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WO1992001775A1 - Liquid enzyme preparation - Google Patents

Liquid enzyme preparation Download PDF

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Publication number
WO1992001775A1
WO1992001775A1 PCT/EP1991/001334 EP9101334W WO9201775A1 WO 1992001775 A1 WO1992001775 A1 WO 1992001775A1 EP 9101334 W EP9101334 W EP 9101334W WO 9201775 A1 WO9201775 A1 WO 9201775A1
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WO
WIPO (PCT)
Prior art keywords
enzyme
enzyme preparation
enzymes
weight
preparation according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1991/001334
Other languages
German (de)
French (fr)
Inventor
Wolfgang Drees
Albrecht Weiss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1992001775A1 publication Critical patent/WO1992001775A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 invention relates to a liquid, essentially anhydrous enzyme preparation which can be used, for example, as a stock solution for the production of liquid detergents or the like.
  • enzyme solutions of hydrolases, especially proteases are not per se stable in storage. This applies in particular to such enzyme Solutions which are to be used for liquid detergents, since in the purification of the enzyme solutions apparently, in addition to impurities, substances which cause stabilization are also removed.
  • German patent application P 39 18 761 proposes a liquid, water-containing enzyme preparation which contains 1.5 to 20% by weight hydrolases, 20 to 40% by weight propylene glycol and 0.5 to 5% by weight boric acid and / or contains their soluble salts.
  • the enzyme concentrate described there is in the form of a solution which also necessarily contains enzyme stabilizers.
  • the invention thus relates to an essentially anhydrous, liquid enzyme preparation containing 5 to 20% by weight of enzymes, 20 to 60% by weight of precipitant and ad 100% by weight of organic water-miscible solvents.
  • the enzyme preparations according to the invention are suitable for the assembly of a large number of enzymes.
  • Liquid preparations of hydrolases can preferably be prepared in this way.
  • the proteases in particular the proteases of the subtilisin type, are preferred among the hydrolases, but other proteases, such as metalloproteases or animal proteases, can also be prepared in this way.
  • proteases such as those in detergents, in particular liquid detergents, are currently preferred be used.
  • related hydrolases such as, for example, ylases, lipases, cellulases or the like, can also be packaged in this way.
  • the enzymes are dissolved in the organic water-miscible solvent and precipitated with a precipitant, so that they are present as a dispersion. It is preferred to carry out the precipitation step with stirring in order to ensure fine particle size.
  • Alcohols are primarily suitable as organic water-dilutable solvents, and among these in particular polyfunctional alcohols.
  • Particularly preferred polyfunctional alcohols are propylene glycol and / or glycerol.
  • other glycols and the di- and trimers of the abovementioned are also suitable.
  • the person skilled in the art can easily determine the solubility by means of a preliminary test. In the vast majority of cases, however, 1,2-propylene glycol has proven to be the most suitable proposal.
  • surfactants have proven themselves primarily as precipitants, since these prevent or delay sedimentation of the enzyme preparations according to the invention which are present in dispersion.
  • nonionic surfactants are preferred.
  • suitable surfactants the person skilled in the art will primarily use products which are liquid at room temperature. Ethoxylates of alcohols with 6 to 20 C atoms or of alkylphenols with 8 to 12 C atoms in the alkyl part have proven successful. It is known that such products can be produced with any degree of ethoxylation.
  • the low-ethoxylated types (1 to 10 mol, in particular 2 to 5 mol, ethylene oxide / mol alcohol or alkylphenol) are preferred for the purposes of the invention.
  • the enzyme preparations according to the invention can also contain further auxiliaries.
  • substances against loss of activity of the enzyme can also be used.
  • boric acid and its salts, insofar as they are soluble or dispersible in the preparations can be added.
  • Lower carboxylic acids, in particular polyfunctional carboxylic acids such as tartaric acid or citric acid, can also be present. The amount of such substances should not exceed 10% by weight of the total preparation and should be at least 1% by weight.
  • the corresponding enzymes in solid form are used, which can be obtained by precipitation or drying of enzyme solutions.
  • the solid enzymes are then first dissolved in the water-miscible organic solvent and the precipitant is added with stirring until a dispersion has formed. If desired, further auxiliaries can then be added. It is possible to heat slightly during the dissolving process and to cool during the precipitation step, but the low temperature stability of the enzymes above about 60 ° C. must be taken into account.
  • the enzyme preparations according to the invention can be used as a stock solution in the production of liquid detergents and the like.
  • a subtilisin protease which is customary in detergents, was precipitated from concentrated solution in a customary manner, filtered off, dispersed in acetone and filtered off again.
  • 1 g of the enzyme powder thus obtained with the specific protease activity of 2,500,000 HPE / g was then dissolved in 5 g of 1,2-propylene glycol with stirring over a period of 2 hours. With further stirring, 6.6 g of an ethoxylated tallow alcohol (3 mol EO / ol tallow alcohol) were then added. Due to the addition of tallow alcohol, the enzyme precipitated out in a very finely divided form without sedimentation. The result was a thin, well pourable dispersion with a specific activity of 193,000 HPE / g.

