CA2199260A1 - A cleaning composition comprising lipase and amylase enzymes - Google Patents
A cleaning composition comprising lipase and amylase enzymesInfo
- Publication number
- CA2199260A1 CA2199260A1 CA 2199260 CA2199260A CA2199260A1 CA 2199260 A1 CA2199260 A1 CA 2199260A1 CA 2199260 CA2199260 CA 2199260 CA 2199260 A CA2199260 A CA 2199260A CA 2199260 A1 CA2199260 A1 CA 2199260A1
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- Canada
- Prior art keywords
- composition according
- cleaning composition
- weight
- present
- amount
- 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.)
- Abandoned
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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
- C11D3/38618—Protease or amylase in liquid compositions only
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- 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
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
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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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A novel liquid enzyme cleaning composition for removing heated food soils such as those found in ovens, and the method of its use by application of the composition to a cool surface bearing such food soils. The composition includes enzymes that are active in the pH range 10-14 and comprise a mixture of a lipase and an amylase, and, optionally, a protease. The composition also contains an alkali metal silicate. The composition preferably contains non-ionic surfactant and is buffered.
Description
W096/07723 0 a~ ~ 2~0 PCTIUS9S/11105 A CLEANING COMPOSITION COMPRISING LIPASE AND AMYI ASE ENZYMES
FIELD OF THE INVENTION
This invention relates to cleaning compositions, and particularly to cleaning compositions for use on ovens.
BA~CKGROIJND AL~T
Cleaning compositions for use on sl~rf~ s that have been subjected to Sp~ hlg by food products at high temperatures are well known. Such sl~rf~res, for example in ovens, quickly become coated with food residues that can become baked on at high temperatures These residues from food subjected to high te~ c.dlul~;s will be described herein as burnt-on food soils.
Removal of burnt-on food soils is considerably more difficult than removal of food stains from, for example, textile m~t~ri~l~. The high temp~ldlulcs to which such food soils have been subjected causes their removal to require very aggressive chlomic~l compositions that are usually either very acidic or more usually very ~lkslline. In particular, known oven cleaning compositions tend to have a quite extreme pH and particularly tend to be strongly 20 ~lk~lin~ since it has been believed that burnt-on food soils can only be removed by such aggressive m~t( ri~l~. These compositions are often used under severe treating conditions, including oxi~li7in~ and recl~cin~ conditions at high te~ .dLIlres.
Cleaning compositions have been proposed that contain active enzymes, such as washing powders and d~tclgen~. However, these compositions typically have been proposed 25 for washing conditions a~ç~-.ate for ~extile m~ttori~l~7 for example L~ )el~Lures below 55C and pH's below 11.
SUMMARY OF THE INVENTION
The liquid, enzyme-based cle~nin~; composition of the invention is sllrnm~ri7~1 in that it includes a lipase en_yrne active at a pH of from 10 to 14; an amylase enzyme also W 0 96/07723 0 ~ ~ ~9 260 - 2 - PC~rrUS9S/11105 active at a pH of from 10 to 14; at least one alkali-stable non-ionic or anionic s--nf~rt~nt; an alkali metal silicate; and an inert diluent. The composition is buffered at a pH of 10 to 14.
The method of the invention is summarized in that a method of cleaning a surface ' bearing burnt-on food soils includes the steps of applying the composition of claim 1 to the 5 food soils at a cool surface temperature; allowing the food soils to soften; and removing the food soils. Preferably the surface tcl,lp~,ldl~re does not exceed about 50C.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention there is provided a cleaning composition for burnt-on food soils, particularly suitable for use on ovens, that is enzyme based. The enzyme colll~ollent is active in the pH range of 10-14. Incorporation of enzymes into cleaning compositions of this type would not normally have been considered since enzymes are known to be ra~her fragile and to be deactivated rather easily. It is surprising to find an 15 enzyme-co~ -g composition that is effective particularly at pH's in excess of 10.
According to the present invention, there is provided an enzyme-based cleaning composition compri~ing a lipase enzyme, an amylase enzyme, an alkali-metal silicate, and an alkali-stable s~ rt~nt which composition is buffered to m~int~in the pH of the composition in the range from 10-14, and preferably from 10-12.5. The o~Limulll pH is approximately 20 12.5. The invention also provides a method of cle~ning surfaces that have been subjected to food residues at high lenl~.dlu.cs, such as ovens and other cooking sl~ rçs, ~tili7.ing the said enzymatic composition for cle~ning .
All amounts stated in this description are based on the total weight of the composition of the invention. The enzymes used in the invention are preferably ~ik~liphilic. If enzymes 25 so le~ign~ted are not commercially available, enzymes can be selected on the basis of activity against the relevant components of the soil (e.g. amylase against starch components) as a function of pH. Those skilled in the art can readily identify commercially or otherwise available enzymes with sufficient activity at the pH of the composition to be useful as components of a cl~ning composition and particularly those that would have an activity at 30 the o~lhllu~ll pH ofthe product, 12.5.
W096/07723 _3 PCT/U~95/11105 Lipase enzymes used in the present invention are those enzymes that promote hydrolysis of triglycerides into mono and diglycerides, glycerol, and free fatty acids, all of which are more soluble than the original fat triglyceride. A nurnber of different lipase enzymes are commercially available, having been used in fabric cleaning formulations for the 5 removal offat-co~ ;lli--g stains such as the stains resulting from cooking fat, salad oils, butter, and fat based sauces. A preferred lipase for use in the present invention is Lipolase, m~nllf~ctured by Novo Nordisk Indus~ry. This is a 1,3-specific lipase that cleaves ester bonds in the positions 1 and 3 of a triglyceride.
Amylase enzyrnes are those that hydrolyze starches to soluble ~lextrin~ and 10 oligosaccharide. Amylases have been used in fabric cleaning compositions to remove starch-cont~inin~ stains, such as those made from pasta, chocolate, and gravy products, by way of example, only. Amylase enzymes hydrolyze 1,4-alpha glucosidic bonds in an amylose or amylopectin. A pl~r~ d amylase is Termamyl~ which is a commercially available enzyme m~nllf~rtllred by Novo Nordisk Industry, being alpha amylase prepared by fPrment~tion of 15 Rnci~u~ licheniformis.
