EP0028866B1 - Eine Formate und Calciumionen enthaltende stabile, wässrige Enzymzusammensetzung - Google Patents

Eine Formate und Calciumionen enthaltende stabile, wässrige Enzymzusammensetzung Download PDF

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Publication number
EP0028866B1
EP0028866B1 EP19800201059 EP80201059A EP0028866B1 EP 0028866 B1 EP0028866 B1 EP 0028866B1 EP 19800201059 EP19800201059 EP 19800201059 EP 80201059 A EP80201059 A EP 80201059A EP 0028866 B1 EP0028866 B1 EP 0028866B1
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EP
European Patent Office
Prior art keywords
enzyme
composition
compositions
calcium
per litre
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Expired
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EP19800201059
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English (en)
French (fr)
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EP0028866A1 (de
Inventor
George J. Kaminsky
James C. Letton
Ronald S. Christy
Mark J. Yunker
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT80201059T priority Critical patent/ATE8406T1/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 stabilised aqueous enzyme compositions which contain detergent compounds.
  • a stabilised aqueous enzyme composition containing a detergent, surfactant, an enzyme, a low molecular weight primary or secondary alcohol, and a water-soluble calcium salt derived from an organic acid, characterised in that:
  • the detergent surfactant can be a nonionic, anionic, cationic, zwitterionic, amphoteric or semi-polar nonionic surfactant, or a mixture thereof.
  • the surfactant comprises a substantial portion of nonionic surfactant together with either an anionic surfactant, a semi-polar nonionic surfactant, or a cationic surfactant or a mixture thereof.
  • the surfactants preferably comprise from 10% to 75%, more preferably from 20% to 50%, of the composition.
  • Nonionic surfactants are conventionally 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.
  • Nonionic surfactants have the general formula RA(CH 2CH 20)nH 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 usually varies from 2 to 24.
  • 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.
  • suitable nonionic surfactants can be found in U.S. Patent 4,111,855.
  • Synthetic anionic surfactants can be represented by the general formula R'S0 3 M wherein R 1 represents a hydrocarbon group such as a straight or branched alkyl radical containing from 8 to 24 carbon atoms or an alkyl phenyl radical containing from 9 to 15 carbon atoms in the alkyl group.
  • M is a salt forming cation which typically is sodium, potassium, ammonium, monoalkanol-ammonium, di- alkanolammonium, trialkanolammonium, or magnesium cation or a mixture thereof.
  • a preferred synthetic anionic surfactant is a water-soluble salt of an alkylbenzene sulfonic acid containing from 9 to 15 carbon atoms in the alkyl group.
  • 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.
  • Other suitable anionic surfactants are disclosed in U.S. Patent 4,170,565, Flesher et al, issued October 9, 1979.
  • Suitable anionic surfactants can include soaps and fatty acids containing from 8 to 24 carbon atoms, but it should be recognised that such soaps and fatty acids to tend to tie up calcium ions and thus are preferably limited to from 1% to 25%, most preferably from 10% to 20%.
  • 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 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 atom positions being filled by hydrogens, Y is selected from: wherein p is from 1 to 12, wherein p is from 1 to 12, and (9) mixtures thereof.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulphonium 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-solubilising 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 heterocylic secondary and ternary amines in which the aliphatic moieth 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 of alkyl groups or 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 carbon atoms and 2 moieties of alkyl groups or hydroxyl 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 an alkyl or hydroxy alkyl moiety of from 1 to 3 carbon atoms.
  • the enzyme component herein is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%.
  • the preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units per litre, preferably from 15 to 70 Anson units per litre, most preferably from 20 to 40 Anson units per litre. A proteolytic activity of from 3 to 5 Anson units per gram of product is desirable.
  • Other enzymes, including amylolytic enzymes can also be included.
  • the enzyme component is characterised by an isoelectric point of from 8.5 to 10, preferably from 9 to 9.5.
