EP0352244A2 - Stabilized enzymatic liquid detergent - Google Patents

Stabilized enzymatic liquid detergent Download PDF

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Publication number
EP0352244A2
EP0352244A2 EP89850212A EP89850212A EP0352244A2 EP 0352244 A2 EP0352244 A2 EP 0352244A2 EP 89850212 A EP89850212 A EP 89850212A EP 89850212 A EP89850212 A EP 89850212A EP 0352244 A2 EP0352244 A2 EP 0352244A2
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EP
European Patent Office
Prior art keywords
detergent composition
composition according
enzyme
detergent
weight
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.)
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EP89850212A
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German (de)
French (fr)
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EP0352244A3 (en
Inventor
Dorrit Aaslyng
Jadwiga Palicka
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.)
Novo Nordisk AS
Nouryon Surface Chemistry AB
Original Assignee
Novo Nordisk AS
Berol Nobel Nacka AB
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Priority claimed from DK403988A external-priority patent/DK403988D0/en
Priority claimed from DK525488A external-priority patent/DK525488D0/en
Application filed by Novo Nordisk AS, Berol Nobel Nacka AB filed Critical Novo Nordisk AS
Publication of EP0352244A2 publication Critical patent/EP0352244A2/en
Publication of EP0352244A3 publication Critical patent/EP0352244A3/en
Withdrawn legal-status Critical Current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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds

Definitions

  • This invention concerns stabilized enzymatic liquid detergent compositions for cleaning a wide range of items including hard surfaces and soft goods such as textiles both for commercial and home use. More particularly, the invention relates to a stabilized composition comprising a relatively unstable enzyme.
  • Liquid enzymatic detergents are well-known in the prior art.
  • the enzymes incorporated in liquid detergents have mostly been Bacillus proteases, but the prior art also suggests that incorporation of enzymes other than Bacillus proteases may be useful, e.g. other enzyme types (such as amylases, lipases and cellulases) as well as enzymes of non-Bacillus origin (e.g. fungal enzymes).
  • a major problem which is encountered with such compositions is that of ensuring a sufficient stability of the enzymes in the compositions during storage.
  • One approach to overcoming this stability problem lies in selecting, from among the available enzymes, one with relatively good stability in conventional liquid detergents.
  • Esperase product of Novo-Nordisk A/S
  • a protease from an alkalophilic Bacillus prepared according to US 3,723,250.
  • R Esperase
  • This invention relates to liquid detergents comprising such a relatively unstable enzyme and particularly to improving the stability of the enzyme during storage.
  • the prior art deals extensively with stabilization of enzymes in liquid detergents. It is known that a number of commonly used detergent ingredients, such as detergent builders, may destabilize enzymes, so enzyme stability can be improved by eliminating these or reducing their amount. The prior art also teaches stabilization of enzymes by incorporation of various compounds that are not detergent active. JP-A 57-158,718 discloses enzyme stabilization in toothpaste by addition of dimethyl alkyl betaine.
  • It is the object of this invention to provide a liquid detergent composition comprising a relatively unstable enzyme having improved enzyme stability during storage without the need for incorporating detergent-inactive materials.
  • the amphoteric compounds which are used for enzyme stabilization in detergents according to the present invention are advantageous in comparison with alkyl betaines in that they in addition to the enzyme stabilization effect have very good washing performance in combination with nonionic tensides. They also give a fabric softening and bactericidal effect.
  • the object of the invention is achieved by providing a stabilized enzymatic liquid detergent composition comprising an effective amount of a microbial enzyme, said enzyme having less than 300/0 residual activity when tested by adding the enzyme to a liquid test detergent and storing for 2 weeks at 40° C, said test detergent containing 12% of alcohol ethoxylate (C12/C13 alcohol with an average of 6.5 moles of ethylene oxide), 5% of linear alkylbenzene sulfonate (dodecylbenzene sulfonate), 5% of citric acid and 4% of triethanolamine (% by weight) in water adjusted to a pH of 9.2 with NaOH said stabilized detergent composition comprising from about 1 to 50% by weight of an amphoteric surfactant having the general formula (I)
  • the group R is, as said above, a hydrocarbon group with 7 to 22 carbon atoms, suitably 12 to 22 and preferably 12 to 20.
  • the hydrocarbon group can be straight or branched, saturated or unsaturated and optionally contain substituents such as hydroxyl or carboxyl groups.
  • the group R may also contain one or several, up to about 20, ethylene oxide groups.
  • the group R is preferably an alkyl or alkenyl group but may also be a cycloalkyl-alkyl group, an aralkyl or aralkenyl group wherein the alkyl or alkenyl group contains at least 6 carbon atoms. It is preferred that R is a hydrocarbon group originating from coconut, tallow or oleic fatty acid.
  • Preferred compounds of formula (I) have the formula (II): where Q is CH 2 -COOM or CH 2 CH 2 -COOM, y is 1, 2 or 3, and where M, R, x and B are as indicated above. Preferably all groups B are groups Q.
  • Particularly preferred compounds of formula (II) have the formula (III): where R is defined as above, and y is 1, 2 or 3. Mixtures of compounds having different values for y of above formulae II and III respectively are also preferred. R in these compounds preferably originates from tallow acid.
  • enzyme stabilization is obtained by incorporation of a certain type of amphoteric surfactant that is itself detergent active.
  • the incorporation of non-active material solely for the purpose of enzyme stabilization can be avoided or reduced.
  • Amphoteric compounds of the type disclosed above as well as their use in detergents are previously known and reference is made to European patent applications 160507, 162600 and 214868 and to 2nd Word Surfactants Congress, Paris, 24-27 May 1988, Proceedings pp. 449-475, J. Palicka. These references disclose the amphoteric compounds and their general bactericidal, detergent properties etc and their use together with various additives such as other surfactants, bleaching agents, enzymes, builders, foaming agents etc.
  • the enzyme used in the composition of the invention is relatively unstable in the sense that it retains less than 300/0 of its activity after two weeks storage at 37° C in a test detergent of specified composition (detergent C-LAS of example I).
  • Microbial enzymes suitable for the present compositions include proteases, lipases, amylases and cellulases.
  • the enzymes are derived from microbial sources, such as Bacillus and fungi.
  • the detergent composition of the invention will usually also contain a nonionic surfactant, e.g. about 3-200/0 by weight. Further, the composition may optionally contain anionic surfactant and/or a second amphoteric surfactant, e.g. about 3-15% by weight. It may be preferable that the composition is essentially free of anionic surfactant, as this may destabilize some enzymes.
  • Suitable surfactants are:
  • the liquid detergent of the invention may be aqueous, e.g. containing 20-70% of water and 0-20% of solvent, or containing 1-200/ 0 of water and 5-25% of solvent. Satisfactory enzyme stability may be obtained even at water contents above 500/0. Alternatively, it may be essentially free of water (e.g. water content below 10/ 0 ), and will then typically contain 10-30 0 /o of solvent.
  • Typical solvents are mono- and divalent lower alcohols and glycol ethers.
  • the detergent composition of the invention may be built (i.e. comprising a detergent builder) or unbuilt (i.e. essentially free of a detergent builder). Enzyme stability is generally better in an unbuilt composition, but it may be desired to include a builder for improved detergency.
  • a built composition typically contains about 1-40%, by weight, of a builder such as zeolite, phosphate, phosphonate, citrate, NTA, EDTA or DTPA.
  • a soluble calcium salt is preferably included in an amount giving about 1-20 ⁇ -mol/l as Ca, as calcium stabilizes many detergent enzymes. pH will typically be neutral or alkaline, particularly preferred between 8-10.
  • the compositions may also contain, depending on the intended use, additives such as fabric conditioner (e.g. quaternary ammonium salts, typically 1-5%), foam boosters (e.g. 1-50/o), bactericides (e.g. 1-5 0 /o), optical brighteners (eg 0.1-1%), dyes e.g. 0.1-1%) and perfumes (eg 0.1-1%).
  • Samples of essentially unbuilt and zeolite-built liquid detergents with various water content were prepared with the following general composition (% by weight, as active material):
  • the polyacrylate was Alcosperse 409, and the phosponate was Dequest 2006.
  • the non-ionic surfactant was alcohol ethoxylate; for detergents B, BI and Z it consisted of the following Dobanol types (Shell): 25-9, 23-6.5 and 23-3 in the ratio 3:1:1, and for detergent C it consisted of Dobanol 23-6.5 only.
  • the anionic/amphoteric surfactant in each formulation was one of the following:
  • washing tests were made with three different detergents of formulation BI of Example I, containing 0.5% (by weight) of Savinase 8.0L (alkalophilic Bacillus protease). The tests were made with freshly prepared detergent, and with detergent after two weeks storage at 37°C.
  • the anionic/surfactant in each of the three detergents was as follows:
  • the washing conditions were as follows:

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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

Stabilized enzymatic liquid detergent compositions for cleaning a wide range of items including hard surfaces and soft goods such as textiles both for commercial and home use. The detergent compositions comprise a relatively unstable enzyme and certain amphoteric compounds.

Description

    TECHNICAL FIELD
  • This invention concerns stabilized enzymatic liquid detergent compositions for cleaning a wide range of items including hard surfaces and soft goods such as textiles both for commercial and home use. More particularly, the invention relates to a stabilized composition comprising a relatively unstable enzyme.
    • BACKGROUND ART
  • Liquid enzymatic detergents are well-known in the prior art. The enzymes incorporated in liquid detergents have mostly been Bacillus proteases, but the prior art also suggests that incorporation of enzymes other than Bacillus proteases may be useful, e.g. other enzyme types (such as amylases, lipases and cellulases) as well as enzymes of non-Bacillus origin (e.g. fungal enzymes). A major problem which is encountered with such compositions is that of ensuring a sufficient stability of the enzymes in the compositions during storage. One approach to overcoming this stability problem lies in selecting, from among the available enzymes, one with relatively good stability in conventional liquid detergents. One such enzyme is Esperase(R) (product of Novo-Nordisk A/S), a protease from an alkalophilic Bacillus, prepared according to US 3,723,250. However, other less stable enzymes may be desirable due to economy, washing performance etc. This invention relates to liquid detergents comprising such a relatively unstable enzyme and particularly to improving the stability of the enzyme during storage.
  • The prior art deals extensively with stabilization of enzymes in liquid detergents. It is known that a number of commonly used detergent ingredients, such as detergent builders, may destabilize enzymes, so enzyme stability can be improved by eliminating these or reducing their amount. The prior art also teaches stabilization of enzymes by incorporation of various compounds that are not detergent active. JP-A 57-158,718 discloses enzyme stabilization in toothpaste by addition of dimethyl alkyl betaine.
  • It is the object of this invention to provide a liquid detergent composition comprising a relatively unstable enzyme having improved enzyme stability during storage without the need for incorporating detergent-inactive materials. The amphoteric compounds which are used for enzyme stabilization in detergents according to the present invention are advantageous in comparison with alkyl betaines in that they in addition to the enzyme stabilization effect have very good washing performance in combination with nonionic tensides. They also give a fabric softening and bactericidal effect.
    • STATEMENT OF THE INVENTION
  • The object of the invention is achieved by providing a stabilized enzymatic liquid detergent composition comprising an effective amount of a microbial enzyme, said enzyme having less than 300/0 residual activity when tested by adding the enzyme to a liquid test detergent and storing for 2 weeks at 40° C, said test detergent containing 12% of alcohol ethoxylate (C12/C13 alcohol with an average of 6.5 moles of ethylene oxide), 5% of linear alkylbenzene sulfonate (dodecylbenzene sulfonate), 5% of citric acid and 4% of triethanolamine (% by weight) in water adjusted to a pH of 9.2 with NaOH
    said stabilized detergent composition comprising from about 1 to 50% by weight of an amphoteric surfactant having the general formula (I)
    Figure imgb0001
    • R is C7 - C22 hydrocarbon group
    • R1 is H or Ci - C6 alkyl,
    • X is 2 or 3,
    • y is 1 to 4
    • Q is (R2 COOM) where
    • R2 is Ci - C6 alkylene and
    • M is H, an alkali metal, alkaline earth metal, and ammonium or substituted ammonium ion,
    • and B is hydrogen or has the same meaning as Q.
  • The group R is, as said above, a hydrocarbon group with 7 to 22 carbon atoms, suitably 12 to 22 and preferably 12 to 20. The hydrocarbon group can be straight or branched, saturated or unsaturated and optionally contain substituents such as hydroxyl or carboxyl groups. The group R may also contain one or several, up to about 20, ethylene oxide groups. The group R is preferably an alkyl or alkenyl group but may also be a cycloalkyl-alkyl group, an aralkyl or aralkenyl group wherein the alkyl or alkenyl group contains at least 6 carbon atoms. It is preferred that R is a hydrocarbon group originating from coconut, tallow or oleic fatty acid. Preferred compounds of formula (I) have the formula (II):