The composition of the invention can contain a protease as an optional, additional enzyme. Proteases are enzymes that hydrolyses protein to peptides that can be readily dissolved. Proteases have previously been incorporated into fabric cleaning compositions such as laundry detergents. A preferred ploteasl;; is the cornmercial product Savinase(~ also 20 available from Novo Nordisk Industry. Savinase~ is a proteolytic enzyme prepared by submerged ferment~tiQn of an alkalophilic species of Bacillus and is an endo-protease of the serine type, with broad substrate specificity.
Each of the enzymes types used are present in from 0.1 to 4% by weight of the composition. The particular enzymes disclosed above are only non-limiting examples of 25 their types. It should be noted that a wide range of commercially available lipase, amylase, and protease enzymes are available.
Since the compositions of the invention are generally inten-11?cl for oven cleaning, they should be of sufficient viscosity to hold them on a vertical surface for an effective time, i.e.
for a time sufficient to effect or at least f~.ilit~te the removal of burnt-on food soils. In order 30 to achieve such a viscosity, it may be nPceS~ry to add a thickener, in addition to the other colll~ollents of the co~ u~ilion. The amount of the thickener will depend on the nature of wo96/o7723 ~ g9 26 0 PCl`/US95/11105 the thickener itself and of the other components in the composition. It may be that the other components in the composition, along with their other ~lOp~l lies, also will act as a thickener for the purpose of giving the a~lv~fiate viscosity to the composition, making unnecessary the addition of a separate component specifically as a thickener. A composition primarily 5 inten~f d for application to burnt-on food soils on horizontal ~nrf~ces, such as stove tops, could be in a more fluid form.
When present as a separate component that is provided primarily to increase composition viscosity, the thickener should be present in the range of from 0.05 to 6 percent by weight and preferably from 0.2 to 6 percent. The thickeners can be selected from the 10 group con~i~tin~ of inorganic materials, organic polymeric materials, and cc,ln~lible mixtures thereof.
Suitable inorganic thickeners include, by way of example only, colloidal silica,smectite clays such as bentonite, attapulgite, Laponite, m~gn~sium alumino-silicate, and compatible mixtures thereof. Polymeric organic thickeners can be biopolymers (such as 15 ~nth~n or welan gum) or synthetic polymers (such as polyacrylates or hydrophobically modified polyu~ ~le). Coll~ cially available examples of such synthetic polymers may be selected from the CARBOPOL(~) polymers produced by B.F. Goodrich or the RHEOVIS~ polymers available from Allied Colloids. Preferably the thicken~r is a cro~linked polyacrylate. Commercial examples of cros~linked polyacrylates may be selected 20 from the ACRYSOL (~ polymers produced by Rohm & Haas. When the thickener is ahydrophobically modified polyul~;lL~le thickener, it should more preferably be present in the range of from 1 to 2 percent by weight.
The alkali metal silicate compounds in the composition assist in fat break-down and provide alkalinity. They also assist as d~ builders and act as corrosion inhibitors.
25 Particular alkali metal silicates that can be employed are those having a Na2O:SiO2 ratio in the range 1:2 to 2:1. The ~Lillluln range is from 1:1 to 2:1. These alkali metal silicates will usually be present in the range 5-35 weight percent and preferably 5-25 weight percent, although the precise amount may depend on the nature of the surfactant.
The amount of silicate will also be rl~ttqrmine~l to some extent by the nature of the 30 buffer used. Thus the pl~r~ d buffer employing an alkali metal carbonate, and preferably sodium c~b~ , may allow a reduced amount of silicate to be present. Decreasing the 0~ 99260 WO 96107723 PCT/US9~/lllO~i amount of silicate present, though it cannot be reduced to 0, is advantageous in that it reduces the amount of electrolyte, which increases the shelf life of the formula. Also, silicates sometimes have adverse effects on skin, making it desirable to reduce the amount of silicates so as to ~ ç the side effects of the composition, should it come in contact with 5 ull~lolccted skin.
The composition of the invention must be buffered, although it may be that components in the composition, e.g. the silicate, will provide a sufficient bu~clillg effect so as not to require an independent buffer. The buffer colll~ollcllL~ in the composition should be selected to retain the composition's pH in the range of from 10-14, preferably from 10-13, 10 and optimally at about 12.5. If a specific buffer is required, a wide variety of buffer compositions are available and known to those skilled in the art. Carbonate buffers and particularly alkali metal (e.g. sodium) carbonate buffers are ~lercllcd because of the high pH
ofthe colll~osilion. Preferably carbonate is added in amounts ranging from 0.5 to 12 weight percent.
To enable the composition to wet and penetrate the m~teri~l~ to be rernoved, thecomposition p lcr~ bly co~t~inC a surfactant. Pler~.lcd sllrf~t~nt~ are those that are alkali stable and have an HLB (lly~uphile-lipophile balance) in the range of 12-20 and preferably in the range 13-16. The HLB is a measure of the relative water solubility of the snrf~ct~nt and gives an indication of the relative ~JlU~l lions of hydrophobic and hydrophilic portions in 20 the molecule. The ~llrf~rt~nt~ preferably are non-ionic, but anionic ~ulr~cl~ll~ may be used.
It is only rarely that a cationic snrf~ct~nt will be operable.
Preferable non-ionic ~nrf~l~t~nt~ include nonyl phenol ethoxylates (preferably 9 and 20 mole ethoxylates), alkyl glucosides, C l 1 oxo-alcohol ethoxylates co~ at least 7 moles of ethylene oxide, short chain fat~ acid polyethylene glycol ethers CO~ i"g at least 5 25 moles of ethylene oxide, and iso-C 13 oxo-alcohol ethoxylates cont~ining at least 8 moles of ethylene oxide, or compatible nlixlule~ thereof. Alkyl and aryl capped m~t~ri~l~ can also be employed.
