EP0376705A1 - Flüssige enzymatische Detergenszusammensetzungen - Google Patents

Flüssige enzymatische Detergenszusammensetzungen Download PDF

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Publication number
EP0376705A1
EP0376705A1 EP89313624A EP89313624A EP0376705A1 EP 0376705 A1 EP0376705 A1 EP 0376705A1 EP 89313624 A EP89313624 A EP 89313624A EP 89313624 A EP89313624 A EP 89313624A EP 0376705 A1 EP0376705 A1 EP 0376705A1
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EP
European Patent Office
Prior art keywords
composition
weight
liquid detergent
enzymes
detergent
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.)
Withdrawn
Application number
EP89313624A
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English (en)
French (fr)
Inventor
Martin Scott Cardinali
Jack Thomas Mccown
Thomas Weber
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0376705A1 publication Critical patent/EP0376705A1/de
Withdrawn legal-status Critical Current

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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 enzymatic liquid detergent compositions comprising lipolytic enzymes ex Humicola lanuginosa or Thermomyces lanuginosus and proteolytic enzymes
  • Enzymatic liquid detergent compositions are well-known in the art. Most of the prior proposals are however concerned with enzymatic liquid detergent compositions which contain a proteolytic enzyme ingredient, or a mixture thereof with amylolytic enzymes.
  • lipases have recently been proposed for inclusion in detergent compositions, see e.g. U.S. Patent 4,707,291 (Thom et al.), they have been mainly considered for inclusion in particulate detergent compositions.
  • European Patent Application 0258,068 a particular lipase ex Humicola lanuginosa is proposed as a detergent additive, also for inclusion in liquid detergent compositions.
  • 1, 2 - propanediol and calcium salts improve the stability of this lipase in liquid systems. Sorbitol has only a slight stabilizing effect.
  • the present invention is particularly concerned with the above lipases ex Humicola lanuginosa or Thermomyces lanuginosus, hereinafter collectively referred to as ex Humicola lanuginosa.
  • these lipases like all enzymes, are proteins, they are susceptible to proteolytic attack by proteolytic enzymes, which further reduces the stability of these lipases in compositions also comprising proteolytic enzymes.
  • a lower aliphatic alcohol and a salt of a lower carboxylic acid in a proteolytic enzyme containing liquid detergent composition which comprises a detergent-active system which consists predominantly of a nonionic detergent significantly improves the storage stability of lipolytic enzymes ex Humicola lanuginosa in such liquid detergent compositions in the presence of proteolytic enzymes.
  • the present invention relates to a proteolytic enzymes containing liquid detergent composition
  • a detergent-active system which consists predominantly of a nonionic detergent, and furthermore comprising a lipolytic enzyme ex Humicola lanuginosa , a lower aliphatic alcohol and a salt of a lower carboxylic acid as the essential components.
  • the first essential component of the liquid detergent composition is the nonionic detergent.
  • Nonionic detergents are well-known in the art. They are normally reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • nonionic detergents are alkyl (C6-C22) phenol-ethylene oxide condensation products, with generally 5-25 moles of ethylene oxide per mole of alkylphenol, the condensation products of aliphatic C8-C18 primary or secondary, linear or branched chain alcohols with generally 5-40 moles of ethylene oxide, and products made by condensation of ethylene oxide and propylene oxide with ethylenediamine.
  • Other nonionic detergents include the block copolymers of ethylene oxide and propylene oxide, alkylpolyglycosides, tertiary amine-oxides and dialkylsulphoxides.
  • the condensation products of the alcohols with ethylene oxide are the preferred nonionic detergents.