    Figure imgb0002
    where Q is CH2-COOM or CH2CH2-COOM,
    y is 1, 2 or 3, and
    where M, R, x and B are as indicated above. Preferably all groups B are groups Q.
  • Particularly preferred compounds of formula (II) have the formula (III):
    Figure imgb0003
    where R is defined as above, and y is 1, 2 or 3. Mixtures of compounds having different values for y of above formulae II and III respectively are also preferred. R in these compounds preferably originates from tallow acid.
  • According to the invention, enzyme stabilization is obtained by incorporation of a certain type of amphoteric surfactant that is itself detergent active. Thus, the incorporation of non-active material solely for the purpose of enzyme stabilization can be avoided or reduced.
  • Amphoteric compounds of the type disclosed above as well as their use in detergents are previously known and reference is made to European patent applications 160507, 162600 and 214868 and to 2nd Word Surfactants Congress, Paris, 24-27 May 1988, Proceedings pp. 449-475, J. Palicka. These references disclose the amphoteric compounds and their general bactericidal, detergent properties etc and their use together with various additives such as other surfactants, bleaching agents, enzymes, builders, foaming agents etc.
    • DETAILED DESCRIPTION OF THE INVENTION Microbial enzyme
  • The enzyme used in the composition of the invention is relatively unstable in the sense that it retains less than 300/0 of its activity after two weeks storage at 37° C in a test detergent of specified composition (detergent C-LAS of example I). Microbial enzymes suitable for the present compositions include proteases, lipases, amylases and cellulases. The enzymes are derived from microbial sources, such as Bacillus and fungi. Some specific examples of detergent enzymes follow, each identified by enzyme type, microbial source and reference to a commercial product and/or a patent publication:
    • - Protease of Bacillus, especially from B. licheniformis (e.g. Alcalase(R) and from alkalophilic Bacillus strains according to US 3,723,250 (e.g. Savinas(R)) (both available from Novo Industri A/S)
    • - Alpha-amylase of Bacillus, especially B. licheniformis. Termamyl(R) (Novo Industri A/S).
    • - Protease of Fusarium, especially F. oxysporum, US 3,652,399 (Takeda), PCT/DK 89/00001.
    • - Cellulase of Humicola, especially H. insolens. Celluzyme(R) (Novo Industri A/S), US 4,435,307 (Novo).
    • - Lipase of Humicola, especially H, lanuginosa. Lipolase(R) (Novo), EP 305,216 (Novo) and US 4,810,414 (Novo). The detergent of the invention may contain two or more detergent enzymes. Examples are combinations of any two of the above enzymes, especially combinations of a Bacillus protease and any one of the above enzymes.
    Other surfactants
  • The detergent composition of the invention will usually also contain a nonionic surfactant, e.g. about 3-200/0 by weight. Further, the composition may optionally contain anionic surfactant and/or a second amphoteric surfactant, e.g. about 3-15% by weight. It may be preferable that the composition is essentially free of anionic surfactant, as this may destabilize some enzymes.
  • Examples of suitable surfactants are:
    • - Nonionics: Nonyl phenol ethoxylate, alcohol ethoxylate.
    • - Anionics: linear alkylbenzene sulfonate, secondary alkane sulfonate, alcohol ethoxylate sulfate, alpha olefin sulfonate.
    • - 2nd amphoteric: Iminodipropionate (e.g. Ampholak YCE, available from Berol Nobel Nacka AB, Sweden), iminopropionate and ampho carboxyglycinate (e.g. Ampholak XCO-30)
    Other ingredients
  • The liquid detergent of the invention may be aqueous, e.g. containing 20-70% of water and 0-20% of solvent, or containing 1-200/0 of water and 5-25% of solvent. Satisfactory enzyme stability may be obtained even at water contents above 500/0. Alternatively, it may be essentially free of water (e.g. water content below 10/0), and will then typically contain 10-300/o of solvent.
  • Typical solvents are mono- and divalent lower alcohols and glycol ethers.
