GB2079305A - Liquid enzyme detergent - Google Patents

Liquid enzyme detergent Download PDF

Info

Publication number
GB2079305A
GB2079305A GB8120184A GB8120184A GB2079305A GB 2079305 A GB2079305 A GB 2079305A GB 8120184 A GB8120184 A GB 8120184A GB 8120184 A GB8120184 A GB 8120184A GB 2079305 A GB2079305 A GB 2079305A
Authority
GB
United Kingdom
Prior art keywords
polyol
cross
polymer
liquid
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.)
Granted
Application number
GB8120184A
Other versions
GB2079305B (en
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
Original Assignee
Unilever PLC
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 filed Critical Unilever PLC
Publication of GB2079305A publication Critical patent/GB2079305A/en
Application granted granted Critical
Publication of GB2079305B publication Critical patent/GB2079305B/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions

Landscapes

  • 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

Stable, aqueous, built liquid enzymatic detergent compositions can be obtained by the inclusion in an aqueous, built liquid enzymatic detergent composition of a mixture of a polyol and boric acid or an equivalent thereof in a weight ratio of polyol to boric acid more than 1, and a neutralised cross-linked polyacrylate polymer.

Description

SPECIFICATION Liquid enzymatic detergent composition The present invention relates to a stable, aqueous built liquid enzymatic detergent composition. Aqueous liquid enzymatic detergent compositions are well-known in the art. The major problem which is encountered with such compositions is that of ensuring a sufficient storage-stability of the enzymes in these compositions. There have already been various proposals for the inclusion of special stabilizing agents in such liquid enzymatic detergent compositions, especially unbuilt liquid enzymatic detergents.
In the case of built liquid enzymatic detergent compositions, however, there is not only the additional problem of the possible effect of the builder material on the enzymes, but also the effect of the builder material on the overall physical (storage) stability of the liquid composition.
It has already been proposed to use a mixture of a polyol and boric acid or an equivalent thereof in enzymatic liquid detergent compositions, whereby the ratio of the polyol to the boric acid is smaller than1. These mixtures are preferably used in unbuilt liquids.
It has been found that, for built liquids, this ratio should be greater than 1 if no special measures are taken to keep the pH of the composition constant, but that the presence of builder materials do cause a physical stability problem, in that the compositions tend to separate into different phases.
According to the invention it has now been found that stable, aqueous, built liquid enzymatic detergent compositions can be obtained by the inclusion in an aqueous, built liquid enzymatic detergent composition of a mixture of polyol and boric acid or an equivalent thereof in a weight ratio of more than 1, and a particular cross-linked polymer to be defined more fully hereafter. By using these three ingredients, a stable, aqueous built enzymatic liquid detergent composition can be obtained, which has a satisfactory enzyme stability, especially at a higher pH, as well as a satisfactory physical storage stability.
The invention will now be explained in more detail.
The polyols for use in the present invention contain only C-, H- and O-atoms. They are free from other (functional) substituting atoms such as N-, Sand the like. The polyols should contain at least 2 hydroxy groups and may contain even up to 6 hydroxy groups. Typical examples of polyols particularly suitable for use in the present invention are diols such as 1 2-propanediol, ethylene-glycol, erythritan, polyols such as glycerol, sorbitol, mannitol, glucose, fructose, lactose, etc.
In general, the polyol is present in an amount of at least 1, preferably at least 4% by weight of the final composition, up to 25% by weight. Preferably the amount ranges from 5-15% by weight of the final composition.
The boric acid or the boron-equivalent thereof, such as boric oxide, borax and other alkali metal borates capable of reacting with a polyol, such as sodium, ortho-, meta- and pyroborates, is used in an amount such that the weight ratio of the polyol to the boron compound is more than 1 (calculated on the basis of borax). This means that the boron compound is used in an amount that is smaller than the amount of the polyol. Generally the amount of the polyol varies from > 100-200%, and preferably from > 100-160% by weight of the boric acid or equivalent thereof (calculated on the basis of borax).
The cross-linked polymer to be used in the present invention is a water-soluble polymer of acrylic acid cross-linked with not more than 10% of a vinyl group-containing cross-linking agent. These crosslinked polymers are more fully described in French Patent Specification No. 1,159,560.