  • suitable protoelytic enzymes include many species which are known to be adapted for use in detergent compositions and, in fact, have been used in detergent compositions.
  • Sources of the enzymes include commercial enzyme preparations such as "Alcalase”* sold by Novo Industries, and “Maxatase”(s sold by Gist-Brocades, Delft, The Netherlands, which contain from 10% to 20% enzyme.
  • Another preferred enzyme composition for use herein is available, under the trade mark ESPERASEc, from Novo Industries A/S, Copenhagen, Denmark.
  • the low molecular weight primary or secondary alcohol is exemplified by methanol, ethanol, propanol, or isopropanol.
  • Monohydric alcohols are preferred for solubilising the surfactant but polyols containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups can be used and can provide improved enzyme stability.
  • polyols include propylene glycol, ethylene glycol and glycerine.
  • Ethanol is a particular preferred alcohol.
  • the composition contains from 0% to 20%, preferably from 5% to 15%, most preferably from 9% to 11.4% of the alcohol.
  • the formate is either formic acid or a water-soluble salt thereof, e.g. sodium formate.
  • the formates are surprisingly much more effective than other short chain carboxylic salts like the acetates and the propionates.
  • the formic acid or formate is used at a level from 0.1% to 10%, preferably from 0.3% to 3%, more preferably from 0.5% to 1.5% when the product pH is below 8.5 and from 3% to 10%, preferably from 4% to 8%, when the product pH is from 8.5 to 10.
  • Any water-soluble calcium salt can be used as a source of enzyme-accessible calcium ions, including calcium acetate, calcium formate and calcium propionate.
  • the level of enzyme-accessible calcium ions in the composition is from 0.1 to 10 millimoles of calcium ion per litre, provided that the amount of calcium ion per litre of the composition is from 0.1 to 2 millimoles at pHs below 8.5.
  • soap or fatty acid is present, the preferred level is from 2 to 6 millimoles of calcium ion per litre.
  • the pH of the composition is from 6.5 to 10, preferably from 7 to 8.5 to obtain a combination of enzyme stability and detergency.
  • a pH of from 8.5 to 10 preferably 9 to 10 is best for detergency. Both high and low pH adversely affects enzyme stability and low pH gives up too much detergent effectiveness.
  • Suitable pH buffers include mono-, di- and tri-ethanolamines. When the composition pH is from 8.5 to 10 triethanolamine is the best buffer. When soap or fatty acid is present, the preferred pH is from 7 to 7.5.
  • the balance of the composition is water.
  • the composition can contain optional ingredients, including perfumes, dyes, opacifiers, optical brighteners, suds, suppressors, pH adjusting agents, etc. Disclosures of suitable ingredients can be found in the patents and patent applications referred to above.
  • the composition is essentially free of materials such as detergent builders which tie up calcium ions to permit sufficient enzyme-accessible calcium ions to be present, although with the formate, excellent stability is achieved with very low levels of calcium ions, especially in the low pH range.
  • homogeneous aqueous detergent compositions of this invention comprise: (a) from 20% to 50% by weight of an organic synthetic surface-active agent; (b) from 3% to 15% by weight of a saturated fatty acid having 10 to 16 carbon atoms in the alkyl chain; (c) from 0.025% to about 1% by weight of an enzyme; (d) from 0.1 % to 3% by weight of formic acid or a water-soluble salt thereof; and (e) less than 2 millimoles of enzyme-accessible calcium per litre of the detergent composition, the pH of the composition, measured as is at 20°C, being from 6.5 to 8.5.
  • the saturated fatty acids preferably have from 12 to 14 carbon atoms in the alkyl chain
  • the detergent enzymes are represented by proteases or mixtures of proteases and amylases
  • formate is represented by formic acid
  • the enzyme-accessible calcium is present in an amount of from 0.5 to 1.5 millimoles per litre of the detergent composition
  • the pH of the composition as is, in the range from 7 to 7.5.
  • the saturated fatty acid component is incorporated in an amount of from 3% to 15%, preferably from 5% to 11 %.
  • the saturated fatty acids have from 10 to 16, preferably 12 or 14 carbon atoms in the alkyl chain.
  • the most preferred fatty acids are either lauric acid or lauric and myristic fatty acid in a mixture of 5:1 to 1 :1.
  • the compositions herein can comprise certain amounts of unsaturated fatty acids having, for example, 16 or 18 carbon atoms in the alkyl chain.