Typical anionic surfactants are ~lk~lin.o metal and alkylolamine alkyl sulfonates, p~U~lll sulfonates, and ~lk~line metal alkyl phenol sulfonates.
Normally one would use either an anionic sllrf~rt~nt or a non-ionic ~,-, r~ as ll~ixlulGs of anionic and non-ionic sllrf~ t~nt~ tend to be ineffective. Mixtures of surfactants W0 96/07723 ~ 2 8 ~ 6 - PCT/US95/11105 are not normally compatible because of the high ~lk~linity, tending to separate. However, by very careful choice of the ~ ~-;ate sllrf~ct~nt system, anionic/non-ionic sllrf~rt~nt mixtures are possible and are not excluded from the invention.
The amount of sllrf~ct~nt present is usually from 0.5 to 10 weight percent. With5 anionic surf~rt~nt~, it is also desirable that a co-builder be present, partly to assist in avoiding the salting-out of the surfactant. A wide variety of co-builders are used with anionic surfactants in the various applications of these sllrf~t~nt~ Preferred co-builders that are useful for anionic systems are alkali metal polyphosph~tP~ alkali metal salts of organic acids, and alkali metal salts of polymeric acids. More preferably the co-builder is at least one of 10 STPP (sodium tri polyphosphate) and alkali metal salts of citric acid, gluconic acid, polyacrylic acid, and modified polyacrylic acid. Compatible mixtures of the above mentioned co-builders can be ~ltili7to~1 In addition, the silicate component of the composition can contribute as a co-builder. Preferably the co-builder (other than the silicate component) is present in the amount of 0.5-12 percent by weight.
Co-builders are usually less nPcess~ry in non-ionic surfactant systems since there is less likelihood of inactivation by calcium ions. Nevertheless, co-builders may still be n.oces~ry if it is found that the calcium ions present in the composition are having an adverse effect.
Preferably the compositions include hydrotropes, i.e. compounds that have the 20 property of increasing the aqueous solubility of any insoluble organic chemicals present.
Useful hydrotropes are cllm~nl~slllfonate, sodium _ylene sulphonate, phosphate esters, and sodium toluene sulphonate. Compatible lmxlules of the above mentioned hyd-~ tlopes can be used if desired. Preferably said h~dl~ opes are present in the amount of 0.2-2.5 percent by weight.
Removal of bDt-on food soils can be enhanced by the use of penetrating solvents.The presence of these solvents also can assist in stabili_ing the en7yme content of the composition. Suitable solvents are those organic liquids that soften and penetrate into resin-type materials, for example those solvents found in paints. The particularly l ler~ d solvents are those that are found also to enhance the stability of the en_ymes. Suitable 30 solvents are glycol ethers (e.g. those sold under the trade name Cellosolve), esters, glycol ether acet~t~, methyl pyrrolidone, and 1,3-dimethyl-2-imiti~7~lidinone. Cnmp~tihle ~ W096/~7723 ~ 9 260 PCT~S95/lllos ulc;s of the above mentioned solvents can be used. More preferably, the mentioned solvents are present in the amount of from 2-10 percent by weight.
- The compositions of the invention can contain other conventional cleaning composihon colll~onents, if they do not m~t~n~lly detriment~lly affect the enzymatic 5 pr~llies of the system. Such components include, for example, sequestering agents, dyes, bleaches, bleach activators, foam control agents, and fragrances.
The composition of the invention also includes appropriate diluents for application, although the composition may be ~l~a.cd in a concenb-ated form for dilution prior to use.
The preferred diluent (apart from the penetrating solvents discussed above) is water and will 10 usually comprise at least 70% and preferably at least 75% by weight of the composition.
The composition of the invention can be applied directly without further dilution, for example by water, and can be applied by brushing or by spraying from a spray device, including an aerosol dispenser. In the case of an aerosol dispenser, the inclusion of a foaming agent in the composition will result in a foam that covers the surface to be treated. The 15 surface to be treated should preferably be cold, which shall mean commonly experienced room l~ cldlules. If warm, the surface should not be of a L~ dLule s~lffi~iently high as to be deleterious to the enzymes in the composition. Tel,lpe.~l lres not in excess of 50C are d.
The invention will be illustrated by the following Ex~llples.
wo 96/07723 ~ 6 ~ 8 - PCT/USg5/1110 FXAl\IPT.F 1.
The following were combined in the stated percentages by weight. Compositions described in Columns A and B are examples of specific formulations that have been made, 5 while Column C states the pl~r~lled ranges of ingredients:
Name Percentage Comp Comp C
ACRYSOL* ICS-I - 5.0 5.0 0.05-6 A commercial polyacrylate resin supplied by Rohm & Haas.
Sodium Metasilicate - 5.0 5.3 5-35 A commercial product METSO 510*
supplied by Crosfields Plc ETHYLAN* BAB 20 - 1.0 1.1 0.5-10 Nonionic surfactant supplied by Akcros Chemicals Hexyl CELL(~SOLVE* - 3.0 2.7 2-10 Ethylene glycol monohexyl ether supplied by Union Carbide Sodium Carbonate 1.5 1.2 0.5-12 Sodium Citrate 5.0 3.8 0.5-12 LIPOLASE* 100LTYPEEX- 2.5 2.5 0.1-4 A commercial lipase supplied by Novo Nordisk Tnd~ ries TERMAMYL* 300 TYPE DX - 2.0 2.0 0.1-4 A commercial amylase supplied by Novo Nordisk Industry Water 75.00 76.4 70-75 * Trade Name or Registered Trade Mark The compositions of Example 1 were viscous fluids which, when applied to the vertical walls of an oven, r~m~inPd in position for sufficient time to effect cleaning. When the compositions were applied to a surface co~ ."i,~ l with burnt-on food soils in a test of 10 the type recommen~le~l by the Vitreous Enamel Council, the soils softened and were easily removable after 16 hours.
WO 96/07723 ~ 2 1 9 ~ 2 6 Q PCT/US95/11105 F,XAl\IPT,F 2.