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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)

Abstract

The aim of the invention is to improve the storage life of stock solutions of enzymes. Proposed to achieve this is a substantially water-free, liquid enzyme preparation containing 5-20 wt % of enzymes and 20-60 wt % of precipitating agent and made up to 100 wt % with organic solvents miscible with water.

Description

'Flüssige Enzymzubereituπg" 'Liquid enzyme preparation'

Die Erfindung betrifft eine flüssige im wesentlichen wasserfreie Enzymzubereitung, die beispielsweise als Stammlösung zur Herstellung von Flüssigwaschmitteln oder dergleichen verwendet werden kann.The invention relates to a liquid, essentially anhydrous enzyme preparation which can be used, for example, as a stock solution for the production of liquid detergents or the like.

Es ist bekannt, in Waschmitteln, auch Flüssigwaschmitteln, Enzyme, insbesondere Proteasen, einzusetzen. Für den Einsatz in festen Waschmitteln werden die Enzyme zu festen körnigen Zubereitungen aufgearbeitet. Mit dem Voranschreiten der Flüssigwaschmittel besteht ein Bedarf auch für derartige Zubereitungen, lagerfähige Stammlö- sungen herstellen zu können, die dann in einem nachfolgenden Ver¬ arbeitungsschritt dem Flüssigwaschmittel zugesetzt werden können.It is known to use enzymes, in particular proteases, in detergents, including liquid detergents. The enzymes are processed into solid granular preparations for use in solid detergents. As liquid detergents advance, there is also a need for such preparations to be able to produce stockable stock solutions which can then be added to the liquid detergent in a subsequent processing step.

Enzymlösungen von Hydrolasen, insbesondere Proteasen, sind jedoch per se nicht lagerstabil. Dies gilt insbesondere für solche Enzym- lösungen, die für Flüssigwaschmittel eingesetzt werden sollen, da bei der Aufreinigung der Enzymlösungen anscheinend neben Verunrei¬ nigungen auch Stoffe entfernt werden, die eine Stabilisierung be¬ dingen.However, enzyme solutions of hydrolases, especially proteases, are not per se stable in storage. This applies in particular to such enzyme Solutions which are to be used for liquid detergents, since in the purification of the enzyme solutions apparently, in addition to impurities, substances which cause stabilization are also removed.

In der deutschen Patentanmeldung P 39 18 761 wird eine flüssige, wasserhaltige Enzymzubereitung vorgeschlagen, die 1,5 bis 20 Gew.-% Hydrolasen, 20 bis 40 6ew.-% Propylenglykol und 0,5 bis 5 Gew.-% Borsäure und/oder deren lösliche Salze enthält. Das dort beschrie¬ bene Enzymkonzentrat liegt in Form einer Lösung vor, die zwingend auch Enzymstabilisatoren enthält.German patent application P 39 18 761 proposes a liquid, water-containing enzyme preparation which contains 1.5 to 20% by weight hydrolases, 20 to 40% by weight propylene glycol and 0.5 to 5% by weight boric acid and / or contains their soluble salts. The enzyme concentrate described there is in the form of a solution which also necessarily contains enzyme stabilizers.