  • unsaturated fatty acids are oleic fatty acid and palmitoleic fatty acid.
  • the enzyme component is incorporated in an amount of from 0.025 to 1 %, preferably from 0.05% to 0.2%.
  • the preferred proteolytic enzyme component should give to the composition a proteolytic activity of at least 4 Anson units, preferably from 10 to 20 Anson units, per litre of the liquid detergent composition.
  • the enzyme component can be represented by a mixture of proteases and amylases. The proteolytic activity of that mixture is as defined hereinbefore.
  • the enzyme component is characterised by an isoelectric point of from 8.0 to 10, preferably from 8.5 to 9.5.
  • the formic acid or water-soluble salt thereof is used in an amount from 0.1% to 3%, preferably from 0.5% to 1.5%.
  • compositions herein comprise from 0.1 to 2, 'preferably from 0.5 to 1.5, millimoles of enzyme-accessible calcium per litre of the homogeneous enzyme containing detergent composition.
  • the preferred compositions are substantially free of sequestrants, for example, polyacids capable of forming calcium complexes which are soluble in the composition. However, minor amounts of sequestrants such as polyacids or mixtures of polyacids can be used.
  • the enzyme-accessible calcium is defined as the amount of calcium ions effectively available to the enzyme component.
  • the calcium sequestration resulting from e.g., 0.5% of a mixture of polyphosphonates and polyacids as exemplified hereinafter can represent 1 to 1.5 millimoles of calcium per litre of product.
  • the total calcium incorporated into the compositions is thus comprised of the enzyme-accessible calcium and also the calcium sequestered by the low levels of polyacids. From a practical standpoint the enzyme-accessible calcium is therefore the soluble calcium in the composition in the absence of any strong sequestrants, e.g., having an equilibrium constant of complexation with calcium equal to or greater than 1.5 at 20°C.
  • the pH of these preferred compositions is 6.5 to 8.5, preferably from 7 to 7.5 to obtain a combination of enzyme stability and detergency. Both high and low pH can adversely affect enzyme stability.
  • compositions herein frequently contain a series of optional ingredients which are used for the known functionality in conventional levels. While the inventive compositions are premised on aqueous enzyme-containing detergent compositions containing a critical ternary system as fully explained above, it is frequently desirable to use a phase regulant. This component together with water constitutes then the solvent matrix for the claimed liquid compositions.
  • Suitable phase regulants are well-known in liquid detergent technology and, for example, can be represented by lower aliphatic alcohols having from 2 to 6 carbon atoms and from 1 to 3 hydroxyl groups, ethers of diethylene glycol and lower aliphatic monoalcohols having from 1 to 4 carbon atoms.
  • phase regulants are: ethanol; n-propanol; isopropanol; butanol; 1,2-propanediol; 1,3-propanediol; n-hexanol; monomethyl-, -ethyl-, -propyl, and mono-butyl ethers and di-ethylene glycol.
  • a low molecular weight alcohol which may already be present can also function as a phase regulant.
  • Additional phase regulants having a relatively high boiling point and low vapor pressure can also be used provided they do not react with the other ingredients of the compositions.
  • phase regulants suitable for use herein.
  • these hydrotropes include salts of alkylarylsulfonates having up to 3 carbon atoms in the alkylgroup, e.g., sodium, potassium, ammonium and ethanolamine salts of xylene-, toluene-, ethylbenzene-, cumene-, and isopropylbenzene sulfonic acids.
  • the phase regulant is frequently used in an amount from 5% to 20%; the sum of phase regulant and water is normally in the range from 65% to 35%.
  • compositions herein can contain a series of further optional ingredients which are mostly used in additive levels, usually below 5%.
  • additives include; polyacids, suds regulants, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners.
  • a preferred additive is represented by a polyacid or mixture of polyacids in an amount below 1 %.
  • Suitable polyacids can include: citric, cyclohexane-1,1-dicarboxylic, cyclopropane-1,1-dicarboxylic, dimethylmalic, glutaric, o-hydroxybenzoic, m-hydroxybenzoic, p-hydroxybenzoic, itaconic, methyl- succinic, sodium tripolyphosphates, and nitrilotriacetic acid.
  • Preferred polyacid species for use herein can be represented by citric acid and organo-phosphonic acids and mixtures thereof.