The following were combined in the stated percentages by weight. The composition described in Column A is an example of a specific formulation that has been made, while Column B states the ~.c;r~lled ranges of ingredients:
Name Percentage Carbopol*- 2.0 0.05-6 A commercial cross-linked polyacrylate supplied by B. F. Goodrich Sodium Metasilicate - 5.3 5-35 A commercial product METSO 510* supplied by Crosfields Plc ETHYLAN* BAB 20 - 1.0 0.5-10 Nonionic surfactant supplied by Akcros Chemie~lc Hexyl CELLOSOLVE* - 2.6 2-10 Ethylene glycol monohexyl ether (supplied by Union Carbide) Sodium Carbonate 1.1 0.5-12 Sodium Citrate 3.8 0.5-12 LIPOLASE* 100L TYPEEX- 2.5 0.1-4 A colnm~orcial lipase supplied by Novo Nordisk Industry TERMAMYL* 300 TYPE DX - 2.0 0.1-4 A commercial amylase supplied by Novo Nordisk Industry Water 797 70 75 * Trade Name or Regi~L~d Trade Mark The composition of Example 2 was a viscous fluid which, when applied to the vertical walls of an oven, rem~ined in position for sufficient time to effect cle~nin~ When applied to a surface cn"lS.",i,.i1le-1 with burnt-on food soils in a test ofthe type leco~ en-~ed by the Vitreous Enamel Council, the soils softened and were easily removable after 16 hours.
The invention is not limited to the Examples, which are only illustrative. Tn~1e~-1 the invention is in accordance with the claims.
FIELD OF THE INVENTION
This invention relates to cleaning compositions, and particularly to cleaning compositions for use on ovens.
BA~CKGROIJND AL~T
Cleaning compositions for use on sl~rf~ s that have been subjected to Sp~ hlg by food products at high temperatures are well known. Such sl~rf~res, for example in ovens, quickly become coated with food residues that can become baked on at high temperatures These residues from food subjected to high te~ c.dlul~;s will be described herein as burnt-on food soils.
Removal of burnt-on food soils is considerably more difficult than removal of food stains from, for example, textile m~t~ri~l~. The high temp~ldlulcs to which such food soils have been subjected causes their removal to require very aggressive chlomic~l compositions that are usually either very acidic or more usually very ~lkslline. In particular, known oven cleaning compositions tend to have a quite extreme pH and particularly tend to be strongly 20 ~lk~lin~ since it has been believed that burnt-on food soils can only be removed by such aggressive m~t( ri~l~. These compositions are often used under severe treating conditions, including oxi~li7in~ and recl~cin~ conditions at high te~ .dLIlres.
Cleaning compositions have been proposed that contain active enzymes, such as washing powders and d~tclgen~. However, these compositions typically have been proposed 25 for washing conditions a~ç~-.ate for ~extile m~ttori~l~7 for example L~ )el~Lures below 55C and pH's below 11.
SUMMARY OF THE INVENTION
The liquid, enzyme-based cle~nin~; composition of the invention is sllrnm~ri7~1 in that it includes a lipase en_yrne active at a pH of from 10 to 14; an amylase enzyme also W 0 96/07723 0 ~ ~ ~9 260 - 2 - PC~rrUS9S/11105 active at a pH of from 10 to 14; at least one alkali-stable non-ionic or anionic s--nf~rt~nt; an alkali metal silicate; and an inert diluent. The composition is buffered at a pH of 10 to 14.
The method of the invention is summarized in that a method of cleaning a surface ' bearing burnt-on food soils includes the steps of applying the composition of claim 1 to the 5 food soils at a cool surface temperature; allowing the food soils to soften; and removing the food soils. Preferably the surface tcl,lp~,ldl~re does not exceed about 50C.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention there is provided a cleaning composition for burnt-on food soils, particularly suitable for use on ovens, that is enzyme based. The enzyme colll~ollent is active in the pH range of 10-14. Incorporation of enzymes into cleaning compositions of this type would not normally have been considered since enzymes are known to be ra~her fragile and to be deactivated rather easily. It is surprising to find an 15 enzyme-co~ -g composition that is effective particularly at pH's in excess of 10.
According to the present invention, there is provided an enzyme-based cleaning composition compri~ing a lipase enzyme, an amylase enzyme, an alkali-metal silicate, and an alkali-stable s~ rt~nt which composition is buffered to m~int~in the pH of the composition in the range from 10-14, and preferably from 10-12.5. The o~Limulll pH is approximately 20 12.5. The invention also provides a method of cle~ning surfaces that have been subjected to food residues at high lenl~.dlu.cs, such as ovens and other cooking sl~ rçs, ~tili7.ing the said enzymatic composition for cle~ning .
All amounts stated in this description are based on the total weight of the composition of the invention. The enzymes used in the invention are preferably ~ik~liphilic. If enzymes 25 so le~ign~ted are not commercially available, enzymes can be selected on the basis of activity against the relevant components of the soil (e.g. amylase against starch components) as a function of pH. Those skilled in the art can readily identify commercially or otherwise available enzymes with sufficient activity at the pH of the composition to be useful as components of a cl~ning composition and particularly those that would have an activity at 30 the o~lhllu~ll pH ofthe product, 12.5.
W096/07723 _3 PCT/U~95/11105 Lipase enzymes used in the present invention are those enzymes that promote hydrolysis of triglycerides into mono and diglycerides, glycerol, and free fatty acids, all of which are more soluble than the original fat triglyceride. A nurnber of different lipase enzymes are commercially available, having been used in fabric cleaning formulations for the 5 removal offat-co~ ;lli--g stains such as the stains resulting from cooking fat, salad oils, butter, and fat based sauces. A preferred lipase for use in the present invention is Lipolase, m~nllf~ctured by Novo Nordisk Indus~ry. This is a 1,3-specific lipase that cleaves ester bonds in the positions 1 and 3 of a triglyceride.