Da Lösungen im allgemeinen Veränderungs- und Alterungsprozessen viel stärker ausgesetzt sind als Feststoffe, haben sich die Erfinder die Aufgabe gestellt, eine Enzymzubereitung zu schaffen, die zwar auch flüssig und schüttbar ist, jedoch das Enzym nicht physikalisch ge¬ löst, sondern zumindest teilweise in dispergierter, also fester Form enthält.Since solutions in general are much more exposed to change and aging processes than solids, the inventors have set themselves the task of creating an enzyme preparation which is also liquid and pourable, but which does not dissolve the enzyme physically, but at least partially in a dispersed manner contains solid form.

Gegenstand der Erfindung ist somit eine im wesentlichen wasserfreie, flüssige Enzymzubereitung, enthaltend 5 bis 20 Gew.-% Enzyme, 20 bis 60 Gew.-% Fällungsmittel und ad 100 Gew.-% organische wasser¬ mischbare Lösungsmittel.The invention thus relates to an essentially anhydrous, liquid enzyme preparation containing 5 to 20% by weight of enzymes, 20 to 60% by weight of precipitant and ad 100% by weight of organic water-miscible solvents.

Die erfindungsgemäßen Enzymzubereitungen eignen sich zur Konfektio¬ nierung einer Vielzahl von Enzymen. Bevorzugt können auf diesem Wege flüssige Zubereitungen von Hydrolasen hergestellt werden. Unter den Hydrolasen sind die Proteasen, insbesondere die Proteasen vom Subtilisin-Typ bevorzugt, jedoch können auch andere Proteasen, wie Metallo-Proteasen oder tierische Proteasen auf diesem Wege konfek¬ tioniert werden. Unter den Proteasen sind derzeitig solche Proteasen bevorzugt wie sie in Waschmitteln, insbesondere Flüssigwaschmitteln eingesetzt werden. Es können aber auch verwandte Hydrolasen, wie beispielsweise A ylasen, Lipasen, Cellulasen oder dergleichen in dieser Weise konfektioniert werden.The enzyme preparations according to the invention are suitable for the assembly of a large number of enzymes. Liquid preparations of hydrolases can preferably be prepared in this way. The proteases, in particular the proteases of the subtilisin type, are preferred among the hydrolases, but other proteases, such as metalloproteases or animal proteases, can also be prepared in this way. Among the proteases, proteases such as those in detergents, in particular liquid detergents, are currently preferred be used. However, related hydrolases, such as, for example, ylases, lipases, cellulases or the like, can also be packaged in this way.

Zur Herstellung der erfindungsgemäßen Zubereitungen werden die En¬ zyme in dem organischen wassermischbaren Lösungsmittel gelöst und mit einem Fällungsmittel ausgefällt, so daß sie als Dispersion vor¬ liegen. Dabei ist es bevorzugt, den Fällungsschritt unter Rühren durchzuführen, um Feinteiligkeit zu gewährleisten.To prepare the preparations according to the invention, the enzymes are dissolved in the organic water-miscible solvent and precipitated with a precipitant, so that they are present as a dispersion. It is preferred to carry out the precipitation step with stirring in order to ensure fine particle size.

Als organische wasserverdünnbare Lösungsmitteln sind in erster Linie Alkohole geeignet und unter diesen insbesondere mehrfunktionelle Alkohole. Besonders bevorzugte mehrfunktionelle Alkohole sind Propy¬ lenglykol und/oder Glycerin. Geeignet sind jedoch auch andere Gly- kole sowie die Di- und Trimeren der genannten. Zum Auffinden eines geeigneten Lösungsmittels kann der Fachmann in einfacher Weise durch einen Vortest die Löslichkeit feststellen. In den allermeisten Fällen hat sich allerdings 1,2-Propylenglykol als der geeignetste Vorschlag erwiesen.Alcohols are primarily suitable as organic water-dilutable solvents, and among these in particular polyfunctional alcohols. Particularly preferred polyfunctional alcohols are propylene glycol and / or glycerol. However, other glycols and the di- and trimers of the abovementioned are also suitable. To find a suitable solvent, the person skilled in the art can easily determine the solubility by means of a preliminary test. In the vast majority of cases, however, 1,2-propylene glycol has proven to be the most suitable proposal.