  • The detergent composition of the invention may be built (i.e. comprising a detergent builder) or unbuilt (i.e. essentially free of a detergent builder). Enzyme stability is generally better in an unbuilt composition, but it may be desired to include a builder for improved detergency. A built composition typically contains about 1-40%, by weight, of a builder such as zeolite, phosphate, phosphonate, citrate, NTA, EDTA or DTPA.
  • A soluble calcium salt is preferably included in an amount giving about 1-20 µ-mol/l as Ca, as calcium stabilizes many detergent enzymes. pH will typically be neutral or alkaline, particularly preferred between 8-10. The compositions may also contain, depending on the intended use, additives such as fabric conditioner (e.g. quaternary ammonium salts, typically 1-5%), foam boosters (e.g. 1-50/o), bactericides (e.g. 1-50/o), optical brighteners (eg 0.1-1%), dyes e.g. 0.1-1%) and perfumes (eg 0.1-1%).
    • EXAMPLE I
  • Samples of essentially unbuilt and zeolite-built liquid detergents with various water content were prepared with the following general composition (% by weight, as active material):
    Figure imgb0004
  • The polyacrylate was Alcosperse 409, and the phosponate was Dequest 2006. The non-ionic surfactant was alcohol ethoxylate; for detergents B, BI and Z it consisted of the following Dobanol types (Shell): 25-9, 23-6.5 and 23-3 in the ratio 3:1:1, and for detergent C it consisted of Dobanol 23-6.5 only.
  • The anionic/amphoteric surfactant in each formulation was one of the following:
    • Reference:
    • - LAS (anionic), linear dodecylbenzene sulfonate, Sulfosoft (Berol)
    • - SAS (anionic), secondary alkane (C12) sulfonate, Hostapur SAS 60 (Hoechst)
    • - AES (anionic), alcohol ethoxylate sulfate (C12/C15 alcohol with 3 ethoxysulfate groups), Dobanol 25-3S (Shell)
    • - AOS (anionic), alpha olefin sulfonate (Ethyl corp.)
  • Invention:
    • - Ampholak 7TX (amphoteric of invention mixture of compounds of formula III with different values for y)
    • - 7TX + LAS, ratio 2:1
    • - 7TX + Ampholak YCE (2nd amphoteric), in the ratio 3:1
  • One of the following enzymes was added to each detergent sample:
    • - 1% of Savinase 8.0L (alkalophilic Bacillus protease)
    • - 1.50/0 of Celluzyme (Humicola cellulase)
    • - 0.5% of Lipolase(R) 100L (fungal lipase).
  • The samples were stored at 37° C for two weeks, the enzyme activity was measured before and after storage, and the results were expressed as residual activity in % of initial activity:
    Figure imgb0005
  • For all formulations tried, it is seen that complete substitution of anionic with amphoteric surfactant according to the invention improves the storage stability of the enzyme.
    • EXAMPLE II
  • Washing tests were made with three different detergents of formulation BI of Example I, containing 0.5% (by weight) of Savinase 8.0L (alkalophilic Bacillus protease). The tests were made with freshly prepared detergent, and with detergent after two weeks storage at 37°C. The anionic/surfactant in each of the three detergents was as follows:
    • Reference: LAS (anionic). Invention: Ampholak 7TX (amphoteric), 7TX+LAS (2:1).
  • The following standard soiled fabrics (available from Eidgenossische Material-Prüfungs-Anstalt, St. Gallen, Switzerland) were used:
    • EMPA 116, cotton soiled with blood, milk and ink.
    • EMPA 112, cotton soiled with cocoa, milk and sugar.
    • EMPA 117, polyester/cotton soiled with milk and ink.
  • The washing conditions were as follows:
    • Machine: Cylinda 9500 (frontloaded)
    • Program: Main wash 60°C
    • Number of washing cycles: 3
    • Water: 5 1
    • Detergent dosage: 5 ml/I
    • Water hardness: 5 °dH (degrees German hardness)
    • Wash load: 1 kg clean fabrics + 40x40 cm test fabric
  • Light reflectance was measured on washed fabric (W), soiled fabric (S) and clean fabric (C), and % detergency was calculated as (W-S)/(C-S). Finally, the % retention of detergency was calculated from detergency before and after storage. Results:
    Figure imgb0006
  • It is seen that on each of the three test fabrics, detergents according to the invention (columns 2 and 3) show clearly improved detergency after storage and retention of detergency. Particularly, the detergent with complete substitution of anionic surfactant with amphoteric according to the invention (column 2) shows a remarkable retention of detergency: better than 85% on each test fabric.