  • nonionic detergents may be used as well as mixtures thereof.
  • the nonionic detergent or detergents may form the sole detergent-active system in the liquid detergent composition, or they may be in admixture with other detergent-active compounds such as anionic, cationic, zwitterionic or ampholytic detergent-active compounds, as long as the nonionic detergent constitutes the major part of the detergent-active system.
  • the nonionic detergent should form at least 50%, usually at least 60%, preferably at least 70% by weight of the detergent-active system.
  • the total amount of detergent-active compound in the composition ranges from 10-90, usually from 15-70% by weight.
  • the second essential ingredient of the present invention is the lipolytic enzyme.
  • This lipolytic enzyme is a fungal lipase producible by Humicola lanuginosa and Thermomyces lanuginosus.
  • fungal lipases as defined above are the lipases ex Humicola lanuginosa, as described in the aforesaid European Patent Application 0258,068 (NOVO), as well as the lipase obtained by cloning the gene from Humicola lanuginosa and expressing this gene in Aspergillus oryzae, commercially available from NOVO Industri A/S under the trade name "Lipolase”®.
  • This Lipolase is a preferred lipase for use in the present invention.
  • the lipases of the present invention are included in the liquid detergent composition in such an amount that the final composition has a lipolytic enzyme activity of from 100 to 0.005 LU/mg, preferably 25 to 0.05 LU/mg of the composition.
  • lipases can be used in their non-purified form or in a purified form, e.g. purified with the aid of well-known adsorption methods, such as phenyl sepharose adsorption techniques.
  • the third essential ingredient of the present invention is the lower aliphatic alcohol.
  • This alcolhol can be methanol, ethanol, propanol and isopropanol or mixtures thereof.
  • a preferred alcohol is ethanol.
  • the amount of lower aliphatic alcohol to be used in the present invention depends to some extent on the composition of the liquid detergent, but in general it varies from 1 - 10% by weight, preferably from 2 - 8% by weight of the final composition.
  • the fourth essential ingredient of the present invention is the salt of the lower aliphatic carboxylic acid.
  • This acid contains from 1 - 3 carbon lower aliphatic carboxylic acid.
  • This acid contains from 1 - 3 carbon atoms, such as formic acid, acetic acid and propionic acid. It may be included in the liquid detergent composition as an acid, the salt being formed in situ therein by methathesis, or the salt of the acid may be included in the liquid detergent composition.
  • Suitable salts are the water-soluble alkalimetal and mono-, di- and triethanolamine salts. Particularly preferred is sodium formate.
  • the amount of the salt of the lower aliphatic carboxylic acid used in the present invention ranges from 0.1 - 5% by weight, preferably from 0.5 - 3.5% by weight of the final composition. Naturally, mixtures of salts of these lower aliphatic carboxylic acids can be used.
  • the fifth essential ingredient of the present invention is the proteolytic enzyme.
  • This enzyme can be of vegetable, animal or microorganism origin. Preferably it is of the latter origin, which includes yeasts, fungi, molds and bacteria. Particularly preferred are bacterial subtilisin type proteases, obtained from e.g. particular strains of B. subtilis and B. licheniformis. Examples of suitable commercially available proteases are Alcalase®, Savinase®, Esperase®, all of NOVO Industri A/S; Maxatase® and Maxacal® of Gist-Brocades; Kazusase® of Showa Denko; BPN and BPN′ proteases and so on.
  • the amount of proteolytic enzyme, included in the composition ranges from 0.1- 50 GU/mg, based on the final composition. Naturally, mixtures of different proteolytic enzymes may be used.
  • a GU is a glycine unit, which is the amount of proteolytic enzyme which under standard incubation conditions produces an amount of terminal NH2-groups equivalent to 1 microgramme/ml of glycine.