Als Fällungsmittel haben sich in erster Linie Tenside bewährt, da diese ein Sedimentieren der in Dispersion vorliegenden erfindungs¬ gemäßen Enzymzubereitungen verhindern bzw. verzögern. Unter den Tensiden sind nichtionische Tenside bevorzugt. Zur Auswahl geeig¬ neter Tenside wird der Fachmann in erster Linie auf bei Raumtem¬ peratur in Substanz flüssige Produkte zurückgreifen. Bewährt haben sich Ethoxylate von Alkoholen mit 6 bis 20 C-Atomen bzw. von Al- kylphenolen mit 8 bis 12 C-Atomen im Alkylteil. Bekanntlich sind derartige Produkte mit beliebigen Ethoxylierungsgraden herstellbar. Für die erfindungsgemäßen Zwecke sind die niedrig ethoxylierten Ty¬ pen (1 bis 10 mol, insbesondere 2 bis 5 mol Ethylenoxid/mol Alkohol bzw. Alkylphenol) bevorzugt. Die erfindungemäßen Enzymzubereitungen können darüber hinaus noch weitere Hilfsstoffe enthalten. So können beispielsweise Stoffe gegen Aktivitätsverlust des Enzyms mit eingesetzt werden. So können bei¬ spielsweise Borsäure und ihre Salze, soweit in den Zubereitungen löslich oder dispergierbar, beigegeben werden. Auch niedere Carbon¬ säuren, insbesondere mehrfunktionelle Carbonsäuren wie Weinsäure oder Zitronensäure können zugegen sein. Die Menge derartiger Stoffe soll dabei 10 Gew.-% der Gesamtzubereitung nicht übersteigen und mindestens 1 Gew.-% betragen.Surfactants have proven themselves primarily as precipitants, since these prevent or delay sedimentation of the enzyme preparations according to the invention which are present in dispersion. Among the surfactants, nonionic surfactants are preferred. For the selection of suitable surfactants, the person skilled in the art will primarily use products which are liquid at room temperature. Ethoxylates of alcohols with 6 to 20 C atoms or of alkylphenols with 8 to 12 C atoms in the alkyl part have proven successful. It is known that such products can be produced with any degree of ethoxylation. The low-ethoxylated types (1 to 10 mol, in particular 2 to 5 mol, ethylene oxide / mol alcohol or alkylphenol) are preferred for the purposes of the invention. The enzyme preparations according to the invention can also contain further auxiliaries. For example, substances against loss of activity of the enzyme can also be used. For example, boric acid and its salts, insofar as they are soluble or dispersible in the preparations, can be added. Lower carboxylic acids, in particular polyfunctional carboxylic acids such as tartaric acid or citric acid, can also be present. The amount of such substances should not exceed 10% by weight of the total preparation and should be at least 1% by weight.

Zur Herstellung der erfindungsgemäßen Enzymzubereitungen geht man von den entsprechenden Enzymen in fester Form aus, die durch Fällen oder Trocknen von Enzymlösungen gewonnen werden können. Die festen Enzyme werden dann zunächst in dem mit Wasser mischbaren organischen Lösungsmittel gelöst und es wird unter Rühren das Fällungsmittel zugegeben bis eine Dispersion entstanden ist. Daraufhin können ge- wünschtenfalls weitere Hilfsstoffe zugegeben werden. Es ist möglich, bei dem Lösevorgang leicht zu erwärmen und beim Fällungsschritt zu kühlen, jedoch ist dabei die oberhalb von ca. 60°C geringe Tempera¬ turstabilität der Enzyme zu beachten.To prepare the enzyme preparations according to the invention, the corresponding enzymes in solid form are used, which can be obtained by precipitation or drying of enzyme solutions. The solid enzymes are then first dissolved in the water-miscible organic solvent and the precipitant is added with stirring until a dispersion has formed. If desired, further auxiliaries can then be added. It is possible to heat slightly during the dissolving process and to cool during the precipitation step, but the low temperature stability of the enzymes above about 60 ° C. must be taken into account.