Especially suitable are the water-soluble polymers of acrylic acid, cross-linked with about 1% of a polyallyl ether of sucrose having an average of about 5.8 allyl groups for each sucrose molecule, the polymer having a molecular weight in excess of 1,000,000. Examples of such polymers are Carbopol 934,940 and 941. Carbopol is the Registered Trademark of B. F. Goodrich Co. Ltd., the manufacturers of these polymers. The preferred polymer is Carbopol 941. The cross-linked polymer is used in the present invention in an amount of 0.1-2.0, preferably 0.25-1.0 and especially preferably 0.4-0.8% by weight of the total composition. These cross-linked polymers are normally acidic, and it is essential that they are present in the final composition in a neutralized form.In this respect it has been found that this neutralization should preferably be carried out in situ; separately neutralized polymer (i.e. by first dispersing the acidic polymer in water and subsequently adding a suitable base) did not provide a fully satisfactory stable liquid composition. The neutralization in situ is carried out by adding the polymer to an aqueous medium which contains a suitable alkaline material in a sufficient amount to at least partially, and preferably fully neutralize the polymer. In this respect it has been found that borax is a particularly suitable alkaline material.
The aqueous liquid compositions in which the stabilizing systems of the invention are incorporated are aqueous, built, liquid enzymatic detergent compositions further comprising as essential ingredients enzymes, builders and active detergents.
The enzymes to be incorporated can be proteolytic, amylolytic and cellulolytic enzymes as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH acitivity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Although the liquid compositions of the present invention may have a near-neutral pH value, the present invention is of particular benefit for enzymatic liquid detergents with a pH of 7.5 or above, especially those incorporating bacterial proteases of which the pH-optima lie in the range between 8.0 and 11.0, but it is to be understood that enzymes with a somewhat lower or higher pH-optimum can still be used in the compositions of the invention, benefiting from it.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase D (ex Gist-Brocades N.V., Delft, Holland) and Alcalaseg (ex Novo Industri A/S, Copenhagen, Denmark).
As stated above, the present invention is of particular benefit for enzymatic liquid detergents incorporating enzymes with pH-acitivity andlor stability of above 8.0, such as enzymes also commonly called high-aikaline enzymes.
Particularly suitable is a protease, obtained from a strain of Bacillus, having maximum activity throughou the pH-range of 8-12, developed and sold by Novo Industri AyS under the registrated trade name Esperases. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
High-alkaline amylases and cellulase can also be used, e.g. amylases obtained from a special strain of B. licheniformis, described in more detail in British Patent Specification No. 1,296,839 (Novo).
The enzymes can be incorporated in any suitable form, e.g. as a granulate (marumes, prills etc.), or as a liquid concentrate. The granulate form has often advantages.
The amount of enzymes present in the liquid composition may vary from 0.001 to 10% by weight, and preferably from 0.01 to 5% by weight.
The liquid detergent compositions of the invention furthermore comprise as essential ingredient an acitve detergent material, which may be an alkali metal or aikanol amine soap of C10C24 fatty acid, including polymerized fatty acids or an anionic, nonionic, cationic, zwitterionic or amphoteric synthetic detergent material, or mixtures of any of these.
Examples of anionic synthetic detergents are salts (including sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of Cg-C20 alkylbenzenesulphonates, Ca-Cz primary or secondary alkanesulphonates, Ca-C24 olefinsulphonates, sulphonated polycarboxylic acids, prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g. as described in British Patent Specification No. 1,082,179, C8-C22 alkylsulphates, C8-C24 alkylpolyglycolethersulphonates (containing up to 10 moles of ethylene oxides); further examples are described in "Surface Active Agents and Detergents" (Vol. I and II) by Schwartz, Perry and Berch.
Examples of nonionic synthetic detergents are the condensation products of ethylene oxide, propylene oxide and/or butyleneoxide with C8-C15 alkyiphenols, C8-C,8 primary or secondary aliphatic alcohols, Cs-C18 fatty acid amides; further examples of nonionics include tertiary amine oxides with one C8-C18 alkyl chain and two C13 alkyl chains. The above reference also describes further examples of nonionics.
The average number of moles of ethylene oxide and/or propylene oxide present in the above nonion ics varies from 1-30; mixtures of various nonionics, including mixtures of nonionics with a lower and a higher degree of alkoxylation, may also be used.
Examples of cationic detergents are the quaternary ammonium compounds such as alkyldimethylammonium halogenides, but such cationics are less preferred for inclusion in enzymatic detergent compositions.
Examples of amphoteric or zwitterionic detergents are N-alkylamino acids, sulphobetaines, condensation products of fatty acids with protein hydrolysates but owing to their relatively high costs they are usually used in combination with anionic or a nonionic detergent. Mixtures of the various types of active detergents may also be used, and preference is given to mixtures of an anionic and a nonionic detergent active. Soaps (in the form of their sodium, potassium, and substituted ammonium salts such as of polymerized fatty acids, may also be used, preferably in conjuction with an anionic and/or a nonionic synthetic detergent.
