EP0271155B2 - Enzymatic dishwashing and rinsing process - Google Patents
Enzymatic dishwashing and rinsing process Download PDFInfo
- Publication number
- EP0271155B2 EP0271155B2 EP87202387A EP87202387A EP0271155B2 EP 0271155 B2 EP0271155 B2 EP 0271155B2 EP 87202387 A EP87202387 A EP 87202387A EP 87202387 A EP87202387 A EP 87202387A EP 0271155 B2 EP0271155 B2 EP 0271155B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- lipase
- pseudomonas
- use according
- dishwashing
- 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.)
- Expired - Lifetime
Links
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
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
Definitions
- the present invention relates to enzymatic dishwashing or rinsing processes using compositions comprising lipolytic enzymes.
- EP-A-0 130 064 (Novo) concerns detergent additives based on Fusarium oxysporum lipase (e.g. 20,000-100,000 LU/g, used in detergent at e.g. 0.2-2% w/w.
- Fusarium oxysporum lipase e.g. 20,000-100,000 LU/g, used in detergent at e.g. 0.2-2% w/w.
- EP-A-0 205 208 discloses enzymatic detergent compositions comprising lipase with 1-40% anionic surfactant and builders.
- the lipases disclosed are those that cross-react with antibody against lipase from Pseudomonas fluorescens 1AM 1057.
- EP 0 206 930 (Unilever) (not prepublished) also discloses enzymatic detergent compositions comprising similar lipases together with combinations of anionic and nonionic detergent.
- dishwashing compositions have been proposed in the art.
- enzymes mainly amylases and/or proteases have been proposed for inclusion in dishwashing compositions.
- Lipases have also been suggested, but have received far less attention that the amylases and/or proteases.
- Dishwashing compositions in particular machine dishwashing compositions which are used in the main wash step of a machine dishwashing operation, have in general a satisfactory cleaning performance. However, frequently the article cleaned with such products still do not have a satisfactory visual appearance after rinsing and drying, showing film or spots.
- main wash liquor is usually carried over from the main wash step to the rinse step, causing some deposition of soil resulting in insoluble calcium salts on the articles to be rinsed, which results in visible film or spots on the articles when they are dry. In particular with glass articles, this causes an unsightly visual appearance.
- the invention provides the use of a lipolytic enzyme as a spot reducing agent a process for machine dishwashing or rinsing, comprising treating dishes with an aqueous liquid having dissolved or dispersed therein an effective amount of an enzymatic dishwashing or rinsing composition comprising from 0.5-10% by weight of a detergent surfactant and from 0-90% by weight of a builder and from 0.005-100 LU/mg of a lipolytic enzyme.
- the lipases used according to the present invention, may be of any suitable origin such as yeasts, fungi and bacteria. Preferably, however, they are of bacterial origin, and particularly preferably they belong to the class of bacterial lipases which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Chromobacter viscosum var lipolyticum NRRL B-3673.
- This lipase has been described in Dutch Patent Specification 154,269 of Toyo Jozo, and the microorganism is available to the public at the United States Department of Agriculture, Agricultural Research Service, Northern Utilisation and Development Division at Peoria, Illinois, under the number NRRL B-3673.
- This lipase will hereinafter be referred to as "Toyo Jozo" lipase.
- the preferred lipases to be used in the present invention should show a positive immunological cross-reaction with the Toyo Jozo lipase antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133 , pages 76-79 (1950)).
- the preparation of the antiserum is carried out as follows: Equal volumes of 0.1 mg/ml antigen and of Freund's adjuvant (complete or incomplete) are mixed until an emulsion is obtained. Two female rabbits are injected with 2 ml samples of the emulsion according to the following scheme:
- the serum containing the required antibody is prepared by centrifugation of clotted blood, taken on day 67.
- the titre of the anti-Toyo Jozo-lipase antiserum is determined by the inspection of precipitation of serial dilutions of antigen and antiserum according to the Ouchterlony procedure. A 2 5 dilution of antiserum was the dilution that still gave a visible precipitation with an antigen concentration of 0.1 mg/ml.
- All lipases showing a positive immunological cross reaction with the Toyo Jozo lipase antibody as hereabove described are preferred lipases for use in the present invention.
- Typical examples thereof are the lipases ex Pseudomonas fluorescens IAM 1057 (available under the trade name Amano-P), the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338, the lipase ex Pseudomonas sp.
- Chromobacter viscosum e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from US Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli .
- the lipases used in the present invention are included in the detergent composition in such an amount that the final detergent composition has a lipolytic enzyme activity of from 100 to 0.005 LU/mg preferably 25 to 0.05 LU/mg of the composition.
- lipases can be used in their non-purified form, or in a purified form, e.g. purified with the aid of well-known adsorption methods, such as a phenylsepharose-adsorption techniques.
- the composition used according to the invention may furthermore comprise the usual ingredients of dishwashing or rinse compositions.
- it may contain one or more alkali salts commonly used in dishwashing compositions.
- it may contain organic and/or inorganic builders such as the alkali metal ortho-, pyro and tripolyphosphates and hexametaphosphates, silicates, carbonates, zeolites, borates, citrates, carboxymethyloxy-succinates, nitrilotriacetates and ethylenediamine-tetraacetates, polymeric polyelectrolytes such as polyacrylates, polymaleates, and other known organic and inorganic builder compounds.
- the amount of builders in the composition varies from 10-90% by weight, generally from 30-70% by weight.
- the composition may also contain a detergent-active compound. If a detergent-active compound is included, it usually is in an amount of from 0.5-10%, usually 1-5%. Any well-known type of detergent active compound may be used, such as soaps, synthetic anionic, non-ionic, amphoteric detergent surfactant and mixtures thereof. Preferably, a nonionic detergent surfactant is used, especially a low-foaming one. Suitable examples of such nonionic detergent surfactants can easily be found in M.Schick "Nonionic Surfactants" (1967).
- composition may furthermore contain other useful additives such as bleaching agents, bleaching agent activators, hydrotropes, fillers, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and alkali metal or alkaline earth metal salts thereof, clays such as hectorites, anti-corrosion agents such as fatty acids, benztriazole and so on.
- Other enzymes such as proteases, amylases, oxidases may also be included.
- the peroxygen type bleaching agents preferably with a bleach precursor such as TAED are suitable for inclusion in the machine dishwashing compositions.
- a typical example of a conventional machine dishwashing composition usually contains an alkali metal tripolyphosphate in an amount of from 20-60%, an alkali metal silicate in an amount of from 40-80%, or an alkali metal disilicate in an amount of 5-30% by weight a peroxy type bleaching agent in an amount of from 1-15%, a low-foaming detergent surfactant in an amount of from 0.5-5%, and minor ingredients such as perfumes, colouring agents, hydrotropes, fillers, etc.
- a rinse composition When formulated as a rinse composition, it may contain from 0.5-10% by weight of a nonionic surfactant, from 5-25% by weight of an inorganic or organic acid, from 1-5% by weight of a hydrotrope, dyes, germicides, clays, silica sols, etc., the balance being water.
- a nonionic surfactant from 5-25% by weight of an inorganic or organic acid, from 1-5% by weight of a hydrotrope, dyes, germicides, clays, silica sols, etc.
- the balance being water.
- the products of the invention can be formulated in any desirable form, such as powders, granulates, cakes, bars, pastes, liquids etc. The invention will further be illustrated by way of example.
- detergent composition dosage 30 g lipase dosage 2.5 g ( 15 LU/ml) water hardness main wash 27° GH flood 9° GH rinse 1 9° GH rinse 2 9° GH final rinse 9° GH wash temperature and time 55°C - 60 minutes articles to be cleaned clean dishes clean glasses test soil 35 g egg-yolk, added at the beginning of the main wash.
- the detergent composition had the following formulation: in gr. sodium tripolyphosphate 11.61 sodium carbonate 2.7 TAED (59.7%) 1.81 sodium perborate 2.43 calcium-Dequest (47.6%) 0.397 sodium disilicate 3.3 low foaming nonionic (Plurafac RA40) 0.405 hectorite clay (Laponite XLS) 0.675 sodium sulphate 5.610 amylase (4.8 Maltose units/mg) 0.540
- the Toyo Jozo lipase was used as lipase.
- the test was carried out in two runs, one without and one with lipase.
- the glasses were appraised by an expert panel as to their visual appearance, and were given a score according to the following scale: Film Spots 1. no film 1. no spots 2. slight film 2. 1-5 spots 3. clear film 3. 5-10 spots 4. heavy film 4. 11-20 spots 5. more than 20 spots
- Example 1 The test of Example 1 was repeated, but under the following different conditions: wash temperature 65°C soil standard soil; at the end of the main wash, clean plates were put in the machine, so that no cleaning took place in the final rinse, but only a carry-over took place. run 1 no lipase added in the final rinse run 2 2.5 g Toyo Jozo lipase was added to the final rinse (15 LU/ml).