  • the liquid detergent compositions of the present invention can furthermore contain one or more other, optional ingredients.
  • optional ingredients are e.g. perfumes, including deoperfumes, colouring materials, opacifiers, soil-suspending agents, soil-release agents, solvents such as propylene glycol, hydrotropes such as sodium cumene-, toluene- and xylenesulphonate as well as urea, alkaline materials such as mono-, di- or triethanol-amine, clays, fabric-softening agents and so on.
  • the liquid detergent composition may be unbuilt or built, and may be aqueous or non-aqueous.
  • the composition may contain from 1 - 60%, preferably 5 - 30% by weight of one or more organic and/or inorganic builder.
  • organic and/or inorganic builder Typical examples of such builders are the alkalimetal ortho-, pyro- and tri- polyphosphates, alkalimetal carbonates, either alone or in admixture with calcite, alkalimetal citrates, alkalimetal nitrilotriacetates, carboxymethyloxy succinates, zeolites, polyacetal carboxylates and so on.
  • a calcium salt may also be advantageous to include a certain amount of a calcium salt to further improve the enzyme stability.
  • a suitable calcium salt is calcium chloride; the calcium salt should be added in such an amount, that from 0.1 - 2 millimoles of enzyme-accessible free calcium (i.e. calcium, not sequestrated by any of the ingredients of the composition, e.g. a builder) is available per kilogramme of the final composition.
  • compositions may furthermore comprise lather boosters, foam depressors, anti-corrosion agents, chelating agents, anti-soil redeposition agents, bleaching agents, other stabilizing agents for the enzymes, activators for the bleaching agents and so on. They may also comprise enzymes other than the proteases and lipases, such as amylases, oxidases and cellulases. In general, the compositions may comprise such other enzymes in an amount of 0.01-10% by weight.
  • the liquid detergent composition is an aqueous composition
  • the balance of the formulation consists of an aqueous medium.
  • the above ingredients together with the essential ingredients make up for the whole formulation.
  • the invention will further be illustrated by way of Example.
  • the stability of Lipolase® in various aqueous systems was assessed at 37 o C over 27 days of storage.
  • the aqueous systems all contained also a proteolytic enzyme Savinase 16.0 L ex NOVO, in an amount equivalent to 30 GU/ml of the system.
  • the aqueous systems contained either 4.9% ethanol, or 2.7% sodium formate, or 16.5% of a nonionic detergent which was a C12 - C15 linear primary alcohol, condensed with 9 moles of ethylene oxide, or a mixture of 4.9% ethanol, 2.7% sodium formate and 16.5% of the nonionic detergent.
  • Figure I shows the results of these stability tests. It can be clearly seen, that the ternary mixture ethanol/sodium formate/nonionic detergent produced an unexpectedly improved lipolytic enzyme storage stability, in comparison with the single components.
  • liquid detergent composition was tested as to the stability of Lipolase therein. % by weight C12-C13 primary linear alcohol, condensed with 9 moles of ethylene oxide 22.6 Sodium coconut alcohol diethyleneglycolethersulphate 5.3 Sodium coconut alcoholsulphate 3.5 Sodium formate 1.9 Ethanol 6.2 Water q.s.
  • composition also contained Lipolase and Savinase in amounts, yielding an activity of 15LU/ml resp. 30 GU/ml at a dosage of the composition of 2 g/l. to a wash liquor.
  • the half-life time at 37 o C of the Lipolase was 7 days. Increasing the amount of sodium formate to 2.7% yielded a half-life time of the Lipolase of more than 1.5 months.
  • Example 3 The same amounts of Lipolase and Savinase of Example 3 were used in the following liquid detergent composition % by weight C12-C15 linear primary alcohol, condensed with 10 moles of ethylene oxide 16.5 Sodium dodecylbenzenesulphonate 3.5 Polyethyleneglycol ester 0.6 Sodium Formate 2.7 Ethanol 4.9 Water q.s.
  • the half-life at 37 o C time of the Lipolase was more than 1.5 months.