Amylase enzyrnes are those that hydrolyze starches to soluble ~lextrin~ and 10 oligosaccharide. Amylases have been used in fabric cleaning compositions to remove starch-cont~inin~ stains, such as those made from pasta, chocolate, and gravy products, by way of example, only. Amylase enzymes hydrolyze 1,4-alpha glucosidic bonds in an amylose or amylopectin. A pl~r~ d amylase is Termamyl~ which is a commercially available enzyme m~nllf~rtllred by Novo Nordisk Industry, being alpha amylase prepared by fPrment~tion of 15 Rnci~u~ licheniformis.
The composition of the invention can contain a protease as an optional, additional enzyme. Proteases are enzymes that hydrolyses protein to peptides that can be readily dissolved. Proteases have previously been incorporated into fabric cleaning compositions such as laundry detergents. A preferred ploteasl;; is the cornmercial product Savinase(~ also 20 available from Novo Nordisk Industry. Savinase~ is a proteolytic enzyme prepared by submerged ferment~tiQn of an alkalophilic species of Bacillus and is an endo-protease of the serine type, with broad substrate specificity.
Each of the enzymes types used are present in from 0.1 to 4% by weight of the composition. The particular enzymes disclosed above are only non-limiting examples of 25 their types. It should be noted that a wide range of commercially available lipase, amylase, and protease enzymes are available.
Since the compositions of the invention are generally inten-11?cl for oven cleaning, they should be of sufficient viscosity to hold them on a vertical surface for an effective time, i.e.
for a time sufficient to effect or at least f~.ilit~te the removal of burnt-on food soils. In order 30 to achieve such a viscosity, it may be nPceS~ry to add a thickener, in addition to the other colll~ollents of the co~ u~ilion. The amount of the thickener will depend on the nature of wo96/o7723 ~ g9 26 0 PCl`/US95/11105 the thickener itself and of the other components in the composition. It may be that the other components in the composition, along with their other ~lOp~l lies, also will act as a thickener for the purpose of giving the a~lv~fiate viscosity to the composition, making unnecessary the addition of a separate component specifically as a thickener. A composition primarily 5 inten~f d for application to burnt-on food soils on horizontal ~nrf~ces, such as stove tops, could be in a more fluid form.
When present as a separate component that is provided primarily to increase composition viscosity, the thickener should be present in the range of from 0.05 to 6 percent by weight and preferably from 0.2 to 6 percent. The thickeners can be selected from the 10 group con~i~tin~ of inorganic materials, organic polymeric materials, and cc,ln~lible mixtures thereof.
Suitable inorganic thickeners include, by way of example only, colloidal silica,smectite clays such as bentonite, attapulgite, Laponite, m~gn~sium alumino-silicate, and compatible mixtures thereof. Polymeric organic thickeners can be biopolymers (such as 15 ~nth~n or welan gum) or synthetic polymers (such as polyacrylates or hydrophobically modified polyu~ ~le). Coll~ cially available examples of such synthetic polymers may be selected from the CARBOPOL(~) polymers produced by B.F. Goodrich or the RHEOVIS~ polymers available from Allied Colloids. Preferably the thicken~r is a cro~linked polyacrylate. Commercial examples of cros~linked polyacrylates may be selected 20 from the ACRYSOL (~ polymers produced by Rohm & Haas. When the thickener is ahydrophobically modified polyul~;lL~le thickener, it should more preferably be present in the range of from 1 to 2 percent by weight.
The alkali metal silicate compounds in the composition assist in fat break-down and provide alkalinity. They also assist as d~ builders and act as corrosion inhibitors.
25 Particular alkali metal silicates that can be employed are those having a Na2O:SiO2 ratio in the range 1:2 to 2:1. The ~Lillluln range is from 1:1 to 2:1. These alkali metal silicates will usually be present in the range 5-35 weight percent and preferably 5-25 weight percent, although the precise amount may depend on the nature of the surfactant.
The amount of silicate will also be rl~ttqrmine~l to some extent by the nature of the 30 buffer used. Thus the pl~r~ d buffer employing an alkali metal carbonate, and preferably sodium c~b~ , may allow a reduced amount of silicate to be present. Decreasing the 0~ 99260 WO 96107723 PCT/US9~/lllO~i amount of silicate present, though it cannot be reduced to 0, is advantageous in that it reduces the amount of electrolyte, which increases the shelf life of the formula. Also, silicates sometimes have adverse effects on skin, making it desirable to reduce the amount of silicates so as to ~ ç the side effects of the composition, should it come in contact with 5 ull~lolccted skin.
The composition of the invention must be buffered, although it may be that components in the composition, e.g. the silicate, will provide a sufficient bu~clillg effect so as not to require an independent buffer. The buffer colll~ollcllL~ in the composition should be selected to retain the composition's pH in the range of from 10-14, preferably from 10-13, 10 and optimally at about 12.5. If a specific buffer is required, a wide variety of buffer compositions are available and known to those skilled in the art. Carbonate buffers and particularly alkali metal (e.g. sodium) carbonate buffers are ~lercllcd because of the high pH
ofthe colll~osilion. Preferably carbonate is added in amounts ranging from 0.5 to 12 weight percent.
To enable the composition to wet and penetrate the m~teri~l~ to be rernoved, thecomposition p lcr~ bly co~t~inC a surfactant. Pler~.lcd sllrf~t~nt~ are those that are alkali stable and have an HLB (lly~uphile-lipophile balance) in the range of 12-20 and preferably in the range 13-16. The HLB is a measure of the relative water solubility of the snrf~ct~nt and gives an indication of the relative ~JlU~l lions of hydrophobic and hydrophilic portions in 20 the molecule. The ~llrf~rt~nt~ preferably are non-ionic, but anionic ~ulr~cl~ll~ may be used.
It is only rarely that a cationic snrf~ct~nt will be operable.
Preferable non-ionic ~nrf~l~t~nt~ include nonyl phenol ethoxylates (preferably 9 and 20 mole ethoxylates), alkyl glucosides, C l 1 oxo-alcohol ethoxylates co~ at least 7 moles of ethylene oxide, short chain fat~ acid polyethylene glycol ethers CO~ i"g at least 5 25 moles of ethylene oxide, and iso-C 13 oxo-alcohol ethoxylates cont~ining at least 8 moles of ethylene oxide, or compatible nlixlule~ thereof. Alkyl and aryl capped m~t~ri~l~ can also be employed.