- the main wash composition had the following formulation: % by weight sodium tripolyphosphate 36 sodium carbonate 9 sodium disilicate 15 TAED 3.8 sodium perborate tetrahydrate 8.8 potassium metaborate 0.35 sodium metaborate 0.85 calcium-Dequest 0.63 Amylase (4.8 MU/mg) 1.8 Esperase (a protease; 675 GU/mg) 1.8 low-foaming nonionic (Plurafac RA 40) 1.35 hectorite (Laponite XLS) 2.25 benzotriazole 0.1 sodium sulphate 14.0 water 9.5
- Example 2 Replacing the Toyo Jozo lipase by the Amano-P lipase or Lipase MY (ex Candida cylindracea ) or Amano AP-6 lipase (ex Aspergillus niger ) in Example 2 gave similar results.
- the following formulation is an example of a rinse aid composition to which lipases can be added: % by weight low-foaming nonionic (Plurafac RA 30) 10 citric acid 18 sodium xylene sulphonate 3.0 dye 0.003 butylated hydroxytoluene 0.1 water q.s.
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)
Description
- The present invention relates to enzymatic dishwashing or rinsing processes using compositions comprising lipolytic enzymes.
- EP-A-0 130 064 (Novo) concerns detergent additives based on Fusarium oxysporum lipase (e.g. 20,000-100,000 LU/g, used in detergent at e.g. 0.2-2% w/w.
- DE-A-1 930 636 (= GB 1 273 545) (Albright & Wilson) concerns cleaning compositions based on protease, lipase and/or decarboxylase (of unspecified type) and surfactant, used inter alia for dishwashing.
- EP-A-0 205 208 (Unilever) (not prepublished) discloses enzymatic detergent compositions comprising lipase with 1-40% anionic surfactant and builders. The lipases disclosed are those that cross-react with antibody against lipase from Pseudomonas fluorescens 1AM 1057.
- EP 0 206 930 (Unilever) (not prepublished) also discloses enzymatic detergent compositions comprising similar lipases together with combinations of anionic and nonionic detergent.
- Thus, enzymatic dishwashing compositions have been proposed in the art. As enzymes, mainly amylases and/or proteases have been proposed for inclusion in dishwashing compositions. Lipases have also been suggested, but have received far less attention that the amylases and/or proteases. Dishwashing compositions, in particular machine dishwashing compositions which are used in the main wash step of a machine dishwashing operation, have in general a satisfactory cleaning performance. However, frequently the article cleaned with such products still do not have a satisfactory visual appearance after rinsing and drying, showing film or spots. Some main wash liquor is usually carried over from the main wash step to the rinse step, causing some deposition of soil resulting in insoluble calcium salts on the articles to be rinsed, which results in visible film or spots on the articles when they are dry. In particular with glass articles, this causes an unsightly visual appearance.
- We have now found that the addition of lipases to a main wash dishwashing composition or to a rinse composition significantly reduced the formation of film or spots on the articles cleaned or rinsed with such a composition.
- Accordingly the invention provides the use of a lipolytic enzyme as a spot reducing agent a process for machine dishwashing or rinsing, comprising treating dishes with an aqueous liquid having dissolved or dispersed therein an effective amount of an enzymatic dishwashing or rinsing composition comprising from 0.5-10% by weight of a detergent surfactant and from 0-90% by weight of a builder and from 0.005-100 LU/mg of a lipolytic enzyme.
- The lipases, used according to the present invention, may be of any suitable origin such as yeasts, fungi and bacteria. Preferably, however, they are of bacterial origin, and particularly preferably they belong to the class of bacterial lipases which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Chromobacter viscosum var lipolyticum NRRL B-3673.
- This lipase has been described in Dutch Patent Specification 154,269 of Toyo Jozo, and the microorganism is available to the public at the United States Department of Agriculture, Agricultural Research Service, Northern Utilisation and Development Division at Peoria, Illinois, under the number NRRL B-3673. This lipase will hereinafter be referred to as "Toyo Jozo" lipase. The preferred lipases to be used in the present invention should show a positive immunological cross-reaction with the Toyo Jozo lipase antibody, using the standard and well-known immunodiffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
- The preparation of the antiserum is carried out as follows:
Equal volumes of 0.1 mg/ml antigen and of Freund's adjuvant (complete or incomplete) are mixed until an emulsion is obtained. Two female rabbits are injected with 2 ml samples of the emulsion according to the following scheme: - day 0 :
- antigen in complete Freund's adjuvant
- day 4 :
- antigen in complete Freund's adjuvant
- day 32 :
- antigen in incomplete Freund's adjuvant
- day 60 :
- booster of antigen in incomplete Freund's adjuvant.