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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)
EP89313624A 1988-12-30 1989-12-27 Flüssige enzymatische Detergenszusammensetzungen Withdrawn EP0376705A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US292298 1981-08-12
US29229888A 1988-12-30 1988-12-30

Publications (1)

Publication Number Publication Date
EP0376705A1 true EP0376705A1 (de) 1990-07-04

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Family Applications (1)

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EP89313624A Withdrawn EP0376705A1 (de) 1988-12-30 1989-12-27 Flüssige enzymatische Detergenszusammensetzungen

Country Status (6)

Country Link
EP (1) EP0376705A1 (de)
JP (1) JPH02227500A (de)
AU (1) AU4724989A (de)
BR (1) BR9000010A (de)
CA (1) CA2006527A1 (de)
ZA (1) ZA899957B (de)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid
EP0486073A3 (en) * 1990-11-14 1993-06-23 The Procter & Gamble Company Liquid detergent composition containing lipase and protease
US5354491A (en) * 1992-08-14 1994-10-11 The Procter & Gamble Company Liquid detergent compositions containing protease and certain β-aminoalkylboronic acids and esters
WO1995017494A1 (de) * 1993-12-23 1995-06-29 Henkel Kommanditgesellschaft Auf Aktien Enzymhaltiges flüssigwaschmittel
WO1995020033A1 (en) * 1994-01-21 1995-07-27 Buckman Laboratories International, Inc. Enzymes for recreational water
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
US5476608A (en) * 1991-12-04 1995-12-19 The Procter & Gamble Company Liquid laundry detergents with citric acid, cellulase, and boricdiol complex to inhibit proteolytic enzyme
US5614484A (en) * 1991-08-21 1997-03-25 The Procter & Gamble Company Detergent compositions containing lipase and terpene
US5691295A (en) * 1995-01-17 1997-11-25 Cognis Gesellschaft Fuer Biotechnologie Mbh Detergent compositions
US5904736A (en) * 1995-04-28 1999-05-18 Henkel Kommanditgesellschaft Auf Aktien Cellulase-containing washing agents
US6153576A (en) * 1996-02-16 2000-11-28 Henkel Kommanditgesellschaft Auf Aktien Transition-metal complexes used as activators for peroxy compounds
US6162783A (en) * 1996-09-24 2000-12-19 The Procter & Gamble Company Liquid detergents containing proteolytic enzyme and protease inhibitors
US6165966A (en) * 1996-09-24 2000-12-26 The Procter & Gamble Company Liquid detergents containing proteolytic enzyme and protease inhibitors
US6180586B1 (en) 1996-09-24 2001-01-30 The Procter & Gamble Company Liquid laundry detergent compositions containing proteolytic enzyme and protease inhibitors
US7098179B2 (en) 2001-10-22 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Cotton active, dirt removing urethane-based polymers
US7316995B2 (en) 2003-02-10 2008-01-08 Henkel Kommanditgesellschaft Auf Aktien Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US7375072B2 (en) 2003-02-10 2008-05-20 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
US7431739B2 (en) 2005-06-08 2008-10-07 Henkel Kommanditgesellschaft Auf Aktien Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol
EP2551336A1 (de) 2011-07-25 2013-01-30 The Procter & Gamble Company Flüssige Waschmittelzusammensetzung mit stabilisiertem Enzym
US8809246B2 (en) 2009-11-12 2014-08-19 Thales Inc. Braided hair washing method
WO2021254824A1 (en) * 2020-06-18 2021-12-23 Basf Se Compositions and their use

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008094726A (ja) 2006-10-06 2008-04-24 Towa Koso Kk マイクロバブル洗浄用組成物、マイクロバブル洗浄方法及びマイクロバブル洗浄装置
CN102712879A (zh) * 2009-12-21 2012-10-03 丹尼斯科美国公司 含有褐色喜热裂孢菌脂肪酶的洗涤剂组合物及其使用方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028866A1 (de) * 1979-11-09 1981-05-20 THE PROCTER & GAMBLE COMPANY Eine Formate und Calciumionen enthaltende stabile, wässrige Enzymzusammensetzung
EP0258068A2 (de) * 1986-08-29 1988-03-02 Novo Nordisk A/S Enzymhaltiger Reinigungsmittelzusatz

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5811196B2 (ja) * 1979-11-09 1983-03-01 ザ、プロクタ−、エンド、ギヤンブル、カンパニ− 安定な水性酵素組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028866A1 (de) * 1979-11-09 1981-05-20 THE PROCTER & GAMBLE COMPANY Eine Formate und Calciumionen enthaltende stabile, wässrige Enzymzusammensetzung
EP0258068A2 (de) * 1986-08-29 1988-03-02 Novo Nordisk A/S Enzymhaltiger Reinigungsmittelzusatz