The amount of the active detergent material varies from 1 to 60%, preferably from 2-40 and especially preferably from 5-25%; when mixtures of e.g. anionics and nonionics are used, the relative weight ratio varies from 10:1 to 1:10, preferably from 6:1 to 1:6.
When a soap is also incorporated, the amount thereof is from 140% by weight.
The liquid compositions of the invention further contain up to 60% of a suitable builder, such as sodium, potassium and ammonium or substituted ammonium pyro- and tripolyphosphates, -ethylenediamine tetraacetates, -nitrilotriacetates, -etherpolycarboxylates, -citrates, -carbonates, -orthophosphates, zeolites, carboxymethyloxysuccinate, etc. Particularly preferred are the polyphosphate builder salts, nitrilotriacetates, zeolites, and mixtures thereof. In general the builders are present in an amount of 1-60, preferably 5-50% by weight of the final composition.
The amount of water present in the detergent compositions of the invention varies from 5 to 70% by weight.
Other conventional materials may also be present in the liquid detergent compositions of the invention, for example soil-suspending agents, hydrotropes, corrosion inhibitors, dyes, perfumes, silicates, optical brighteners, suds boosters, suds depressants such as silicones, germicides, anti-tarnishing agents, opacifiers, fabric softening agents, oxygen-liberating bleaches such as hydrogen peroxide, sodium perborate or percarbonate, diperisophthalic anhydride, with or without bleach precursors, reducing bleaches such as sodium sulphite, buffers and the like.
The pH of the final compostions is near neutral, preferably higher than 7.5 and should preferably lie within the range of 8.0 to 10.0, and is, if necessary, buffered to a value within that range by addition of a suitable buffer system. The pH of the wash liquor, when using the composition, is about 1 pH unit higher than the above values at an in-use concentra tion of about 1%.
The invention will now be further illustrated by way of Example. In the Examples the percentages are by weight. In all the Examples the polymerwas added in an acidic form to the aqueous medium from which the liquid detergent composition was obtained, said medium already containing a sufficient amount of a suitable alkaline material for neutralization of the polymer.
Example I The following composition was prepared: potassium dodecylbenzene sulphonate 10 C13-C15 linear primary alcohol, condensed with 7 moles of ethyleneoxide 5 sodium tripolyphosphate 20 borax 10 glycerol 15 Carbopol 941 0.65 enzyme (Maxatases in the form of slurry) 0.3 fluorescer and perfume 0.25 water to 100.0 The pH of this product was 8.0-8.5; the pH rose to 9.0-9.5 at an in-use concentration of about 1%. The physical storage stability after storing for more than 1 month at room temperature and at 37"C was quite acceptable for practical purposes.The enzyme stability after storing for 1 month at room temperature and at 37"C was abt. 80% (residual activity), respectively 90% (residual activity), and the breakdown of the sodium tripolyphosphate was 15%, respectively 0-5% under these conditions.
Example 2 The following compositions were prepared: a b c d e f g sodium dodecylbenzene suiphonate - - - - 7.5 5 5 C13-C1s linear prim. alcohol, condensed with 7 moles of alkylene oxide (a mixture of ethylene- and propylene oxideinaweightratioof92::8) 10 10 10 10 2.5 5 5 an hydrous sodium tripolyphosphate 20 20 20 20 20 20 20 sorbitol - - - - - - 6 glycerol - 10 20 10 10 10 borax 7 7 7 7 7 7 7 Na20.3.3SiO2 - - - 2.7 - - Carbopol 941 0.8 0.8 0.8 0.8 0.65 0.7 0.7 enzyme (Alcalase or Esperase) * water balance pH 8.5 7.4 6.7 7.7 7.5 7.5 7.5 half-life time of enzymes (in days) at37"C Alcalase 2 55 80 50 100 90 12 Esperase 3 55 140 60 10 40 4 * The enzyme was added in such an amount that the final product had a proteolytic activity of 8.5 GU/mg (733 GU/mg = 1 Anson Unitlg) The compositions were stable for several months at room temperature.
Example 3 The following composition was prepared: wt.% sodium dodecylbenzene sulphonate 6 C1rCrs linear prim. alcohol condensed with 9 moles of ethylene oxide 3 sodium oleate 1 sodium citrate 2.aq 7 zeolite (type 4A) 28 sodium carboxymethylcellulose 0.5 borax 7.5 Carbopol 941 0.2 fluorescer 0.1 glycerol 7.5 or 10 water balance enzyme (Alcalase) (as in Example 2) These liquids were physically stable; the half-life time at 37"C of the enzymes was 10 days with 7.5% glycerol and 11 days with 10% glycerol.
Example 4 The following composition was prepared: vvt.% sodium dodecylbenzene sulphonate 5 C13-C1s linear prim. alcohol condensed with 7 moles of alkylene oxide (a mixture of ethylene- and propylene oxide in a weight ratio of 92:8) 2 anhydrous sodium tripolyphosphate 20 glycerol 10 borax 7 sodium sulphite 5 sodium carboxymethylcellulose 0.4 fluorescer 0.1 Carbopol 941 0.5 Alcalase (1163 glycine units/mg) 0.7 silicon oil 0.25 water balance The enzyme had a half-lifetime of 4 months at 37"C, and the product was physically stable still after 2 months at 3, 23, 37 and 52"C.