Claims (16)

1. A stabilized enzymatic liquid detergent composition, characterized in that it comprises an effective amount of a microbial enzyme, said enzyme having less than 30% residual activity when tested by adding the enzyme to a liquid test detergent and storing for 2 weeks at 40° C, said test detergent containing 12% of alcohol ethoxylate, 5% of linear alkylbenzene sulfonate, 50/0 of citric acid and 40/0 of triethanolamine (% by weight) in water at a pH of 9.2, said stabilized detergent composition being characterized by comprising from about 1 to 50% by weight of an amphoteric surfactant having the general formula (I)
Figure imgb0007
wherein R is a C7 - C22 hydrocarbon group, R1 is H or C1-C6 alkyl, X is 2 or 3, y is 1 to 4, and Q is (R2 COOM) where R2 is Ci - C6 alkylene, M is H, an alkali metal, alkaline earth metal, ammonium or substituted ammonium ion and B is hydrogen or has the same meaning as Q.
2. A detergent composition according to Claim 1, wherein said amphoteric surfactant has the formula (II):
Figure imgb0008
where Q is CH2-COOM or CH2CH2-COOM, y is 1, 2 or 3, and where M, R, x and B are as indicated in claim 1.
3. A detergent composition according to Claim 1, wherein said amphoteric surfactant has the formula (III):
Figure imgb0009
where R is defined as above, and y is 1, 2 or 3.
4. A detergent composition according to any of claims 1-3 wherein the enzyme is a Bacillus enzyme, preferably a protease, an amylase or a cellulase.
5. A detergent composition according to any of Claims 1-3 wherein the enzyme is a fungal detergent enzyme, preferably a protease, a lipase or a cellulase.
6. A detergent composition according to Claim 5, wherein the enzyme is a Fusarium protease, a Humicola lipase or a Humicola cellulase.
7. A detergent composition according to any of Claims 1-6 further containing an effective amount of a second microbial enzyme.
8. A detergent composition according to any of Claims 1-7 containing from about 3 to 400/0 by weight of said amphoteric surfactant.
9. A detergent composition according to any of Claims 1 - 8, further containing from about 1 to 20% by weight of a nonionic surfactant.
10. A detergent composition according to Claims 1 - 9 further containing from about 1 to 20% by weight of an anionic and/or a second amphoteric surfactant.
11. A detergent composition according to Claims 1-10, which is substantially free of a anionic surfactant.
12. A detergent composition according to Claims 1-11 further containing from about 20 to 700/0 by weight of water and from 0 to about 20% by weight of a solvent.
13. A detergent composition according to Claims 1-11 which contains from about 10 to 30% of a solvent, and is essentially free of water.
14. A detergent composition according to Claims 1-13 which is substantially free of a detergent builder.
15. A detergent composition according to Claims 1 -13 containing from about 1 to 400/0 by weight of a detergent builder.
16. A detergent composition according to Claims 1-15, containing a soluble calcium salt in an amount giving from about 1 to 20 millimoles of calcium per liter.
EP19890850212 1988-07-20 1989-06-22 Stabilized enzymatic liquid detergent Withdrawn EP0352244A3 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DK4039/88 1988-07-20
DK403988A DK403988D0 (en) 1988-07-20 1988-07-20 STABILIZED ENZYMATIC LIQUID DETERGENT
DK5254/88 1988-09-21
DK525488A DK525488D0 (en) 1988-09-21 1988-09-21 STABILIZED ENZYMATIC LIQUID DETERGENT

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EP0352244A2 true EP0352244A2 (en) 1990-01-24
EP0352244A3 EP0352244A3 (en) 1990-12-27