  • alkylene-polyamino-polyalkylene phosphonic acids are ethylene diamine tetramethylene- phosphonic acid, hexamethylene diaminetetramethylene-phosphonic acid, diethylene triaminepenta- methylenephosphonic acid, and amino-trimethylenephosphonic acid or the salts thereof.
  • organo-phosphonic acids/salts are preferably used in an amount from 0.1 %-0.8%.
  • compositions under various usage conditions can require the utilisation of a suds regulant. While generally all detergent suds regulants can be utilised, preferred for use herein are alkylated polysiloxanes such as dimethylpolysiloxanes such as dimethylpolysiloxane also frequently termed silicones. The silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01% and 0.2%.
  • opacifiers it can also be desirable to utilise opacifiers inasmuch as they contribute to create a uniform appearance of the concentrated liquid detergent compositions.
  • suitable opacifiers include: polystyrene commercially known as LYTRON 621 ⁇ 9 manufactured by MONSANTO CHEMICAL CORPORATION. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
  • compositions herein can also contain known antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.001% to 0.25% (by reference to total composition). These antioxidants are frequently introduced in conjunction with the fatty acids. While many suitable antioxidants are readily known and available for that purpose especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole or 3-tertiarybutyl-4-hydroxyanisole more commonly known as BHA or butylated hydroxyanisole. Other suitable antioxidants are: 4,4'-thiobis (6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonyl phenol.
  • 21 day stability data follows the same general trend. As can be seen from the above data, the formate is best, followed by the acetate, which is followed by the propionate. The total amount of Ca ++ present is about 1.5 millimoles/litre, (some is added with the enzyme slurry).
  • Liquid detergent compositions were prepared by mixing the individual ingredients listed hereinafter in the stated proportions.
  • compositions 1-4 contained 3 millimoles and compositions 5-7 5 millimoles total of calcium/litre of the composition. However, some of the calcium ion is sequestrated by the phosphonic and sulphonic acid components so that the amount of enzyme-accessible calcium ion in each composition is from 0.1 to 2 millimoles per litre.
  • compositions 2 to 4, 6 and 7 in accordance with this invention were markedly superior vs. comparable compositions 1 and 5 which did not contain the formate stabiliser.
  • compositions 3 and 6 wherein the sodium formate is replaced by a substantially equivalent molar level of triethanolammonium formate, diethanolammonium formate, monoethanolammonium formate, potassium formate lithium formate or ammonium formate.
  • Liquid detergent compositions were prepared by mixing the listed ingredients in the stated proportions.
  • composition A is representative of the prior art.
  • Compositions B and C are reference compositions based on routine variations vs. the art compositions.
  • Composition I is an example of the invention herein.
  • the level of calcium in compositions A and B represents, based on current art khowledge, the minimum needed to achieve acceptable enzyme stability.
  • the amount of calcium in composition C was lowered to the point where phase instability and precipitation would not anymore occur.
  • the testing data are summarised below.
  • composition I in accordance with this invention vs. formulationwise closely related art composition ⁇ A ⁇ or what could be technical variations ⁇ B, C ⁇ of known art formulations.
  • compositions were prepared by mixing the listed components in the indicated proportions.
  • Composition D is what could be a technical variation of the state of art whereas formula IV is an execution of the claimed invention.
  • Composition V is a comparative example using acetic acid instead of formic acid.
  • the residual enzymatic activity (expressed in % of initial activity) were measured following exposure to accelerated storage conditions (48 hours at 40°C).
  • compositions of this invention are prepared by mixing the listed ingredients in a conventional manner.
  • compositions VI ⁇ XII are clear, homogeneous products having a markedly improved enzyme stability, especially upon storage.
  • the above general formula was modified by adding the indicated percentages of alkaline buffering agents (citric acid to trim) to provide the indicated product pH's and by adding the indicated percentages of CaCl 2 and sodium formate.
  • the individual compositions were tested and gave the indicated stability results.