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0486073A3 (en) * 1990-11-14 1993-06-23 The Procter & Gamble Company Liquid detergent composition containing lipase and protease
TR27423A (tr) * 1990-11-14 1995-04-21 Procter & Gamble Lipaz ve proteazi ihtiva eden sivi deterjan.
TR26055A (tr) * 1991-04-30 1994-12-15 Procter & Gamble Bir proteolitik enzimin inhibisyonu icin bir aril boronik asit iceren sivi deterjan.
WO1992019707A1 (en) * 1991-04-30 1992-11-12 The Procter & Gamble Company Liquid detergents with an aryl boronic acid
US5472628A (en) * 1991-04-30 1995-12-05 The Procter & Gamble Company Liquid detergents with an aryl acid for inhibition of proteolytic enzyme
US5614484A (en) * 1991-08-21 1997-03-25 The Procter & Gamble Company Detergent compositions containing lipase and terpene
US5476608A (en) * 1991-12-04 1995-12-19 The Procter & Gamble Company Liquid laundry detergents with citric acid, cellulase, and boricdiol complex to inhibit proteolytic enzyme
US5354491A (en) * 1992-08-14 1994-10-11 The Procter & Gamble Company Liquid detergent compositions containing protease and certain β-aminoalkylboronic acids and esters
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
WO1995017494A1 (de) * 1993-12-23 1995-06-29 Henkel Kommanditgesellschaft Auf Aktien Enzymhaltiges flüssigwaschmittel
WO1995020033A1 (en) * 1994-01-21 1995-07-27 Buckman Laboratories International, Inc. Enzymes for recreational water
US5507952A (en) * 1994-01-21 1996-04-16 Buckman Laboratories International, Inc. Enzymes for recreational water
US5474701A (en) * 1994-01-21 1995-12-12 Buckman Laboratories International, Inc. Enzymes for recreational water
CN1081670C (zh) * 1994-01-21 2002-03-27 巴科曼实验室国际公司 用于再生水的酶
US5855625A (en) * 1995-01-17 1999-01-05 Henkel Kommanditgesellschaft Auf Aktien Detergent compositions
US5691295A (en) * 1995-01-17 1997-11-25 Cognis Gesellschaft Fuer Biotechnologie Mbh Detergent compositions
US5904736A (en) * 1995-04-28 1999-05-18 Henkel Kommanditgesellschaft Auf Aktien Cellulase-containing washing agents
US6153576A (en) * 1996-02-16 2000-11-28 Henkel Kommanditgesellschaft Auf Aktien Transition-metal complexes used as activators for peroxy compounds
US6162783A (en) * 1996-09-24 2000-12-19 The Procter & Gamble Company Liquid detergents containing proteolytic enzyme and protease inhibitors
US6165966A (en) * 1996-09-24 2000-12-26 The Procter & Gamble Company Liquid detergents containing proteolytic enzyme and protease inhibitors
US6180586B1 (en) 1996-09-24 2001-01-30 The Procter & Gamble Company Liquid laundry detergent compositions containing proteolytic enzyme and protease inhibitors
US7098179B2 (en) 2001-10-22 2006-08-29 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Cotton active, dirt removing urethane-based polymers
US7316995B2 (en) 2003-02-10 2008-01-08 Henkel Kommanditgesellschaft Auf Aktien Detergents or cleaning agents comprising a water-soluble building block system and a cellulose derivative with dirt dissolving properties
US7375072B2 (en) 2003-02-10 2008-05-20 Henkel Kommanditgesellschaft Auf Aktien Bleach-containing laundry detergents or cleaning compositions comprising water-soluble builder system and soil release-capable cellulose derivative
US7431739B2 (en) 2005-06-08 2008-10-07 Henkel Kommanditgesellschaft Auf Aktien Boosting the cleaning performance of laundry detergents by polymer of styrene/methyl methacrylate/methyl polyethylene glycol
US8809246B2 (en) 2009-11-12 2014-08-19 Thales Inc. Braided hair washing method
EP2551336A1 (de) 2011-07-25 2013-01-30 The Procter & Gamble Company Flüssige Waschmittelzusammensetzung mit stabilisiertem Enzym
EP2551335A1 (de) 2011-07-25 2013-01-30 The Procter & Gamble Company Flüssige Waschmittelzusammensetzung mit stabilisiertem Enzym
WO2013016368A1 (en) 2011-07-25 2013-01-31 The Procter & Gamble Company Detergent compositions
WO2021254824A1 (en) * 2020-06-18 2021-12-23 Basf Se Compositions and their use

Also Published As

Publication number Publication date
JPH02227500A (ja) 1990-09-10
CA2006527A1 (en) 1990-06-30
BR9000010A (pt) 1990-10-09
ZA899957B (en) 1991-08-28
AU4724989A (en) 1990-07-05

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