Claims (3)

1. An aqueous, built, liquid enzymatic detergent composition comprising enzymes, builders and detergent active materials in an aqueous medium, characterized in that the liquid composition contains a polyol, boric acid or a boron-equivalent thereof in a weight ratio of polyol to the boric acid of more than 1, as well as a neutralized cross-linked polyacrylate polymer.
2. A composition according to claim 1, characterized in thatthe polyol is glycerol, the boronequivalent is borax, and the cross-linked polymer is a polyacrylate, cross-linked with about 1% of a polyallyl ether of sucrose with about 5.8 allyl groups for each sucrose molecule, the polymer having a molecular weight in excess of 1.000.000.
3. A composition according to claim 1 or 2, characterized in that it contains from 1-25% by weight of the polyol and from 0.1-2% by weight of the cross-linked polymer.
4 A composition according to any one of claims 1-3, characterized in that it contains the cross-linked polymer in an in-situ neutralized form
GB8120184A 1980-07-02 1981-06-30 Liquid enzyme detergent Expired GB2079305B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT68042/80A IT1129814B (en) 1980-07-02 1980-07-02 LIQUID ENZYMATIC DETERGENT COMPOSITION

Publications (2)

Publication Number Publication Date
GB2079305A true GB2079305A (en) 1982-01-20
GB2079305B GB2079305B (en) 1984-02-08

Family

ID=11307403

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8120184A Expired GB2079305B (en) 1980-07-02 1981-06-30 Liquid enzyme detergent

Country Status (14)