- The serum containing the required antibody is prepared by centrifugation of clotted blood, taken on day 67.
- The titre of the anti-Toyo Jozo-lipase antiserum is determined by the inspection of precipitation of serial dilutions of antigen and antiserum according to the Ouchterlony procedure. A 25 dilution of antiserum was the dilution that still gave a visible precipitation with an antigen concentration of 0.1 mg/ml.
- All lipases showing a positive immunological cross reaction with the Toyo Jozo lipase antibody as hereabove described are preferred lipases for use in the present invention. Typical examples thereof are the lipases ex Pseudomonas fluorescens IAM 1057 (available under the trade name Amano-P), the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338, the lipase ex Pseudomonas sp. available under the trade name Amano-CES, the lipase ex Pseudomonas cepacia, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from US Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
- The lipases used in the present invention are included in the detergent composition in such an amount that the final detergent composition has a lipolytic enzyme activity of from 100 to 0.005 LU/mg preferably 25 to 0.05 LU/mg of the composition.
- A Lipase Unit (LU) is that amount of lipase which produces 1 µmol of titratable fatty acid per minute in a pH stat. under the following conditions: temperature 30°C; pH = 9.0; substrate is an emulsion of 3.3 wt.% of olive oil and 3.3% gum arabic, in the presence of 13 mmo1/1 Ca2+ and 20 mmo1/1 NaC1 in 5 mmo1/1 Tris-buffer.
- Naturally, mixtures of the above lipases can be used. The lipases can be used in their non-purified form, or in a purified form, e.g. purified with the aid of well-known adsorption methods, such as a phenylsepharose-adsorption techniques.
- The composition used according to the invention may furthermore comprise the usual ingredients of dishwashing or rinse compositions. Thus it may contain one or more alkali salts commonly used in dishwashing compositions. Thus, it may contain organic and/or inorganic builders such as the alkali metal ortho-, pyro and tripolyphosphates and hexametaphosphates, silicates, carbonates, zeolites, borates, citrates, carboxymethyloxy-succinates, nitrilotriacetates and ethylenediamine-tetraacetates, polymeric polyelectrolytes such as polyacrylates, polymaleates, and other known organic and inorganic builder compounds.
- Usually, the amount of builders in the composition varies from 10-90% by weight, generally from 30-70% by weight.
- The composition may also contain a detergent-active compound. If a detergent-active compound is included, it usually is in an amount of from 0.5-10%, usually 1-5%. Any well-known type of detergent active compound may be used, such as soaps, synthetic anionic, non-ionic, amphoteric detergent surfactant and mixtures thereof. Preferably, a nonionic detergent surfactant is used, especially a low-foaming one. Suitable examples of such nonionic detergent surfactants can easily be found in M.Schick "Nonionic Surfactants" (1967).
- The composition may furthermore contain other useful additives such as bleaching agents, bleaching agent activators, hydrotropes, fillers, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and alkali metal or alkaline earth metal salts thereof, clays such as hectorites, anti-corrosion agents such as fatty acids, benztriazole and so on. Other enzymes such as proteases, amylases, oxidases may also be included.
- As bleaching agents the peroxygen type bleaching agents, preferably with a bleach precursor such as TAED are suitable for inclusion in the machine dishwashing compositions.
- A typical example of a conventional machine dishwashing composition usually contains an alkali metal tripolyphosphate in an amount of from 20-60%, an alkali metal silicate in an amount of from 40-80%, or an alkali metal disilicate in an amount of 5-30% by weight a peroxy type bleaching agent in an amount of from 1-15%, a low-foaming detergent surfactant in an amount of from 0.5-5%, and minor ingredients such as perfumes, colouring agents, hydrotropes, fillers, etc.
- When formulated as a rinse composition, it may contain from 0.5-10% by weight of a nonionic surfactant, from 5-25% by weight of an inorganic or organic acid, from 1-5% by weight of a hydrotrope, dyes, germicides, clays, silica sols, etc., the balance being water. The products of the invention can be formulated in any desirable form, such as powders, granulates, cakes, bars, pastes, liquids etc. The invention will further be illustrated by way of example.
