EP0256679A1 - Dishwashing compositions - Google Patents

Dishwashing compositions Download PDF

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Publication number
EP0256679A1
EP0256679A1 EP87306403A EP87306403A EP0256679A1 EP 0256679 A1 EP0256679 A1 EP 0256679A1 EP 87306403 A EP87306403 A EP 87306403A EP 87306403 A EP87306403 A EP 87306403A EP 0256679 A1 EP0256679 A1 EP 0256679A1
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EP
European Patent Office
Prior art keywords
composition
weight
enzyme
agents
sodium
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP87306403A
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German (de)
French (fr)
Inventor
Sarah Thomson Galbraith
Alan Kenneth Cross
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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Publication date
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Publication of EP0256679A1 publication Critical patent/EP0256679A1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609Protease or amylase in solid compositions only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/06Phosphates, including polyphosphates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates

Definitions

  • This invention relates to dishwashing compositions and particularly to compositions in the form of a powder suitable for use in automatic dishwashing machines.
  • Detergent compositions for automatic dishwashing machines which comprise a bleaching agent, usually a chlorine-containing bleaching agent, and which are highly alkaline compositions having a solution pH above ll.5.
  • a bleaching agent usually a chlorine-containing bleaching agent
  • highly alkaline compositions having a solution pH above ll.5.
  • These conventional highly alkaline compositions are efficient in cleaning dishes but suffer from a number of disadvantages, notably that they are corrosive towards some metal components, ceramic glazes and pigments.
  • Compositions containing a chlorine bleach have the further disadvantages of odour problems and that due to instability of the bleach they may be difficult to perfume and/or dye and have a limited shelf-life.
  • a detergent composition free from a chlorine bleach and purporting to obviate the disadvantages of conventional dishwashing compositions is proposed in European Patent Application No l35227 A2.
  • This composition is based on a peroxy compound bleach used in combination with an amylolytic enzyme, is mildly alkaline with a solution pH of about 9.3 to about l0.8 and can be presented in the form of a particulate product thereby obviating the disadvantages of using a liquid composition.
  • This composition overcomes many of the disadvantages of the conventional highly alkaline compositions containing a chlorine bleach but still has the disadvantage that it contains a bleaching agent.
  • the present invention is concerned with a bleach-free dishwashing composition which is only mildly alkaline but is at least as effective in cleaning dishes as compositions proposed hitherto.
  • the composition is presented in powder form and exhibits a solution pH under dishwashing conditions in an automatic dishwashing machine of below ll.0 and preferably no greater than about l0.0.
  • a detergent powder composition for use in automatic dishwashing machines comprising -
  • the composition is mildly alkaline and in particular has a solution pH of about l0.0, this being the pH of a solution of 3 g/litre of the composition in water.
  • the alkalinity or solution pH of the composition which should generally be maintained above about 9 in order that the enzymes be effective, is largely established and maintained by components (a), (b) and (c) which exhibit a builder/buffer effect on the solution and are used in sufficient amounts to provide the desired solution pH.
  • the combined weight of builder and buffering agents, components (a), (b) and (c) should be at least 50% of the composition and may be up to 90% or even higher of the composition. Usually, however, the composition will contain an appreciable amount of one or more bulking agents so that the combined weight of components (a), (b) and (c) will be no more than about 70% of the composition.
  • the composition will usually contain one or more bulking agents in an amount of from 30% to 60% by weight. Any bulking agent may be used which does not appreciably inhibit the effectiveness of the enzymes or adversely modify the alkalinity of the composition.
  • Sodium sulphate is a typical and preferred bulking agent and sodium chloride may also be used.
  • Our preferred compositions contain both sodium sulphate and sodium chloride in a ratio of about l:0.5 by weight.
  • the preferred phosphate, component (c), is sodium tripolyphosphate.
  • the composition may contain a low-foaming surfactant and advantageously does contain a small amount, for example up to 5% by weight, of such a component. However we have found that if present, only very small amounts of surfactant are required and in particular amounts below 0.5% by weight.
  • Any low-­foaming surfactant may be employed but will usually be a non-ionic surfactant such as an alkylene oxide condensate in which the alkoxy moity is derived from ethylene oxide or propylene oxide or a mixture thereof.
  • suitable surfactants are the well-known ethoxylated straight-chain alcohols.
  • the surface active agent is biodegradable.
  • the composition contains both an amylolytic enzyme and a proteolytic enzyme.
  • at least one of the enzymes and especially preferably both of the enzymes are in granular form.
  • the enzymes are used in mixtures in which the ratio by weight of amylolytic enzyme: proteolytic enzyme is from l:4 to 4:l and usually from l:2 to 2:l.
  • amylolytic enzyme and any proteolytic enzyme may be used which at pHl0 exhibits at least 50% and preferably at least 60% of its maximum activity.
  • the enzyme mixture is present in the composition in an amount such that the composition has an amylolytic activity of at least l50 KNU (Kilo Novo units), preferably at least 300 KNU, per kilogram and a proteolytic activity of at least 6 Anson units per kilogram.
  • Amylolytic activity in KNU is determined as described in United States Patent Specification No 3,93l,034.
  • Proteolytic activity in Anson units is determined as the amount of enzyme which degrades haemaglobin under standard conditions as described in Journal of General Physiology, Vol 22 (l938), page 79.
  • compositions of the invention may if desired contain other ingredients known for use in automatic dishwasher compositions, for example sequestering agents, soil-suspending agents, corrosion inhibitors, drainage-promoting agents, crystal modifiers, dyes and perfumes.
  • compositions of the invention are presented as powders which can be produced by dry-mixing the powdered/granular materials and spraying any liquid components, e.g. a surfactant, on to the mixture during mixing.
  • liquid components e.g. a surfactant
  • compositions Five powder dishwashing compositions were prepared to the following formulations in which the ingredients are expressed as percentages by weight of the compositions:-
  • the sodium tripolyphosphate was stirred in a Kenwood food mixer and the surfactant (liquid) was added, followed by the other liquid ingredients. When all the liquids had been absorbed, the remaining ingredients were added to and mixed in the composition.
  • the dirty plates being cleaned were soiled by coating them with both a greasy soil and a protein soil and baking them at l50°C in an oven. Some plates were baked for 5 minutes, some for 7.5 minutes and others for l0 minutes.
  • the greasy soil was a mixture of peanut butter (5), butter (2), lard (2.5) and a mineral oil (2), the figures indicating parts by weight.
  • the protein soil was a mixture of raw egg (5) peanut butter (l), lard (l), butter (l) and milk (l), the figures being parts by weight.
  • the dry plates were removed and assessed for cleanliness.
  • the plates were coated with a thin film of activated charcoal and their reflectance was then determined at several points on the surface using a Bosch Light Reflectance meter.
  • the amount of activated charcoal adhering to the surface corresponds to the amount of soil remaining on the plate, being greater the greater the amount of soil.
  • a numerical assessment was derived of the cleanliness of the plates and hence of the cleaning ability of the dishwashing composition. As a blank against which cleanliness was assessed there was taken a new, unsoiled plate which was washed in the machine and assessed for cleanliness as above.

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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 detergent powder composition for dishwashing machines comprising 25-40% amorphous sodium silicate, l0-40% sodium carbonate, l5-40% phosphate builder, 0.25 to 5% of each of an amylolytic enzyme and a proteolytic enzyme and up to 60% of bulking agents and optionally up to 5% surfactant. The preferred builder is sodium tripolyphosphate and the preferred bulking agent is sodium sulphate (optionally together with sodium chloride) in an amount of at least 30%.

Description

  • This invention relates to dishwashing compositions and particularly to compositions in the form of a powder suitable for use in automatic dishwashing machines.
  • Detergent compositions for automatic dishwashing machines are known which comprise a bleaching agent, usually a chlorine-containing bleaching agent, and which are highly alkaline compositions having a solution pH above ll.5. These conventional highly alkaline compositions are efficient in cleaning dishes but suffer from a number of disadvantages, notably that they are corrosive towards some metal components, ceramic glazes and pigments. Compositions containing a chlorine bleach have the further disadvantages of odour problems and that due to instability of the bleach they may be difficult to perfume and/or dye and have a limited shelf-life.
  • A detergent composition free from a chlorine bleach and purporting to obviate the disadvantages of conventional dishwashing compositions is proposed in European Patent Application No l35227 A2. This composition is based on a peroxy compound bleach used in combination with an amylolytic enzyme, is mildly alkaline with a solution pH of about 9.3 to about l0.8 and can be presented in the form of a particulate product thereby obviating the disadvantages of using a liquid composition. This composition overcomes many of the disadvantages of the conventional highly alkaline compositions containing a chlorine bleach but still has the disadvantage that it contains a bleaching agent.
  • The present invention is concerned with a bleach-free dishwashing composition which is only mildly alkaline but is at least as effective in cleaning dishes as compositions proposed hitherto. The composition is presented in powder form and exhibits a solution pH under dishwashing conditions in an automatic dishwashing machine of below ll.0 and preferably no greater than about l0.0.
  • According to the present invention there is provided a detergent powder composition for use in automatic dishwashing machines comprising -
    • (a) 25 to 40% by weight of amorphous sodium silicate powder,
    • (b) l0 to 40% by weight of sodium carbonate,
    • (c) l5 to 40% by weight of a phosphate builder,
    • (d) 0.25 to 5% by weight of each of an amylolytic enzyme and a proteolytic enzyme,
    • (e) up to 60% by weight of bulking agents, and
    • (f) 0 to 5% by weight of a low-foaming surfactant.
  • The composition is mildly alkaline and in particular has a solution pH of about l0.0, this being the pH of a solution of 3 g/litre of the composition in water. The alkalinity or solution pH of the composition, which should generally be maintained above about 9 in order that the enzymes be effective, is largely established and maintained by components (a), (b) and (c) which exhibit a builder/buffer effect on the solution and are used in sufficient amounts to provide the desired solution pH. The optimum relative proportions of components (a), (b) and (c) are readily determined by simple trial for any particular composition but as a guide the ratio by weight is typically about l:l:0.5 of amorphous sodium silicate (a):sodium tripolyphosphate (c):sodium carbonate (b).
  • The combined weight of builder and buffering agents, components (a), (b) and (c) should be at least 50% of the composition and may be up to 90% or even higher of the composition. Usually, however, the composition will contain an appreciable amount of one or more bulking agents so that the combined weight of components (a), (b) and (c) will be no more than about 70% of the composition. As a guide only, we have obtained good cleaning using compositions containing about 65% by weight of components (a), (b) and (c) combined in the ratio of about l:0.5:l.
  • The composition will usually contain one or more bulking agents in an amount of from 30% to 60% by weight. Any bulking agent may be used which does not appreciably inhibit the effectiveness of the enzymes or adversely modify the alkalinity of the composition. Sodium sulphate is a typical and preferred bulking agent and sodium chloride may also be used. Our preferred compositions contain both sodium sulphate and sodium chloride in a ratio of about l:0.5 by weight.
  • The preferred phosphate, component (c), is sodium tripolyphosphate.
  • The composition may contain a low-foaming surfactant and advantageously does contain a small amount, for example up to 5% by weight, of such a component. However we have found that if present, only very small amounts of surfactant are required and in particular amounts below 0.5% by weight. Any low-­foaming surfactant may be employed but will usually be a non-ionic surfactant such as an alkylene oxide condensate in which the alkoxy moity is derived from ethylene oxide or propylene oxide or a mixture thereof. Examples of suitable surfactants are the well-known ethoxylated straight-chain alcohols. Preferably, the surface active agent is biodegradable.
  • The composition contains both an amylolytic enzyme and a proteolytic enzyme. Preferably at least one of the enzymes and especially preferably both of the enzymes are in granular form. The enzymes are used in mixtures in which the ratio by weight of amylolytic enzyme: proteolytic enzyme is from l:4 to 4:l and usually from l:2 to 2:l. We prefer to employ approximately equal amounts (by weight) of proteolytic enzyme and amylolytic enzyme, typically from 0.5 to l.5% by weight of each enzyme based on the weight of the composition.
  • Any amylolytic enzyme and any proteolytic enzyme may be used which at pHl0 exhibits at least 50% and preferably at least 60% of its maximum activity. The enzyme mixture is present in the composition in an amount such that the composition has an amylolytic activity of at least l50 KNU (Kilo Novo units), preferably at least 300 KNU, per kilogram and a proteolytic activity of at least 6 Anson units per kilogram. Amylolytic activity in KNU is determined as described in United States Patent Specification No 3,93l,034. Proteolytic activity in Anson units is determined as the amount of enzyme which degrades haemaglobin under standard conditions as described in Journal of General Physiology, Vol 22 (l938), page 79.
  • The compositions of the invention may if desired contain other ingredients known for use in automatic dishwasher compositions, for example sequestering agents, soil-suspending agents, corrosion inhibitors, drainage-promoting agents, crystal modifiers, dyes and perfumes.
  • The compositions of the invention are presented as powders which can be produced by dry-mixing the powdered/granular materials and spraying any liquid components, e.g. a surfactant, on to the mixture during mixing.
  • The invention is illustrated by the following Examples in which all parts are weight.
  • EXAMPLES l-5
  • Five powder dishwashing compositions were prepared to the following formulations in which the ingredients are expressed as percentages by weight of the compositions:-
    Figure imgb0001
  • The sodium tripolyphosphate was stirred in a Kenwood food mixer and the surfactant (liquid) was added, followed by the other liquid ingredients. When all the liquids had been absorbed, the remaining ingredients were added to and mixed in the composition.
  • A sample of each composition was used to clean dirty plates in a domestic automatic dishwashing machine (Indesit 2260E). The water softener reservoir in the machine was kept topped-up with sodium chloride and a rinse-aid was employed during the rinse cycle of the cleaning operation. l5 g of the powder dishwashing composition was loaded into the machine in each trial.
  • The dirty plates being cleaned were soiled by coating them with both a greasy soil and a protein soil and baking them at l50°C in an oven. Some plates were baked for 5 minutes, some for 7.5 minutes and others for l0 minutes.
  • The greasy soil was a mixture of peanut butter (5), butter (2), lard (2.5) and a mineral oil (2), the figures indicating parts by weight.
  • The protein soil was a mixture of raw egg (5) peanut butter (l), lard (l), butter (l) and milk (l), the figures being parts by weight.
  • After a full wash-cycle (including drying) in the machine, the dry plates were removed and assessed for cleanliness. The plates were coated with a thin film of activated charcoal and their reflectance was then determined at several points on the surface using a Bosch Light Reflectance meter. The amount of activated charcoal adhering to the surface corresponds to the amount of soil remaining on the plate, being greater the greater the amount of soil. Using this technique a numerical assessment was derived of the cleanliness of the plates and hence of the cleaning ability of the dishwashing composition. As a blank against which cleanliness was assessed there was taken a new, unsoiled plate which was washed in the machine and assessed for cleanliness as above.
  • Based on the results of a minimum of ten dishwashing trials, the relative cleaning ability of each composition was determined to be as follows on an arbitrary scale of 0 to ll0:-
    Figure imgb0002
  • For purposes of comparison, plates dirtied as above were washed in the machine using a well-known proprietary dishwashing composition available under the trade name "Finish". The relative cleaning ability of this composition was assessed on the 0 to ll0 scale as 53.

Claims (10)

1. A detergent powder composition for use in automatic dishwashing machines, comprising:-
(a) 25 to 40% by weight of amorphous sodium silicate powder,
(b) l0 to 40% by weight of sodium carbonate,
(c) l5 to 40% by weight of a phosphate builder,
(d) 0.25 to 5% by weight of each of an amylolytic enzyme and a proteolytic enzyme,
(e) up to 60% by weight of bulking agents, and
(f) 0 to 5% by weight of a low-foaming surfactant.
2. A detergent powder composition as claimed in claim l having a solution pH of from 9.0 to ll.0.
3. A composition as claimed in claim l or claim 2 wherein the combined weight of components (a), (b) and (c) is from 50% to 90% by weight of the composition.
4. A composition as claimed in claim l, 2 or 3 wherein the ratio by weight of components (a):(c):(b) is about l:l:0.5.
5. A composition as claimed in any one of claims l to 4 wherein the amount of the bulking agent(s) is at least 30% by weight of the composition.
6. A composition as claimed in any one of the preceding claims wherein the enzymes are in granular form.
7. A composition as claimed in any one of the preceding claims wherein the ratio by weight of amylolytic enzyme:proteolytic enzyme is from l:4 to 4:l.
8. A composition as claimed in claim 7 wherein the amylolytic enzyme and the proteolytic enzyme are present in approximately equal amounts by weight.
9. A composition as claimed in any one of the preceding claims wherein the amount of the surfactant is less than 0.5% by weight of the composition.
l0. A composition as claimed in any one of the preceding claims which contains in addition one or more ingredients selected from sequestering agents, soil-­suspending agents, corrosion inhibitors, drainage-­promoting agents, crystal modifiers, dyes and perfumes.
EP87306403A 1986-08-05 1987-07-20 Dishwashing compositions Withdrawn EP0256679A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8619045 1986-08-05
GB868619045A GB8619045D0 (en) 1986-08-05 1986-08-05 Dishwashing compositions

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EP0256679A1 true EP0256679A1 (en) 1988-02-24

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444415A1 (en) * 1990-02-15 1991-09-04 Hoechst Aktiengesellschaft Detergent composition comprising partially dehydrated disilicate
US5300250A (en) * 1992-01-14 1994-04-05 The Procter & Gamble Company Granular laundry compositions having improved solubility
DE4324202A1 (en) * 1993-05-25 1994-12-01 Henkel Ecolab Gmbh & Co Ohg Process and apparatus for mechanical dishwashing
WO1995012654A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
EP0700265B1 (en) * 1993-05-25 1997-07-30 Henkel-Ecolab GmbH & Co. OHG Machine dish-washing process and device
EP1160312A1 (en) * 2000-05-31 2001-12-05 Yasuo Sadoyama Detergent composition and process for producing composition thereof
EP2117993A1 (en) * 2007-02-01 2009-11-18 JohnsonDiversey, Inc. Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2036673A1 (en) * 1969-07-28 1971-02-11 Gaiser. Conrad Jerome, Reno. Nev (V St A ) Detergent preparation containing amorphous sodium silicate and methods for washing fabrics
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
DE2727463A1 (en) * 1976-06-24 1978-01-05 Procter & Gamble DETERGENT PARTICULARLY SUITABLE FOR USE IN DISHWASHING MACHINES
EP0135226A2 (en) * 1983-08-15 1985-03-27 Unilever N.V. Enzymatic machine-dishwashing compositions
EP0171007A2 (en) * 1984-08-04 1986-02-12 Henkel Kommanditgesellschaft auf Aktien Dish cleaning agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2036673A1 (en) * 1969-07-28 1971-02-11 Gaiser. Conrad Jerome, Reno. Nev (V St A ) Detergent preparation containing amorphous sodium silicate and methods for washing fabrics
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
DE2727463A1 (en) * 1976-06-24 1978-01-05 Procter & Gamble DETERGENT PARTICULARLY SUITABLE FOR USE IN DISHWASHING MACHINES
EP0135226A2 (en) * 1983-08-15 1985-03-27 Unilever N.V. Enzymatic machine-dishwashing compositions
EP0171007A2 (en) * 1984-08-04 1986-02-12 Henkel Kommanditgesellschaft auf Aktien Dish cleaning agent

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0444415A1 (en) * 1990-02-15 1991-09-04 Hoechst Aktiengesellschaft Detergent composition comprising partially dehydrated disilicate
US5096609A (en) * 1990-02-15 1992-03-17 Hoechst Aktiengesellschaft Detergent containing sodium disilicate having a water content of 0.3 to 6% by weight
TR25396A (en) * 1990-02-15 1993-03-01 Hoechst Ag WASHING AGENT WITH VARIOUS AUXILIARY WASHING AGENTS
US5300250A (en) * 1992-01-14 1994-04-05 The Procter & Gamble Company Granular laundry compositions having improved solubility
DE4324202A1 (en) * 1993-05-25 1994-12-01 Henkel Ecolab Gmbh & Co Ohg Process and apparatus for mechanical dishwashing
EP0700265B1 (en) * 1993-05-25 1997-07-30 Henkel-Ecolab GmbH & Co. OHG Machine dish-washing process and device
US6718991B1 (en) 1993-05-25 2004-04-13 Ecolab Gmbh & Co. Ohg Process and an arrangement for machine dishwashing
WO1995012654A1 (en) * 1993-11-03 1995-05-11 The Procter & Gamble Company Control of calcium carbonate precipitation in automatic dishwashing
EP1160312A1 (en) * 2000-05-31 2001-12-05 Yasuo Sadoyama Detergent composition and process for producing composition thereof
EP2117993A1 (en) * 2007-02-01 2009-11-18 JohnsonDiversey, Inc. Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same
EP2117993A4 (en) * 2007-02-01 2012-06-06 Diversey Inc Detergent dispenser assembly and method, flowable detergent powders, and methods for making and using the same

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Publication number Publication date
GB8619045D0 (en) 1986-09-17
AU7625187A (en) 1988-02-11
GB8717084D0 (en) 1987-08-26

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