Country Link
JP (1) JPS604874B2 (en)
AR (1) AR223618A1 (en)
AU (1) AU537950B2 (en)
BR (1) BR8104171A (en)
CA (1) CA1163218A (en)
DE (1) DE3125533C2 (en)
FR (1) FR2486095A1 (en)
GB (1) GB2079305B (en)
IT (1) IT1129814B (en)
MY (1) MY8600451A (en)
NL (1) NL8103169A (en)
NZ (1) NZ197531A (en)
PH (1) PH18505A (en)
ZA (1) ZA814462B (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080223A2 (en) * 1981-11-19 1983-06-01 Unilever N.V. Enzymatic liquid detergent composition
EP0080748A1 (en) * 1981-11-13 1983-06-08 Unilever N.V. Enzymatic liquid cleaning composition
GB2126242A (en) * 1982-08-30 1984-03-21 Colgate Palmolive Co Stabilized enzyme-containing detergent compositions
GB2140818A (en) * 1983-05-31 1984-12-05 Colgate Palmolive Co Stabilized built single-phase liquid detergent composition containing enzymes
GB2140819A (en) * 1983-05-31 1984-12-05 Colgate Palmolive Co Built single-phase liquid anionic detergent composition containing stabilized enzymes
US4532064A (en) * 1983-04-26 1985-07-30 Lever Brothers Company Aqueous enzyme-containing compositions with improved stability
US4537707A (en) * 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid and formate to stabilize enzymes
US4537706A (en) * 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid to stabilize enzymes
GB2178054A (en) * 1985-07-26 1987-02-04 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
GB2178055A (en) * 1985-07-26 1987-02-04 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
US4652394A (en) * 1983-05-31 1987-03-24 Colgate Palmolive Co. Built single phase liquid anionic detergent compositions containing stabilized enzymes
US4670179A (en) * 1986-05-29 1987-06-02 Colgate Palmolive Company Stabilized built single phase liquid detergent composition containing enzymes
US4842769A (en) * 1985-07-26 1989-06-27 Colgate-Palmolive Co. Stabilized fabric softening built detergent composition containing enzymes
US4842767A (en) * 1986-09-10 1989-06-27 Colgate-Palmolive Company Heavy duty built aqueous liquid detergent composition containing stabilized enzymes
US4842758A (en) * 1986-10-31 1989-06-27 Colgate-Palmolive Company Stabilized enzyme system for use in aqueous liquid built detergent compositions
GB2213495A (en) * 1987-12-08 1989-08-16 Donnell Anne O Cleaning liquids
US4900475A (en) * 1985-07-26 1990-02-13 Colgate-Palmolive Co. Stabilized built liquid detergent composition containing enzyme
EP0381262A2 (en) * 1989-01-30 1990-08-08 Unilever N.V. Enzymatic liquid detergent composition
US5004557A (en) * 1985-08-16 1991-04-02 The B. F. Goodrich Company Aqueous laundry detergent compositions containing acrylic acid polymers
WO1991009929A1 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Stabilizers for aqueous cleaning fluids
US5089163A (en) * 1989-01-30 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic liquid detergent composition
WO1992007930A1 (en) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Enzymatic liquid detergent
US5281277A (en) * 1991-04-08 1994-01-25 Tomei Sangyo Kabushiki Kaisha Liquid composition for contact lenses and method for cleaning a contact lens
WO1994024240A1 (en) * 1993-04-08 1994-10-27 The Procter & Gamble Company Secondary (2,3) alkyl sulfate surfactants in stable enzyme-containing detergent compositions
WO1994029424A1 (en) * 1993-06-07 1994-12-22 Buckman Laboratories International, Inc. Synergistically stabilized liquid enzymatic compositions
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
US5472628A (en) * 1991-04-30 1995-12-05 The Procter & Gamble Company Liquid detergents with an aryl acid for inhibition of proteolytic enzyme
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
LT3962B (en) 1993-12-21 1996-05-27 Albright & Wilson Funcional fluids
US5604190A (en) * 1995-06-07 1997-02-18 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
US5723421A (en) * 1995-06-07 1998-03-03 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
EP1247834A1 (en) * 1999-10-21 2002-10-09 Daiso Co., Ltd. Crosslinking agent based on polyallyl ether compound
WO2015200208A1 (en) * 2014-06-24 2015-12-30 3M Innovative Properties Company Low foaming multi enzymatic cleaner

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06122896A (en) * 1992-03-31 1994-05-06 Shiseido Co Ltd Detergent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3781212A (en) * 1972-10-27 1973-12-25 Townsend & Townsend Aerosol enzyme detergents stabilized with carbon dioxide
GB1590445A (en) * 1976-11-01 1981-06-03 Unilever Ltd Enzymatic liquid composition