- In a commercial dishwashing machine tests were carried out under the following conditions:
detergent composition dosage 30 g lipase dosage 2.5 g (= 15 LU/ml) water hardness main wash 27° GH flood 9° GH rinse 1 9° GH rinse 2 9° GH final rinse 9° GH wash temperature and time 55°C - 60 minutes articles to be cleaned clean dishes clean glasses test soil 35 g egg-yolk, added at the beginning of the main wash. - The detergent composition had the following formulation:
in gr. sodium tripolyphosphate 11.61 sodium carbonate 2.7 TAED (59.7%) 1.81 sodium perborate 2.43 calcium-Dequest (47.6%) 0.397 sodium disilicate 3.3 low foaming nonionic (Plurafac RA40) 0.405 hectorite clay (Laponite XLS) 0.675 sodium sulphate 5.610 amylase (4.8 Maltose units/mg) 0.540 - As lipase, the Toyo Jozo lipase was used.
- The test was carried out in two runs, one without and one with lipase.
- The glasses were appraised by an expert panel as to their visual appearance, and were given a score according to the following scale:
Film Spots 1. no film 1. no spots 2. slight film 2. 1-5 spots 3. clear film 3. 5-10 spots 4. heavy film 4. 11-20 spots 5. more than 20 spots - The following results were obtained:
run 1 (no lipase) run 2 (with lipases) average film score 2.3 2.3 average number of spots 250 100 - The test of Example 1 was repeated, but under the following different conditions:
wash temperature 65°C soil standard soil; at the end of the main wash, clean plates were put in the machine, so that no cleaning took place in the final rinse, but only a carry-over took place. run 1 no lipase added in the final rinse run 2 2.5 g Toyo Jozo lipase was added to the final rinse (15 LU/ml). - The main wash composition had the following formulation:
% by weight sodium tripolyphosphate 36 sodium carbonate 9 sodium disilicate 15 TAED 3.8 sodium perborate tetrahydrate 8.8 potassium metaborate 0.35 sodium metaborate 0.85 calcium-Dequest 0.63 Amylase (4.8 MU/mg) 1.8 Esperase (a protease; 675 GU/mg) 1.8 low-foaming nonionic (Plurafac RA 40) 1.35 hectorite (Laponite XLS) 2.25 benzotriazole 0.1 sodium sulphate 14.0 water 9.5 - The following spot and film scores of the glasses were obtained:
run 1 (no lipase) run 2 (with lipases) average film score 1 1 average spot score 5 2.7 - Replacing the Toyo Jozo lipase by the Amano-P lipase or Lipase MY (ex Candida cylindracea) or Amano AP-6 lipase (ex Aspergillus niger) in Example 2 gave similar results.
- The following formulation is an example of a rinse aid composition to which lipases can be added:
% by weight low-foaming nonionic (Plurafac RA 30) 10 citric acid 18 sodium xylene sulphonate 3.0 dye 0.003 butylated hydroxytoluene 0.1 water q.s.
Claims (5)
- Use of a lipolytic enzyme as a spot reducing agent in a process for machine dishwashing or rinsing, comprising treating dishes with an aqueous liquid having dissolved or dispersed therein an effective amount of an enzymatic dishwashing or rinsing composition comprising from 0.5-10% by weight of a detergent surfactant and from 0-90% by weight of a builder and from 0.005-100 LU/mg of a lipolytic enzyme.
- Use according to claim 1, characterised in that the lipase is a bacterial lipase which shows a positive immunological cross-reaction with the antibody of the lipase, produced by Chromobacter viscosum var. lipolyticum NRRL B 3673.
- Use according to claim 2, characterised in that the lipase is producible by the microorganism selected from the group consisting of Pseudomonas fluorescens, Pseudomonas fragi, Pseudomonas nitroreducens var. lipolyticum, Pseudomonas cepacia, Pseudomonas gladioli and Chromobacter viscosum.
- Use according to any of claims 1-3 in a machine dishwashing process, characterised in that there is used a composition containing from 20-60% by weight of an alkali metal silicate, from 1-15% by weight of a peroxy type bleaching agent and from 0.5-5% by weight of a low-foaming nonionic detergent.