Typical anionic surfactants are ~lk~lin.o metal and alkylolamine alkyl sulfonates, p~U~lll sulfonates, and ~lk~line metal alkyl phenol sulfonates.
Normally one would use either an anionic sllrf~rt~nt or a non-ionic ~,-, r~ as ll~ixlulGs of anionic and non-ionic sllrf~ t~nt~ tend to be ineffective. Mixtures of surfactants W0 96/07723 ~ 2 8 ~ 6 - PCT/US95/11105 are not normally compatible because of the high ~lk~linity, tending to separate. However, by very careful choice of the ~ ~-;ate sllrf~ct~nt system, anionic/non-ionic sllrf~rt~nt mixtures are possible and are not excluded from the invention.
The amount of sllrf~ct~nt present is usually from 0.5 to 10 weight percent. With5 anionic surf~rt~nt~, it is also desirable that a co-builder be present, partly to assist in avoiding the salting-out of the surfactant. A wide variety of co-builders are used with anionic surfactants in the various applications of these sllrf~t~nt~ Preferred co-builders that are useful for anionic systems are alkali metal polyphosph~tP~ alkali metal salts of organic acids, and alkali metal salts of polymeric acids. More preferably the co-builder is at least one of 10 STPP (sodium tri polyphosphate) and alkali metal salts of citric acid, gluconic acid, polyacrylic acid, and modified polyacrylic acid. Compatible mixtures of the above mentioned co-builders can be ~ltili7to~1 In addition, the silicate component of the composition can contribute as a co-builder. Preferably the co-builder (other than the silicate component) is present in the amount of 0.5-12 percent by weight.
Co-builders are usually less nPcess~ry in non-ionic surfactant systems since there is less likelihood of inactivation by calcium ions. Nevertheless, co-builders may still be n.oces~ry if it is found that the calcium ions present in the composition are having an adverse effect.
Preferably the compositions include hydrotropes, i.e. compounds that have the 20 property of increasing the aqueous solubility of any insoluble organic chemicals present.
Useful hydrotropes are cllm~nl~slllfonate, sodium _ylene sulphonate, phosphate esters, and sodium toluene sulphonate. Compatible lmxlules of the above mentioned hyd-~ tlopes can be used if desired. Preferably said h~dl~ opes are present in the amount of 0.2-2.5 percent by weight.
Removal of bDt-on food soils can be enhanced by the use of penetrating solvents.The presence of these solvents also can assist in stabili_ing the en7yme content of the composition. Suitable solvents are those organic liquids that soften and penetrate into resin-type materials, for example those solvents found in paints. The particularly l ler~ d solvents are those that are found also to enhance the stability of the en_ymes. Suitable 30 solvents are glycol ethers (e.g. those sold under the trade name Cellosolve), esters, glycol ether acet~t~, methyl pyrrolidone, and 1,3-dimethyl-2-imiti~7~lidinone. Cnmp~tihle ~ W096/~7723 ~ 9 260 PCT~S95/lllos ulc;s of the above mentioned solvents can be used. More preferably, the mentioned solvents are present in the amount of from 2-10 percent by weight.
- The compositions of the invention can contain other conventional cleaning composihon colll~onents, if they do not m~t~n~lly detriment~lly affect the enzymatic 5 pr~llies of the system. Such components include, for example, sequestering agents, dyes, bleaches, bleach activators, foam control agents, and fragrances.
The composition of the invention also includes appropriate diluents for application, although the composition may be ~l~a.cd in a concenb-ated form for dilution prior to use.
The preferred diluent (apart from the penetrating solvents discussed above) is water and will 10 usually comprise at least 70% and preferably at least 75% by weight of the composition.
The composition of the invention can be applied directly without further dilution, for example by water, and can be applied by brushing or by spraying from a spray device, including an aerosol dispenser. In the case of an aerosol dispenser, the inclusion of a foaming agent in the composition will result in a foam that covers the surface to be treated. The 15 surface to be treated should preferably be cold, which shall mean commonly experienced room l~ cldlules. If warm, the surface should not be of a L~ dLule s~lffi~iently high as to be deleterious to the enzymes in the composition. Tel,lpe.~l lres not in excess of 50C are d.
The invention will be illustrated by the following Ex~llples.
wo 96/07723 ~ 6 ~ 8 - PCT/USg5/1110 FXAl\IPT.F 1.
The following were combined in the stated percentages by weight. Compositions described in Columns A and B are examples of specific formulations that have been made, 5 while Column C states the pl~r~lled ranges of ingredients:
Name Percentage Comp Comp C
ACRYSOL* ICS-I - 5.0 5.0 0.05-6 A commercial polyacrylate resin supplied by Rohm & Haas.
Sodium Metasilicate - 5.0 5.3 5-35 A commercial product METSO 510*
supplied by Crosfields Plc ETHYLAN* BAB 20 - 1.0 1.1 0.5-10 Nonionic surfactant supplied by Akcros Chemicals Hexyl CELL(~SOLVE* - 3.0 2.7 2-10 Ethylene glycol monohexyl ether supplied by Union Carbide Sodium Carbonate 1.5 1.2 0.5-12 Sodium Citrate 5.0 3.8 0.5-12 LIPOLASE* 100LTYPEEX- 2.5 2.5 0.1-4 A commercial lipase supplied by Novo Nordisk Tnd~ ries TERMAMYL* 300 TYPE DX - 2.0 2.0 0.1-4 A commercial amylase supplied by Novo Nordisk Industry Water 75.00 76.4 70-75 * Trade Name or Registered Trade Mark The compositions of Example 1 were viscous fluids which, when applied to the vertical walls of an oven, r~m~inPd in position for sufficient time to effect cleaning. When the compositions were applied to a surface co~ ."i,~ l with burnt-on food soils in a test of 10 the type recommen~le~l by the Vitreous Enamel Council, the soils softened and were easily removable after 16 hours.