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* Cited by examiner, † Cited by third party
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WO1994012607A1 (en) * 1992-10-09 1994-06-09 Unilever Plc Hard-surface cleaning compositions comprising solvent, surfactant and lipase
US5356800A (en) * 1992-11-30 1994-10-18 Buckman Laboratories International, Inc. Stabilized liquid enzymatic compositions
US5403515A (en) * 1992-08-25 1995-04-04 Lever Brothers Company, Division Of Conopco, Inc. Liquid cleaning compositions comprising primary alkyl sulphate and non-ionic surfactants
WO1995020033A1 (en) * 1994-01-21 1995-07-27 Buckman Laboratories International, Inc. Enzymes for recreational water
US5562894A (en) * 1991-08-09 1996-10-08 Regents Of The University Of California Amino-acyl-type and catecholamine-type contrast agents for MRI
EP0758678A2 (en) 1995-08-11 1997-02-19 HENKEL-ECOLAB GmbH & CO. OHG Cleaning agent for protective working garment
US5780283A (en) * 1993-12-03 1998-07-14 Buckman Laboratories International, Inc. Enzyme stabilization by oxygen-containing block copolymers
EP0893489A1 (en) * 1997-07-22 1999-01-27 Calgon Corporation Composition and method for cleaning surfaces
WO1999034011A3 (en) * 1997-12-24 2000-02-10 Genencor Int Method of assaying for a preferred enzyme and/or detergent
US6342381B1 (en) 1998-02-27 2002-01-29 Buckman Laboratories Internationals, Inc. Enzyme stabilization with pre-superpolyamide or pre-fiber-forming polyamide oligomers
WO2012055954A1 (en) 2010-10-29 2012-05-03 Ab Enzymes Oy Variants of fungal serine protease
WO2012131023A2 (en) 2011-03-31 2012-10-04 Ab Enzymes Oy Protease enzyme and uses thereof
US8362222B2 (en) 2009-07-08 2013-01-29 Ab Enzymes Oy Fungal protease and use thereof
US8603795B2 (en) 2009-04-30 2013-12-10 Ab Enzymes Oy Fungal protease and use thereof
US8609390B2 (en) 2009-04-30 2013-12-17 Ab Enzymes Oy Fungal serine protease and use thereof
EP2893013A4 (en) * 2012-09-10 2016-04-13 Ecolab Usa Inc Stable liquid manual dishwashing compositions containing enzymes
WO2016096575A1 (en) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Textile treatment agent with improved stain removal
CN114774213A (en) * 2021-05-26 2022-07-22 浙江施维康生物医学材料有限公司 Detergent for textiles and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06248290A (en) * 1993-02-26 1994-09-06 Miyoshi Oil & Fat Co Ltd Cleaning agent composition
JP2000169897A (en) * 1998-12-04 2000-06-20 Kao Corp Liquid detergent composition
JP2002034558A (en) * 2000-07-21 2002-02-05 Nof Corp Stabilized proteolytic enzyme and its usage
JP5721094B2 (en) * 2009-02-27 2015-05-20 学校法人甲南学園 Composition for improving enzyme activity and use thereof
US20140193887A1 (en) * 2011-07-12 2014-07-10 Clariant International Ltd. Use of Secondary Paraffin Sulfonates for Increasing the Cleaning Capacity of Enzymes
ES2554243T3 (en) * 2011-07-12 2015-12-17 Weylchem Switzerland Ag Use of a combination of secondary paraffin sulphonate and amylase to increase the cleaning power of liquid washing agents

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1964088A1 (en) * 1968-12-23 1970-07-02 Procter & Gamble Stabilized aqueous enzyme mixture
FR2146294A1 (en) * 1971-07-16 1973-03-02 Procter Gamble Europ
US4670179A (en) * 1986-05-29 1987-06-02 Colgate Palmolive Company Stabilized built single phase liquid detergent composition containing enzymes

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58132098A (en) * 1982-02-01 1983-08-06 花王株式会社 Detergent composition
JPS60123600A (en) * 1983-12-08 1985-07-02 ライオン株式会社 Liquid detergent composition
JPS60196722A (en) * 1984-03-19 1985-10-05 Lion Corp Cleaner for contact lens