Cited By (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0080748A1 (en) * 1981-11-13 1983-06-08 Unilever N.V. Enzymatic liquid cleaning composition
US4404115A (en) 1981-11-13 1983-09-13 Lever Brothers Company Enzymatic liquid cleaning composition
US4462922A (en) * 1981-11-19 1984-07-31 Lever Brothers Company Enzymatic liquid detergent composition
EP0080223A3 (en) * 1981-11-19 1984-10-03 Unilever Nv Enzymatic liquid detergent composition
EP0080223A2 (en) * 1981-11-19 1983-06-01 Unilever N.V. Enzymatic liquid detergent composition
GB2126242A (en) * 1982-08-30 1984-03-21 Colgate Palmolive Co Stabilized enzyme-containing detergent compositions
GB2168375A (en) * 1982-08-30 1986-06-18 Colgate Palmolive Co Stabilized enzyme-containing detergent compositions
GB2168376A (en) * 1982-08-30 1986-06-18 Colgate Palmolive Co Stabilized enzyme-containing detergent compositions
US4532064A (en) * 1983-04-26 1985-07-30 Lever Brothers Company Aqueous enzyme-containing compositions with improved stability
DE3418295A1 (en) * 1983-05-31 1984-12-06 Colgate Palmolive Co STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING AQUEOUS LIQUID DETERGENT
FR2546901A1 (en) * 1983-05-31 1984-12-07 Colgate Palmolive Co A STABILIZED, STABILIZED, DETERGENT ADJUVANT-LIQUID DETERGENT COMPOSITION CONTAINING ENZYMES, AND A WASHING METHOD USING THE SAME
FR2546902A1 (en) * 1983-05-31 1984-12-07 Colgate Palmolive Co ONE-PHASE LIQUID ANIONIC DETERGENT COMPOSITION COMPRISING A DETERGENT ADJUVANT AND CONTAINING STABILIZED ENZYMES AND A WASHING METHOD USING THE SAME
GB2140819A (en) * 1983-05-31 1984-12-05 Colgate Palmolive Co Built single-phase liquid anionic detergent composition containing stabilized enzymes
GB2140818A (en) * 1983-05-31 1984-12-05 Colgate Palmolive Co Stabilized built single-phase liquid detergent composition containing enzymes
AT394573B (en) * 1983-05-31 1992-05-11 Colgate Palmolive Co STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING, AQUEOUS LIQUID DETERGENT
AT394385B (en) * 1983-05-31 1992-03-25 Colgate Palmolive Co STABILIZED, CLEAR, SINGLE-PHASE, BUILDER AND ENZYME-CONTAINING LIQUID DETERGENT
US4652394A (en) * 1983-05-31 1987-03-24 Colgate Palmolive Co. Built single phase liquid anionic detergent compositions containing stabilized enzymes
US4537707A (en) * 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid and formate to stabilize enzymes
US4537706A (en) * 1984-05-14 1985-08-27 The Procter & Gamble Company Liquid detergents containing boric acid to stabilize enzymes
US4900475A (en) * 1985-07-26 1990-02-13 Colgate-Palmolive Co. Stabilized built liquid detergent composition containing enzyme
GB2178055A (en) * 1985-07-26 1987-02-04 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
GB2178055B (en) * 1985-07-26 1989-10-18 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
GB2178054B (en) * 1985-07-26 1989-10-18 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
US4842769A (en) * 1985-07-26 1989-06-27 Colgate-Palmolive Co. Stabilized fabric softening built detergent composition containing enzymes
GB2178054A (en) * 1985-07-26 1987-02-04 Colgate Palmolive Co Stabilized built liquid detergent composition containing enzymes
US5004557A (en) * 1985-08-16 1991-04-02 The B. F. Goodrich Company Aqueous laundry detergent compositions containing acrylic acid polymers
US4670179A (en) * 1986-05-29 1987-06-02 Colgate Palmolive Company Stabilized built single phase liquid detergent composition containing enzymes
US4842767A (en) * 1986-09-10 1989-06-27 Colgate-Palmolive Company Heavy duty built aqueous liquid detergent composition containing stabilized enzymes
US4842758A (en) * 1986-10-31 1989-06-27 Colgate-Palmolive Company Stabilized enzyme system for use in aqueous liquid built detergent compositions
GB2213495A (en) * 1987-12-08 1989-08-16 Donnell Anne O Cleaning liquids
GB2213495B (en) * 1987-12-08 1992-09-16 Donnell Anne O Cleaning liquids
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease
EP0381262A3 (en) * 1989-01-30 1991-07-31 Unilever N.V. Enzymatic liquid detergent composition
EP0381262A2 (en) * 1989-01-30 1990-08-08 Unilever N.V. Enzymatic liquid detergent composition
US5089163A (en) * 1989-01-30 1992-02-18 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic liquid detergent composition
WO1991009929A1 (en) * 1989-12-22 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Stabilizers for aqueous cleaning fluids
WO1992007930A1 (en) * 1990-11-02 1992-05-14 Henkel Kommanditgesellschaft Auf Aktien Enzymatic liquid detergent
US5281277A (en) * 1991-04-08 1994-01-25 Tomei Sangyo Kabushiki Kaisha Liquid composition for contact lenses and method for cleaning a contact lens
US5472628A (en) * 1991-04-30 1995-12-05 The Procter & Gamble Company Liquid detergents with an aryl acid for inhibition of proteolytic enzyme
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
US5442100A (en) * 1992-08-14 1995-08-15 The Procter & Gamble Company β-aminoalkyl and β-N-peptidylaminoalkyl boronic acids
WO1994024240A1 (en) * 1993-04-08 1994-10-27 The Procter & Gamble Company Secondary (2,3) alkyl sulfate surfactants in stable enzyme-containing detergent compositions
WO1994029424A1 (en) * 1993-06-07 1994-12-22 Buckman Laboratories International, Inc. Synergistically stabilized liquid enzymatic compositions
LT3962B (en) 1993-12-21 1996-05-27 Albright & Wilson Funcional fluids
US5604190A (en) * 1995-06-07 1997-02-18 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
US5723421A (en) * 1995-06-07 1998-03-03 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
US5939369A (en) * 1995-06-07 1999-08-17 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
US5948738A (en) * 1995-06-07 1999-09-07 Alcon Laboratories, Inc. Stable liquid enzyme compositions and methods of use in contact lens cleaning and disinfecting systems
EP1247834A1 (en) * 1999-10-21 2002-10-09 Daiso Co., Ltd. Crosslinking agent based on polyallyl ether compound
EP1247834A4 (en) * 1999-10-21 2005-11-16 Daiso Co Ltd Crosslinking agent based on polyallyl ether compound
WO2015200208A1 (en) * 2014-06-24 2015-12-30 3M Innovative Properties Company Low foaming multi enzymatic cleaner
US20170130171A1 (en) * 2014-06-24 2017-05-11 3M Innovative Properties Company Low foaming multi enzymatic cleaner