WO 96/07723 ~ 2 1 9 ~ 2 6 Q PCT/US95/11105 F,XAl\IPT,F 2.
The following were combined in the stated percentages by weight. The composition described in Column A is an example of a specific formulation that has been made, while Column B states the ~.c;r~lled ranges of ingredients:
Name Percentage Carbopol*- 2.0 0.05-6 A commercial cross-linked polyacrylate supplied by B. F. Goodrich Sodium Metasilicate - 5.3 5-35 A commercial product METSO 510* supplied by Crosfields Plc ETHYLAN* BAB 20 - 1.0 0.5-10 Nonionic surfactant supplied by Akcros Chemie~lc Hexyl CELLOSOLVE* - 2.6 2-10 Ethylene glycol monohexyl ether (supplied by Union Carbide) Sodium Carbonate 1.1 0.5-12 Sodium Citrate 3.8 0.5-12 LIPOLASE* 100L TYPEEX- 2.5 0.1-4 A colnm~orcial lipase supplied by Novo Nordisk Industry TERMAMYL* 300 TYPE DX - 2.0 0.1-4 A commercial amylase supplied by Novo Nordisk Industry Water 797 70 75 * Trade Name or Regi~L~d Trade Mark The composition of Example 2 was a viscous fluid which, when applied to the vertical walls of an oven, rem~ined in position for sufficient time to effect cle~nin~ When applied to a surface cn"lS.",i,.i1le-1 with burnt-on food soils in a test ofthe type leco~ en-~ed by the Vitreous Enamel Council, the soils softened and were easily removable after 16 hours.
The invention is not limited to the Examples, which are only illustrative. Tn~1e~-1 the invention is in accordance with the claims.
Claims (21)
1. A liquid, enzyme-based cleaning composition comprising:
i) a lipase enzyme active at a pH of from 10 to 14;
ii) an amylase enzyme active at a pH of from 10 to 14;
iii) at least one alkali-stable non-ionic or anionic surfactant;
iv) an alkali metal silicate; and v) an inert diluent;
the composition being buffered at a pH of 10 to 14.
i) a lipase enzyme active at a pH of from 10 to 14;
ii) an amylase enzyme active at a pH of from 10 to 14;
iii) at least one alkali-stable non-ionic or anionic surfactant;
iv) an alkali metal silicate; and v) an inert diluent;
the composition being buffered at a pH of 10 to 14.
2. A composition according to claim 1 that also contains a protease active at a pH of 10 to 14.
3. A composition according to claim 1 that is sufficiently viscous to remain on a vertical surface for an effective time sufficient to so soften burnt-on food soils on the surface as to aid in their removal therefrom.
4. A cleaning composition according to claim 3 containing a thickening agent.
5. A cleaning composition according to claim 1 that contains an anionic surfactant and a co-builder.
6. A cleaning composition according to claim 1, wherein said composition furtherincludes a hydrotrope.
7. A cleaning composition according to claim 1 that further includes a penetrating, enzyme-stabilizing organic solvent.
8. A cleaning composition according to claim 7, wherein said solvent is selected from the group consisting of glycol ethers, esters, glycol ether acetates, N-methyl pyrrolidine, 1.3-dimethyl-2-imidazolodinone, and compatible mixtures thereof.
9. A cleaning composition according to claim 1, further including a protease active at pH 10 to 14, a thickener, a hydrotrope, and an anionic surfactant and co-builder, wherein the following components are present in the following amounts based on the total weight of said composition:
i) said lipase enzyme is present in the amount of 0.1 to 4 weight %;
ii) said amylase enzyme is present in the amount of 0.1 to 4 weight %;
iii) said protease is present in the amount of 0.1 to 4 weight %;
iv) said thickening agent is present in the amount of 0.05 to 6 weight %;
v) said anionic surfactant is present in the amount of 0.5 to 10 weight %;
vi) said hydrotrope is present in the amount of 0.2 to 2.5 weight %;
vii) said alkali metal silicate is present in the amount of 5 to 35 weight %;
viii) said co-builder is present in the amount of 0.5 to 12 weight %;
ix) said penetrating solvent is present in the amount of 2 to 10 weight %; and the balance is inert diluent and ancillary ingredients.
i) said lipase enzyme is present in the amount of 0.1 to 4 weight %;
ii) said amylase enzyme is present in the amount of 0.1 to 4 weight %;
iii) said protease is present in the amount of 0.1 to 4 weight %;
iv) said thickening agent is present in the amount of 0.05 to 6 weight %;
v) said anionic surfactant is present in the amount of 0.5 to 10 weight %;
vi) said hydrotrope is present in the amount of 0.2 to 2.5 weight %;
vii) said alkali metal silicate is present in the amount of 5 to 35 weight %;
viii) said co-builder is present in the amount of 0.5 to 12 weight %;
ix) said penetrating solvent is present in the amount of 2 to 10 weight %; and the balance is inert diluent and ancillary ingredients.
10. A cleaning composition according to claim 1, wherein said lipase enzyme and said amylase enzyme are present in amounts such that the weight ratio of said lipase enzyme to said amylase enzyme lies in the range 1:2 to 3:1.
11. A cleaning composition according to claim 4, wherein the thickening agent is selected from the group consisting of an inorganic thickener, an organic polymeric thickener, a hydrophobically modified polyurethane thickener, and compatible mixtures thereof.
12. A cleaning composition according to claim 11, wherein said thickening agent is an inorganic thickener selected from the group consisting of colloidal silica, bentonite, attapulgite, laponite, magnesium alumino-silicate, and compatible mixtures thereof.
13. A cleaning composition according to claim 11, wherein said thickening agent is an organic polymeric thickener selected from the group consisting of xanthan gum, welan gum, a cross-linked polyacrylate polymer, and compatible mixtures thereof.
