1213541A (es)
DE (1) DE3471687D1 (es)
GR (1) GR81415B (es)
IE (1) IE57055B1 (es)
MX (1) MX161307A (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2767187C2 (ru) * 2017-04-25 2022-03-16 НЮТРЕКО АйПи ЭССЕТС Б.В. Связывающее кальций вещество для применения в предотвращении мертворождения

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DE3685768T2 (de) * 1985-04-15 1993-01-21 Procter & Gamble Fluessige reinigungsmittel mit einer anionischen oberflaechenaktiven verbindung, einem verstaerker und einem proteolytischen enzym.
US5223166A (en) * 1986-11-17 1993-06-29 Henkel Kommanditgesellschaft Auf Aktien Preparations and processes for cleaning and disinfecting endoscopes
DE3639322A1 (de) * 1986-11-17 1988-05-26 Henkel Kgaa Verfahren zur reinigung und desinfektion von endoskopen und mittel zur durchfuehrung des verfahrens
DE3816734A1 (de) * 1988-05-17 1989-11-30 Henkel Kgaa Verfahren zur reinigung und desinfektion von hitze- und korrosionsempfindlichen medizinischen geraeten, insbesondere von endoskopen und mittel zur durchfuehrung des verfahrens
US5269960A (en) * 1988-09-25 1993-12-14 The Clorox Company Stable liquid aqueous enzyme detergent
US5605881A (en) * 1993-09-03 1997-02-25 Minolta Co., Ltd. Cleaning liquid for recycling copy medium for electrophotography
JP3081534B2 (ja) * 1995-12-22 2000-08-28 花王株式会社 酵素含有造粒物、その製造法及びこれを含有する組成物

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GB1296839A (es) * 1969-05-29 1972-11-22
IT1106254B (it) * 1976-03-08 1985-11-11 Procter & Gamble Europ Composizione detergente liquida contenente enzimi
DE2633601A1 (de) * 1976-07-27 1978-02-02 Henkel Kgaa Fluessiges, als wasch- und reinigungsmittel verwendbares, enzymhaltiges konzentrat
US4287082A (en) * 1980-02-22 1981-09-01 The Procter & Gamble Company Homogeneous enzyme-containing liquid detergent compositions containing saturated acids
US4305837A (en) * 1980-10-30 1981-12-15 The Procter & Gamble Company Stabilized aqueous enzyme composition
DE3068554D1 (en) * 1979-11-09 1984-08-16 Procter & Gamble Stabilised aqueous enzyme composition containing formate and calcium ions
US4529525A (en) * 1982-08-30 1985-07-16 Colgate-Palmolive Co. Stabilized enzyme-containing detergent compositions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2767187C2 (ru) * 2017-04-25 2022-03-16 НЮТРЕКО АйПи ЭССЕТС Б.В. Связывающее кальций вещество для применения в предотвращении мертворождения

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ATE34767T1 (de) 1988-06-15
GR81415B (es) 1984-12-11
JPS59206497A (ja) 1984-11-22
EP0118933A1 (en) 1984-09-19
MX161307A (es) 1990-09-06
IE840321L (en) 1984-08-14
IE57055B1 (en) 1992-04-08
CA1213541A (en) 1986-11-04
AU2453884A (en) 1984-08-23
DE3471687D1 (en) 1988-07-07

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