Die erfindungsgemäßen Enzymzubereitungen können als Stammlösung bei der Herstellung von Flüssigwaschmitteln und dergleichen eingesetzt werden. The enzyme preparations according to the invention can be used as a stock solution in the production of liquid detergents and the like.

B e i s p i e lExample

Eine in Waschmittel übliche Subtilisin-Protease wurde in üblicher Weise aus konzentrierter Lösung ausgefällt, abfiltriert, in Aceton dispergiert und erneut abfiltriert. 1 g des so erhaltenen Enzympul¬ vers mit der spezifischen Protease-Aktivität von 2.500.000 HPE/g wurde sodann in 5 g 1,2-Propylenglykol unter Rühren während eines Zeitraums von 2 Stunden gelöst. Unter weiterem Rühren wurden dann 6,6 g eines ethoxylierten Talgalkohols (3 mol EO/ ol Talgalkohol) versetzt. Durch den Talgalkoholzusatz fiel das Enzym in feinst verteilter Form aus, ohne zu sedimentieren. Es entstand eine dünnflüssige, gut schüttbare Dispersion mit einer spezifischen Aktivität von 193.000 HPE/g. A subtilisin protease, which is customary in detergents, was precipitated from concentrated solution in a customary manner, filtered off, dispersed in acetone and filtered off again. 1 g of the enzyme powder thus obtained with the specific protease activity of 2,500,000 HPE / g was then dissolved in 5 g of 1,2-propylene glycol with stirring over a period of 2 hours. With further stirring, 6.6 g of an ethoxylated tallow alcohol (3 mol EO / ol tallow alcohol) were then added. Due to the addition of tallow alcohol, the enzyme precipitated out in a very finely divided form without sedimentation. The result was a thin, well pourable dispersion with a specific activity of 193,000 HPE / g.