14. A cleaning composition according to claim 1, wherein the surfactants have a combined HLB within the range of 12-20.
15. A cleaning composition according to claim 14, wherein said surfactants include a non-ionic surfactant selected from the group consisting of nonyl phenol ethoxylates, alkyl glucosides, C11 oxo-alcohol ethoxylates containing at least 7 moles of ethylene oxide, short chain fatty acid polyethylene glycol ethers containing at least 5 moles of ethylene oxide, iso-C13 oxo-alcohol ethoxylates containing at least 8 moles of ethylene oxide, and compatible mixtures thereof.
16. A cleaning composition according to claim 14, wherein said surfactants include an anionic surfactant selected from the group consisting of alkali metal alkyl sulphonates;
alkylolamine alkyl sulphonates; paraffin sulphonates; alkali metal alkyl phenol sulphonates;
and mixtures thereof.
alkylolamine alkyl sulphonates; paraffin sulphonates; alkali metal alkyl phenol sulphonates;
and mixtures thereof.
17. A cleaning composition according to claim 6, wherein said hydrotrope is selected from the group consisting of sodium xylene sulphonate, phosphate esters, sodium toluene sulphonate, and mixtures thereof.
18. A cleaning composition according to claim 1, wherein said alkali metal silicates include Na2O and have an Na2O:SiO2 ratio of from 2:1 to 1:2.
19. A cleaning composition according to claim 1, wherein the diluent is water.
20. A method of cleaning a surface bearing burnt-on food soils comprising the steps of a. applying the composition of claim 1 to the food soils at a cool surface temperature;
b. allowing the food soils to soften; and c. removing the food soils.
b. allowing the food soils to soften; and c. removing the food soils.
21. The method of claim 20 wherein the cool surface temperature is a temperature not in excess of about 50°C.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9417906.6 | 1994-09-06 | ||
| GB9417906A GB9417906D0 (en) | 1994-09-06 | 1994-09-06 | Cleaning compositions |
| GB9504687.6 | 1995-03-08 | ||
| GBGB9504687.6A GB9504687D0 (en) | 1995-03-08 | 1995-03-08 | Cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2199260A1 true CA2199260A1 (en) | 1996-03-14 |
Family
ID=26305571
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2199260 Abandoned CA2199260A1 (en) | 1994-09-06 | 1995-09-06 | A cleaning composition comprising lipase and amylase enzymes |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0779917A4 (en) |
| AU (1) | AU694268B2 (en) |
| BR (1) | BR9508894A (en) |
| CA (1) | CA2199260A1 (en) |
| GB (1) | GB2294942B (en) |
| MX (1) | MXPA97001728A (en) |
| NZ (1) | NZ293401A (en) |
| WO (1) | WO1996007723A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9815419D0 (en) | 1998-07-16 | 1998-09-16 | Reckitt & Colman Inc | Improvements in or realting to organic compositions |
| AU2001281583B2 (en) * | 2000-08-22 | 2004-12-16 | Onebiosci Pty Limited | Anti-graffiti paint formulations and removal |
| US8329630B2 (en) | 2008-04-18 | 2012-12-11 | Ecolab Usa Inc. | Ready to use thickened degreaser and associated methods |
| US8420586B2 (en) | 2008-04-18 | 2013-04-16 | Ecolab Usa Inc. | Thickened oven cleaner comprising a glutamic acid salt or disodium ethanol diglycine chelant |
| CN104781297B (en) | 2012-09-04 | 2019-05-14 | 路博润先进材料公司 | Polyurethane/polyacrylamide impurity dispersion for the gloss application in household care |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EG18543A (en) * | 1986-02-20 | 1993-07-30 | Albright & Wilson | Protected enzyme systems |
| GB8629537D0 (en) * | 1986-12-10 | 1987-01-21 | Unilever Plc | Enzymatic dishwashing composition |
| GB8923788D0 (en) * | 1989-10-23 | 1989-12-13 | Unilever Plc | Enzymatic detergent compositions and their use |
| US5230822A (en) * | 1989-11-15 | 1993-07-27 | Lever Brothers Company, Division Of Conopco, Inc. | Wax-encapsulated particles |
| US5066749A (en) * | 1990-09-11 | 1991-11-19 | National Starch And Chemical Investment Holding Corporation | Hydrophobically-modified polycarboxylates and process for their preparation |
| AU655274B2 (en) * | 1991-05-31 | 1994-12-15 | Colgate-Palmolive Company, The | Nonaqueous liquid, phosphate-free, improved automatic dishwashing composition containing enzymes |
| CA2167482C (en) * | 1993-07-23 | 1999-12-28 | Panos Iakovides | Thickened aqueous detergent compositions with improved cleaning performance with short chain surfactants |
| US5435936A (en) * | 1993-09-01 | 1995-07-25 | Colgate Palmolive Co. | Nonaqueous liquid microemulsion compositions |
-
1995
- 1995-09-06 CA CA 2199260 patent/CA2199260A1/en not_active Abandoned
- 1995-09-06 MX MXPA97001728A patent/MXPA97001728A/en not_active Application Discontinuation
- 1995-09-06 AU AU35830/95A patent/AU694268B2/en not_active Ceased
- 1995-09-06 NZ NZ293401A patent/NZ293401A/en unknown
- 1995-09-06 EP EP95933024A patent/EP0779917A4/en not_active Withdrawn
- 1995-09-06 WO PCT/US1995/011105 patent/WO1996007723A1/en not_active Application Discontinuation
- 1995-09-06 GB GB9518214A patent/GB2294942B/en not_active Expired - Fee Related
- 1995-09-06 BR BR9508894A patent/BR9508894A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU3583095A (en) | 1996-03-27 |
| NZ293401A (en) | 1998-02-26 |
| WO1996007723A1 (en) | 1996-03-14 |
| AU694268B2 (en) | 1998-07-16 |
| GB2294942A (en) | 1996-05-15 |
| GB9518214D0 (en) | 1995-11-08 |
| BR9508894A (en) | 1997-11-18 |
| EP0779917A4 (en) | 1999-03-17 |
| GB2294942B (en) | 1998-07-29 |
| EP0779917A1 (en) | 1997-06-25 |
| MXPA97001728A (en) | 2004-12-03 |
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