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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)

Claims (7)

1. Eine stabilisierte, wässerige Enzymzusammensetzung, enthaltend ein oberflächenaktives Waschmittel, ein Enzym, einen primären oder sekundären Alkohol mit niedrigem Molekulargewicht und ein wasserlösliches, aus einer organischen Säure stammendes Calciumsalz, dadurch gekennzeichnet, daß das oberflächenaktive Waschmittel in einer Menge bis zu 75% vorliegt;
der Alkohol in einer Menge bis zu 20% vorliegt;
das Enzym in einer Menge von 0,025% bis 1% vorliegt;
die Zusammensetzung 0,1% bis 10% Ameisensäure oder ein wasserlösliches Salz davon enthält;
das lösliche Calciumsalz 0,1 bis 10 Millimol enzymzugängliches Calciumion je Liter der Zusammensetzung liefert, und der pH der Zusammensetzung im Bereich von 6,5 bis 10 liegt, mit der Maßgabe, daß die Menge des enzymzugänglichen Calciumions, je Liter der Zusammensetzung 0,1 bis 2 Millimol beträgt, wenn der pH der Zusammensetzung unter 8,5 liegt.
2. Eine Zusammensetzung gemäß Anspruch 1, enthaltend 0,3% bis 3% Ameisensäure oder ein wasserlösliches Salz davon, worin der pH 7,5 bis 8,5 beträgt und das Enzym ein proteolytisches Enzym ist.
3. Eine Zusammensetzung gemäß Anspruch 2, enthaltend 0,5% bis 1,5% Ameisensäure oder ein wasserlösliches Salz davon.
4. Eine Zusammensetzung gemäß Anspruch 3, enthaltend 0,05% bis 0,2% des proteolytischen Enzyms, um einen Enzymaktivitätsspiegel von 15 bis 70 Ansoneinheiten je Liter zu erhalten, wobei das Enzym einen isoelektrischen Punkt von 8,0 bis 10 hat.
5. Eine Zusammensetzung gemäß Anspruch 1, enthaltend ferner Triethanolamin als ein alkalisches Puffermittel.
6. Eine Zusammensetzung gemäß Anspruch 1, enthaltend 4% bis 8% Natriumformiat und 4 bis 8 Millimol enzymzugängliches Calciumion je Liter, wobei der pH der Zusammensetzung 9 bis 9,5 beträgt und das Enzym ein proteolytisches Enzym ist.
7. Eine Zusammensetzung gemäß Anspruch 1, welche im wesentlichen von Carbonationen frei ist.
EP19800201059 1979-11-09 1980-11-07 Eine Formate und Calciumionen enthaltende stabile, wässrige Enzymzusammensetzung Expired EP0028866B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80201059T ATE8406T1 (de) 1979-11-09 1980-11-07 Eine formate und calciumionen enthaltende stabile, waessrige enzymzusammensetzung.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US9290679A 1979-11-09 1979-11-09
US92906 1979-11-09
US12385780A 1980-02-22 1980-02-22
US123857 1980-02-22

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EP0028866A1 EP0028866A1 (de) 1981-05-20
EP0028866B1 true EP0028866B1 (de) 1984-07-11

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4529525A (en) * 1982-08-30 1985-07-16 Colgate-Palmolive Co. Stabilized enzyme-containing detergent compositions
DE3471687D1 (en) * 1983-02-14 1988-07-07 Procter & Gamble Stabilized aqueous enzyme composition
US4661287A (en) * 1983-10-05 1987-04-28 Colgate-Palmolive Company Stable soil release promoting enzymatic liquid detergent composition
US4486329A (en) * 1983-10-17 1984-12-04 Colgate-Palmolive Company Liquid all-purpose cleaner
AU4724989A (en) * 1988-12-30 1990-07-05 Unilever Plc Enzymatic liquid detergent composition
US5447649A (en) * 1990-03-01 1995-09-05 Novo Nordisk A/S Lipase containing liquid pre-spotter and use of such pre-spotter
US5358656A (en) * 1991-12-31 1994-10-25 Lever Brothers Company, Division Of Conopco, Inc. Compositions comprising glyceroglycolipids having an amine linkage as a surfactant or cosurfactant
US5635464A (en) * 1992-02-19 1997-06-03 The Procter & Gamble Company Aqueous hard surface detergent compositions containing calcium ions
CA2181125A1 (en) * 1995-07-14 1997-01-15 Gladys S. Gabriel Stabilization of enzymes in laundry detergent compositions
CN1238001A (zh) * 1996-09-24 1999-12-08 普罗格特-甘布尔公司 含有蛋白水解酶、肽醛和钙离子的液体洗涤剂
US20060270571A1 (en) * 2005-05-26 2006-11-30 Burke Peter A Deactivation of mineral encapsulated nanobacteria
WO2024012894A1 (en) * 2022-07-15 2024-01-18 Basf Se Alkanolamine formates for enzyme stabilization in liquid formulations

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA940070A (en) * 1968-12-23 1974-01-15 Jim S. Berry Stabilized aqueous enzyme composition
BE759360A (de) * 1969-11-25 1971-05-24 Procter & Gamble Europ
IT1106254B (it) * 1976-03-08 1985-11-11 Procter & Gamble Europ Composizione detergente liquida contenente enzimi

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EP0028866A1 (de) 1981-05-20

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