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1964088A1 (en) * 1968-12-23 1970-07-02 Procter & Gamble Stabilized aqueous enzyme mixture
FR2146294A1 (en) * 1971-07-16 1973-03-02 Procter Gamble Europ
US4670179A (en) * 1986-05-29 1987-06-02 Colgate Palmolive Company Stabilized built single phase liquid detergent composition containing enzymes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
2nd WORLD SURFACTANTS CONGRESS PARIS, 24-27 MAY 1988, PROCEEDINGS, pages 449 - 475, J. PALICKA *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5562894A (en) * 1991-08-09 1996-10-08 Regents Of The University Of California Amino-acyl-type and catecholamine-type contrast agents for MRI
US5403515A (en) * 1992-08-25 1995-04-04 Lever Brothers Company, Division Of Conopco, Inc. Liquid cleaning compositions comprising primary alkyl sulphate and non-ionic surfactants
WO1994012607A1 (en) * 1992-10-09 1994-06-09 Unilever Plc Hard-surface cleaning compositions comprising solvent, surfactant and lipase
US5356800A (en) * 1992-11-30 1994-10-18 Buckman Laboratories International, Inc. Stabilized liquid enzymatic compositions
US5780283A (en) * 1993-12-03 1998-07-14 Buckman Laboratories International, Inc. Enzyme stabilization by oxygen-containing block copolymers
US5474701A (en) * 1994-01-21 1995-12-12 Buckman Laboratories International, Inc. Enzymes for recreational water
CN1081670C (en) * 1994-01-21 2002-03-27 巴科曼实验室国际公司 Enzymes for recreational water
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
EP0758678A2 (en) 1995-08-11 1997-02-19 HENKEL-ECOLAB GmbH & CO. OHG Cleaning agent for protective working garment
EP0893489A1 (en) * 1997-07-22 1999-01-27 Calgon Corporation Composition and method for cleaning surfaces
WO1999034011A3 (en) * 1997-12-24 2000-02-10 Genencor Int Method of assaying for a preferred enzyme and/or detergent
US7122334B2 (en) 1997-12-24 2006-10-17 Genencor International, Inc. Method of assaying wash performance of enzymes on a microtiter plate
US6342381B1 (en) 1998-02-27 2002-01-29 Buckman Laboratories Internationals, Inc. Enzyme stabilization with pre-superpolyamide or pre-fiber-forming polyamide oligomers
US8877912B2 (en) 2009-04-30 2014-11-04 Ab Enzymes Oy Nucleic acids encoding fungal serine protease
US8937170B2 (en) 2009-04-30 2015-01-20 Ab Enzymes Oy Nucleic acids encoding fungal protease
US8603795B2 (en) 2009-04-30 2013-12-10 Ab Enzymes Oy Fungal protease and use thereof
US8609390B2 (en) 2009-04-30 2013-12-17 Ab Enzymes Oy Fungal serine protease and use thereof
US8362222B2 (en) 2009-07-08 2013-01-29 Ab Enzymes Oy Fungal protease and use thereof
WO2012055954A1 (en) 2010-10-29 2012-05-03 Ab Enzymes Oy Variants of fungal serine protease
US8945900B2 (en) 2010-10-29 2015-02-03 Ab Enzymes Oy Variants of fungal serine protease
WO2012131023A2 (en) 2011-03-31 2012-10-04 Ab Enzymes Oy Protease enzyme and uses thereof
US9404164B2 (en) 2011-03-31 2016-08-02 Ab Enzymes Oy Protease enzyme and uses thereof
US10221377B2 (en) 2011-03-31 2019-03-05 Ab Enzymes Oy Protease enzyme and uses thereof
EP2893013A4 (en) * 2012-09-10 2016-04-13 Ecolab Usa Inc Stable liquid manual dishwashing compositions containing enzymes
US9745543B2 (en) 2012-09-10 2017-08-29 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
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US10723974B2 (en) 2012-09-10 2020-07-28 Ecolab Usa Inc. Stable liquid manual dishwashing compositions containing enzymes
WO2016096575A1 (en) * 2014-12-17 2016-06-23 Henkel Ag & Co. Kgaa Textile treatment agent with improved stain removal
CN114774213A (en) * 2021-05-26 2022-07-22 浙江施维康生物医学材料有限公司 Detergent for textiles and preparation method thereof
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