Claims

P a t e n t a n s p r ü c h e Patent claims 1. Im wesentlichen wasserfreie, flüssige Enzymzubereitung enthal¬ tend1. Containing essentially water-free, liquid enzyme preparation 5 bis 20 Gew.-% Enzyme 20 bis 60 Gew.-% Fällungsmittel und ad 100 Gew.-% organische wassermischbare Lösungsmittel.5 to 20% by weight of enzymes 20 to 60% by weight of precipitant and ad 100% by weight of organic water-miscible solvents. 2. Enzymzubereitung nach Anspruch 1, dadurch gekennzeichnet, daß als Enzyme Hydrolasen, insbesondere Proteasen und/oder Amylasen enthalten sind.2. Enzyme preparation according to claim 1, characterized in that hydrolases, in particular proteases and / or amylases are contained as enzymes. 3. Enzymzubereitung nach einem der Ansprüche 1 oder 2, dadurch ge¬ kennzeichnet, daß als Fällungsmittel nichtionische Tenside, ins¬ besondere ethoxylierte Alkohole und/oder ethoxylierte Alkylphe- nole eingesetzt werden.3. Enzyme preparation according to one of claims 1 or 2, characterized in that nonionic surfactants, in particular ethoxylated alcohols and / or ethoxylated alkylphenols, are used as precipitants. 4. Enzymzubereitung nach einem der Ansprüche 1 bis 3, dadurch ge¬ kennzeichnet, daß als organische Lösungsmittel Alkohole, insbe¬ sondere mehrfunktionelle Alkohole eingesetzt werden.4. Enzyme preparation according to one of claims 1 to 3, characterized in that the organic solvents used are alcohols, in particular polyfunctional alcohols. 5. Enzymzubereitung nach einem der Ansprüche 1 bis 4, dadurch ge¬ kennzeichnet, daß als organische Lösungsmittel Propylenglykol und/oder Glycerin eingesetzt werden.5. Enzyme preparation according to one of claims 1 to 4, characterized ge indicates that propylene glycol and / or glycerol are used as organic solvents. 6. Enzymzubereitung nach einem der Ansprüche 1 bis 5, dadurch ge¬ kennzeichnet, daß als weitere Hilfsstoffe Aktivitätsstabilisa¬ toren in Mengen von 1 bis 10 Gew.-% eingesetzt werden. 6. Enzyme preparation according to one of claims 1 to 5, characterized ge indicates that activity stabilizers are used as additional auxiliaries in amounts of 1 to 10 wt .-%. 7. Verfahren zur Herstellung von Enzymzubereitungen nach den An¬ sprüchen 1 bis 6, dadurch gekennzeichnet, daß man das Enzym in dem organischen wassermischbaren Lösungsmittel löst und die Lö¬ sung durch Zugabe des Fällungsmittels unter Rühren in eine Dispersion umwandelt.7. Process for the preparation of enzyme preparations according to claims 1 to 6, characterized in that the enzyme is dissolved in the organic water-miscible solvent and the solution is converted into a dispersion by adding the precipitant with stirring. 8. Verwendung der Enzymzubereitungen nach den Ansprüchen 1 bis 7 als Stammlösung für die Herstellung von Flüssigwaschmitteln. 8. Use of the enzyme preparations according to claims 1 to 7 as a stock solution for the production of liquid detergents.
PCT/EP1991/001334 1990-07-25 1991-07-17 Liquid enzyme preparation Ceased WO1992001775A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904023601 DE4023601A1 (en) 1990-07-25 1990-07-25 LIQUID ENZYME PREPARATION
DEP4023601.3 1990-07-25

Publications (1)

Publication Number Publication Date
WO1992001775A1 true WO1992001775A1 (en) 1992-02-06

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025560A1 (en) * 1993-05-05 1994-11-10 Allied Colloids Limited Enzyme dispersions, their production and compositions containing them

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11503465A (en) * 1996-01-31 1999-03-26 ギスト ブロカデス ベスローテン フェンノートシャップ Use of compositions containing stabilized biologically active compounds
CA2388541A1 (en) * 1999-04-01 2000-10-12 The Procter & Gamble Company A detergent composition containing a metallo-protease
WO2013148492A1 (en) 2012-03-29 2013-10-03 Novozymes A/S Use of enzymes for preparing water soluble films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472783A (en) * 1966-02-02 1969-10-14 Winston B Smillie Nonionic detergent compositions
DE1957010A1 (en) * 1969-11-13 1971-06-16 Roehm Gmbh Biologically active liquid or semi-fluid clea - ning material
US3860536A (en) * 1970-01-02 1975-01-14 Cpc International Inc Enzyme-detergent combination
WO1988006183A1 (en) * 1987-02-13 1988-08-25 Röhm Gmbh Liquid composition of enzymes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3472783A (en) * 1966-02-02 1969-10-14 Winston B Smillie Nonionic detergent compositions
DE1957010A1 (en) * 1969-11-13 1971-06-16 Roehm Gmbh Biologically active liquid or semi-fluid clea - ning material
US3860536A (en) * 1970-01-02 1975-01-14 Cpc International Inc Enzyme-detergent combination
WO1988006183A1 (en) * 1987-02-13 1988-08-25 Röhm Gmbh Liquid composition of enzymes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994025560A1 (en) * 1993-05-05 1994-11-10 Allied Colloids Limited Enzyme dispersions, their production and compositions containing them
AU687395B2 (en) * 1993-05-05 1998-02-26 Ciba Specialty Chemicals Water Treatments Limited Enzyme dispersions, their production and compositions containing them

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Publication number Publication date
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