- Use according to any of claims 1-3 in a machine rinsing process, characterised in that there is used a composition containing, in an aqueous medium, from 0.5-10% by weight of a nonionic surfactant, from 5-25% by weight of an organic or inorganic acid and from 1-5% by weight of a hydrotrope.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8629538 | 1986-12-10 | ||
GB868629538A GB8629538D0 (en) | 1986-12-10 | 1986-12-10 | Enzymatic dishwashing & rinsing composition |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0271155A2 EP0271155A2 (en) | 1988-06-15 |
EP0271155A3 EP0271155A3 (en) | 1988-08-17 |
EP0271155B1 EP0271155B1 (en) | 1991-09-04 |
EP0271155B2 true EP0271155B2 (en) | 2000-09-06 |
Family
ID=10608788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP87202387A Expired - Lifetime EP0271155B2 (en) | 1986-12-10 | 1987-12-02 | Enzymatic dishwashing and rinsing process |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0271155B2 (en) |
JP (1) | JPS63161086A (en) |
AU (1) | AU609755B2 (en) |
BR (1) | BR8706685A (en) |
DE (1) | DE3772726D1 (en) |
ES (1) | ES2025635T5 (en) |
GB (1) | GB8629538D0 (en) |
ZA (1) | ZA879297B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109563449A (en) * | 2016-06-23 | 2019-04-02 | 诺维信公司 | Purposes, composition and the method for removing dirt of enzyme |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0697997B2 (en) * | 1985-08-09 | 1994-12-07 | ギスト ブロカデス ナ−ムロ−ゼ フエンノ−トチヤツプ | New enzymatic detergent additive |
BE1001436A3 (en) * | 1988-02-22 | 1989-10-31 | Synfina Sa | New lipase and detergent compositions containing. |
GB8813687D0 (en) * | 1988-06-09 | 1988-07-13 | Unilever Plc | Enzymatic dishwashing & rinsing composition |
GB8813688D0 (en) * | 1988-06-09 | 1988-07-13 | Unilever Plc | Enzymatic dishwashing composition |
JPH0277498A (en) * | 1988-09-14 | 1990-03-16 | Lion Corp | Detergent composition for use in automatic dishwasher |
US4908150A (en) * | 1989-02-02 | 1990-03-13 | Lever Brothers Company | Stabilized lipolytic enzyme-containing liquid detergent composition |
JPH02245129A (en) * | 1989-03-17 | 1990-09-28 | Novo Nordisk As | Enzymatically removing method for stain on stock |
GB8923788D0 (en) * | 1989-10-23 | 1989-12-13 | Unilever Plc | Enzymatic detergent compositions and their use |
JP2620384B2 (en) * | 1989-12-20 | 1997-06-11 | 花王株式会社 | Dishwashing composition for automatic dishwashers |
JPH0699715B2 (en) * | 1990-07-11 | 1994-12-07 | 花王株式会社 | Detergent composition for automatic dishwasher |
GB2247025A (en) * | 1990-08-13 | 1992-02-19 | Unilever Plc | Enzymatic dishwashing and rinsing composition |
US5527484A (en) * | 1991-05-31 | 1996-06-18 | Colgate-Palmolive Co. | Phosphate containing powdered automatic dishwashing composition with enzymes |
DE4324106C1 (en) * | 1993-05-25 | 1994-09-15 | Henkel Ecolab Gmbh & Co Ohg | Method and device for the metered addition of active ingredients to a rinsing machine |
TR28788A (en) | 1993-05-25 | 1997-03-25 | Henkel Ecolab Gmbh & Co Ohg | Methods and equipment for machine-dishwashing cleaning. |
HUT73758A (en) * | 1993-08-10 | 1996-09-30 | Procter & Gamble | Manual dishwashing composition comprising lipase enzymes |
US5772786A (en) * | 1993-08-13 | 1998-06-30 | The Procter & Gamble Company | Detergent composition comprising lime soap dispersant and lipase enzymes |
ATE189696T1 (en) * | 1995-08-25 | 2000-02-15 | Henkel Kgaa | USE OF LIPASES IN LOW ALKALINE AGENTS FOR MACHINE DISHWASHING |
MX2009009378A (en) | 2007-03-09 | 2009-09-22 | Danisco Us Inc Genencor Div | Alkaliphilic bacillus species a-amylase variants, compositions comprising a-amylase variants, and methods of use. |
JP5599113B2 (en) | 2008-06-06 | 2014-10-01 | ダニスコ・ユーエス・インク | Saccharification enzyme composition and saccharification method thereof |
CN102131924B (en) | 2008-06-06 | 2017-06-09 | 丹尼斯科美国公司 | Variant alpha amylase and its application method from bacillus subtilis |
EP2310521A2 (en) | 2008-06-06 | 2011-04-20 | Danisco US Inc. | Production of glucose from starch using alpha-amylases from bacillus subtilis |
BRPI0920891B1 (en) | 2008-09-25 | 2023-01-10 | Danisco Us Inc | ALPHA-AMYLASE MIXTURE AND METHOD FOR PRODUCING A FERMENTABLE SUGAR |
WO2011049945A2 (en) | 2009-10-23 | 2011-04-28 | Danisco Us Inc. | Methods for reducing blue saccharide |
JP5246300B2 (en) * | 2011-06-14 | 2013-07-24 | Jfeスチール株式会社 | Body side structure |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2071237A5 (en) † | 1969-12-22 | 1971-09-17 | Kronwitter Wolfram | Dish washers - using amylase as cleaning agent |
DE2062465A1 (en) † | 1970-12-18 | 1972-06-22 | Henkel & Cie. GmbH, 4000 Düsseldorf | Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate |
US4101457A (en) † | 1975-11-28 | 1978-07-18 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing composition |
US4162987A (en) † | 1976-06-24 | 1979-07-31 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing detergent composition |
EP0005131A2 (en) † | 1978-04-21 | 1979-10-31 | Peter Michael John Bedding | Methods and materials for cleaning soft contact lenses |
EP0139329A2 (en) † | 1983-10-20 | 1985-05-02 | Unilever N.V. | Dishwashing compositions |
EP0171008A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0171006A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0171007A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0266904A2 (en) † | 1986-10-07 | 1988-05-11 | Unilever Plc | Machine dish washing composition containing dipicolinic acid |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1372034A (en) * | 1970-12-31 | 1974-10-30 | Unilever Ltd | Detergent compositions |
US3950277A (en) * | 1973-07-25 | 1976-04-13 | The Procter & Gamble Company | Laundry pre-soak compositions |
US4421664A (en) * | 1982-06-18 | 1983-12-20 | Economics Laboratory, Inc. | Compatible enzyme and oxidant bleaches containing cleaning composition |
DK289083A (en) * | 1983-06-23 | 1984-12-24 | Novo Industri As | LIPASE, PROCEDURE FOR PREPARING THEREOF AND ITS APPLICATION |
GB8514708D0 (en) * | 1985-06-11 | 1985-07-10 | Unilever Plc | Enzymatic detergent composition |
GB8514707D0 (en) * | 1985-06-11 | 1985-07-10 | Unilever Plc | Enzymatic detergent composition |
DK154572C (en) * | 1985-08-07 | 1989-04-24 | Novo Industri As | ENZYMATIC DETERGENT ADDITIVE, DETERGENT AND METHOD FOR WASHING TEXTILES |
JPS62129397A (en) * | 1985-11-29 | 1987-06-11 | ライオン株式会社 | Detergent composition |
JPH0689355B2 (en) * | 1986-05-06 | 1994-11-09 | サンスタ−株式会社 | Cleaning composition |
JPS6434560A (en) * | 1987-07-30 | 1989-02-06 | Seiko Epson Corp | Die structure |
JPS6434559A (en) * | 1987-07-30 | 1989-02-06 | Seiko Epson Corp | Structure for taking out cavity |
-
1986
- 1986-12-10 GB GB868629538A patent/GB8629538D0/en active Pending
-
1987
- 1987-12-02 EP EP87202387A patent/EP0271155B2/en not_active Expired - Lifetime
- 1987-12-02 DE DE8787202387T patent/DE3772726D1/en not_active Expired - Fee Related
- 1987-12-02 ES ES87202387T patent/ES2025635T5/en not_active Expired - Lifetime
- 1987-12-08 JP JP62310794A patent/JPS63161086A/en active Pending
- 1987-12-08 AU AU82223/87A patent/AU609755B2/en not_active Ceased
- 1987-12-09 BR BR8706685A patent/BR8706685A/en not_active IP Right Cessation
- 1987-12-10 ZA ZA879297A patent/ZA879297B/en unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2071237A5 (en) † | 1969-12-22 | 1971-09-17 | Kronwitter Wolfram | Dish washers - using amylase as cleaning agent |
DE2062465A1 (en) † | 1970-12-18 | 1972-06-22 | Henkel & Cie. GmbH, 4000 Düsseldorf | Scouring agent - for dish washing machines, contg aminopolycarboxylic acid and alkali silicate |
US4101457A (en) † | 1975-11-28 | 1978-07-18 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing composition |
US4162987A (en) † | 1976-06-24 | 1979-07-31 | The Procter & Gamble Company | Enzyme-containing automatic dishwashing detergent composition |
EP0005131A2 (en) † | 1978-04-21 | 1979-10-31 | Peter Michael John Bedding | Methods and materials for cleaning soft contact lenses |
EP0139329A2 (en) † | 1983-10-20 | 1985-05-02 | Unilever N.V. | Dishwashing compositions |
EP0171008A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0171006A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0171007A2 (en) † | 1984-08-04 | 1986-02-12 | Henkel Kommanditgesellschaft auf Aktien | Dish cleaning agent |
EP0266904A2 (en) † | 1986-10-07 | 1988-05-11 | Unilever Plc | Machine dish washing composition containing dipicolinic acid |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109563449A (en) * | 2016-06-23 | 2019-04-02 | 诺维信公司 | Purposes, composition and the method for removing dirt of enzyme |
Also Published As
Publication number | Publication date |
---|---|
EP0271155B1 (en) | 1991-09-04 |
JPS63161086A (en) | 1988-07-04 |
EP0271155A3 (en) | 1988-08-17 |
BR8706685A (en) | 1988-07-19 |
AU8222387A (en) | 1988-06-16 |
DE3772726D1 (en) | 1991-10-10 |
ES2025635T5 (en) | 2001-01-16 |
ES2025635T3 (en) | 1992-04-01 |
GB8629538D0 (en) | 1987-01-21 |
AU609755B2 (en) | 1991-05-09 |
ZA879297B (en) | 1989-08-30 |
EP0271155A2 (en) | 1988-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0271155B2 (en) | Enzymatic dishwashing and rinsing process | |
US5133893A (en) | Enzymatic detergent composition | |
US4873016A (en) | Enzymatic detergent composition | |
CA1335969C (en) | Enzymatic dishwashing composition containing lipolytic enzyme and bleaching agent | |
US4769173A (en) | Enzymatic detergent and bleaching composition | |
EP0271154B1 (en) | Enzymatic detergent composition | |
US5551990A (en) | Enzymatic dishwashing and rinsing composition | |
EP0271156B1 (en) | Enzymatic dishwashing composition | |
EP0341999B1 (en) | Enzymatic detergent composition | |
JPS63161084A (en) | Enzyme detergent composition | |
EP0373850B1 (en) | Enzyme-containing detergent compositions and their use | |
US5292448A (en) | Enzymatic detergent composition | |
US4861509A (en) | Enzymatic detergent and bleaching composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19880708 |
|
17Q | First examination report despatched |
Effective date: 19890303 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
REF | Corresponds to: |
Ref document number: 3772726 Country of ref document: DE Date of ref document: 19911010 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2025635 Country of ref document: ES Kind code of ref document: T3 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN TFP/PATENT Effective date: 19920529 |
|
26 | Opposition filed |
Opponent name: THE PROCTER & GAMBLE COMPANY Effective date: 19920603 Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN TFP/PATENT Effective date: 19920529 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: THE PROCTER & GAMBLE COMPANY. Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN TFP |
|
RAP4 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: UNILEVER PLC Owner name: UNILEVER N.V. |
|
PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
|
R26 | Opposition filed (corrected) |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN * 920603 T Effective date: 19920529 |
|
EAL | Se: european patent in force in sweden |
Ref document number: 87202387.4 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19951121 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19951201 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19951220 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19961203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Effective date: 19961231 Ref country code: CH Effective date: 19961231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19970701 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19970701 |
|
EUG | Se: european patent has lapsed |
Ref document number: 87202387.4 |
|
APAC | Appeal dossier modified |
Free format text: ORIGINAL CODE: EPIDOS NOAPO |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PLAW | Interlocutory decision in opposition |
Free format text: ORIGINAL CODE: EPIDOS IDOP |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20000906 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
ET3 | Fr: translation filed ** decision concerning opposition | ||
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20001222 Year of fee payment: 14 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: DC2A Kind code of ref document: T5 Effective date: 20001130 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20011112 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20011126 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20011130 Year of fee payment: 15 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021202 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021203 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030701 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20030901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20021203 |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051202 |