Also Published As

Publication number Publication date
AU7237981A (en) 1982-01-07
IT8068042A0 (en) 1980-07-02
FR2486095A1 (en) 1982-01-08
FR2486095B1 (en) 1983-11-04
DE3125533A1 (en) 1982-06-09
BR8104171A (en) 1982-03-16
PH18505A (en) 1985-08-02
ZA814462B (en) 1983-02-23
NZ197531A (en) 1983-12-16
AU537950B2 (en) 1984-07-19
NL8103169A (en) 1982-02-01
IT1129814B (en) 1986-06-11
AR223618A1 (en) 1981-08-31
MY8600451A (en) 1986-12-31
CA1163218A (en) 1984-03-06
JPS5740599A (en) 1982-03-06
GB2079305B (en) 1984-02-08
JPS604874B2 (en) 1985-02-07
DE3125533C2 (en) 1985-11-21

Similar Documents

Publication Publication Date Title
CA1163218A (en) Liquid enzymatic detergent composition
US4462922A (en) Enzymatic liquid detergent composition
US4404115A (en) Enzymatic liquid cleaning composition
US4532064A (en) Aqueous enzyme-containing compositions with improved stability
US4261868A (en) Stabilized enzymatic liquid detergent composition containing a polyalkanolamine and a boron compound
CA1092036A (en) Enzymatic liquid detergent compositions
US5089163A (en) Enzymatic liquid detergent composition
US5551990A (en) Enzymatic dishwashing and rinsing composition
EP0425214A2 (en) Enzyme-containing detergent compositions and their use
US5112518A (en) Enzymatic dishwashing composition containing a chlorine-type bleaching agent
AU618036B2 (en) Machine dishwashing compositions
CA1092037A (en) Enzymatic liquid detergent composition
US5501820A (en) Aqueous enzymatic detergent compositions
EP0842254B1 (en) Dingy fabric clean-up with amylase enzyme in detergent compositions
EP0506695B1 (en) Enzymatic liquid detergent compositions and their use
EP0319053A2 (en) Improved phosphate-free detergent bleach compositions

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee