WO1997035953A1 - Spray-dried component comprising chelant - Google Patents

Spray-dried component comprising chelant Download PDF

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Publication number
WO1997035953A1
WO1997035953A1 PCT/US1997/004651 US9704651W WO9735953A1 WO 1997035953 A1 WO1997035953 A1 WO 1997035953A1 US 9704651 W US9704651 W US 9704651W WO 9735953 A1 WO9735953 A1 WO 9735953A1
Authority
WO
WIPO (PCT)
Prior art keywords
spray
chelant
dried component
weight
component according
Prior art date
Application number
PCT/US1997/004651
Other languages
French (fr)
Inventor
Scott John Donoghue
Achille Jules Edmond Doumen
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8223811&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1997035953(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002249268A priority Critical patent/CA2249268C/en
Priority to US09/155,161 priority patent/US5958866A/en
Priority to JP09534515A priority patent/JP3093283B2/en
Priority to BR9708333A priority patent/BR9708333A/en
Publication of WO1997035953A1 publication Critical patent/WO1997035953A1/en

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/36—Organic compounds containing phosphorus

Definitions

  • the present invention relates to a spray-dried component comprising a chelant, in particular diethylene triamine penta(methylene phosphonic acid) or its salts.
  • a chelant in particular diethylene triamine penta(methylene phosphonic acid) or its salts.
  • Such components are useful in granular detergent products, and also as intermediate products in the manufacture of bar soap, detergent tablets and other detergent forms such as extrudates, agglomerates and the like.
  • US-A-4 259 200 discloses phosphonates complexed with calcium, magnesium, zinc or aluminium ions, the molar ratio of metal ion to phosphonate being at least 1 :1. It is disclosed that the magnesium and the phosphonate can be premixed in any suitable solvent, including water, optionally mixed with other detergent components and spray-dried. Improved storage stability in bleaching compositions is sought.
  • EP-A-0 225 309 discloses the addition of salts of alkali or alkaline earth metals into particles comprising diethylene triamine penta(methylene phosphonic acid) for the purpose of improving free-flow and storage properties.
  • the amount of sulphate is 60% to 200% of the dry weight of the chelant, corresponding to a weight ratio of metal ion salt to chelant of from 0.6: 1 to 2: 1.
  • Preferred water content after spray-drying is less than 10% by weight of the particle.
  • spray-dried components may be prepared having a high chelant content (at least 50% by weight) and which still maintain good free-flowing properties.
  • the object of the present invention is to provide a spray-dried component which is in the form of a free-flowing particle with high chelant activity Summary of the Invention
  • a spray-dried component comprising: i) at least 50%, preferably at least 60%, by weight of a chelant; ii) from 1% to 25%, preferably from 5% to 10%, by weight of a alkali metal, or alkaline earth metal sulphate; and iii) preferably less than 10% by weight free moisture.
  • the chelant is preferably a phosphonic or succinic acid, or salt of phosphonic or succinic acid, more preferably the chelant is selected form the group consisting of diethylene triamine penta(methylene phosphonic acid), ethylene diamine-N,N'-disuccinic acid, or mixtures, or salts thereof.
  • the alkaline earth metal is preferably magnesium.
  • the spray-dried component of the present invention comprises a chelant.
  • Chelants are used, for example in detergent compositions, for their ability to complex with metal irons such as iron and/or manganese forming soluble chelates.
  • Suitable chelants can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelants and mixtures thereof.
  • Useful amino carboxylates include ethylenediaminetetracetates ("EDTA”), N- hydroxyethylethylene diaminetriacetates, nitrilotriacetates, ethylene diamine tetraproprionates, triethylene tetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.
  • EDTA ethylenediaminetetracetates
  • N- hydroxyethylethylene diaminetriacetates N- hydroxyethylethylene diaminetriacetates
  • nitrilotriacetates nitrilotriacetates
  • ethylene diamine tetraproprionates triethylene tetraaminehexacetates
  • diethylenetriaminepentaacetates diethylenetriaminepentaacetates
  • ethanoldiglycines alkali metal, ammonium, and substituted
  • Useful amino phosphonates include ethylenediaminetetrakis (methylenephosphonates), sold as DEQUEST®. Preferably these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Particularly preferred chelants are diethylene triamine penta(methylene phosphonic acid) (“DTPMP”) and ethylene diamine tetra(methylene phosphonic acid) (EDTMP).
  • Polyfunctionally-substituted aromatic chelants are also useful in the components herein. See US-A-3 812 044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenze ⁇ es such as l,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelant for use herein is ethylene diamine-N,N'-disuccinate ("EDDS"), especially the [S,S] isomer as described in US-A-4 704 233, issued on November 3, 1987, to Hartman and Perkins.
  • EDDS ethylene diamine-N,N'-disuccinate
  • magnesium sulphate is preferred for use in the present invention, magnesium sulphate being the most preferred.
  • Epsom salts; MgSO4 . 7H2O, i.e. the hydrated, crystalline form of magnesium sulphate with seven moles of water is particularly preferred.
  • the chelants used in the present invention may be conveniently provided from commercially available sources in aqueous solution. Typical commercially available solutions have a chelant activity of from about 40% to about 60% by weight.
  • the spray- dried component may be produced by mixing such an aqueous solution with the required amount of the sulphate, with the addition of more water if necessary to reduce total solids content, and then forming granules by spraying the solution into a conventional counter- current or co-current spray-drying tower. In the tower water is evaporated by hot gas, usually hot air, preferably to a level of less than 10% by weight of free moisture in the finished spray-dried component.
  • the spray-dried granules may pass through further drying and/or cooling steps in conventional process equipment, such as a fluid bed. Oversize and fines fractions are normally removed, for example, by passing the granules over vibrating screen.
  • Further processing including additional granulation steps, agglomeration or compaction, as well as dry mixing with other components may be to provide finished products such as detergent powders, bar soaps and tablets. Examples
  • DTPMP is hepta sodium salt of diethylene triamine penta(methylene phosphonic acid)
  • the spray-dried component produced in these examples have a bulk density of from 500 g/1 to 700 g/1.
  • the component absorbs very little moisture after manufacture (e.g. from atmospheric humidity) and hence flowability and caking problems are minimsed or eliminated even in environments of high temperature and high humidity.

Abstract

The present invention relates to a spray-dried component which is in the form of a free-flowing particle with high chelant activity comprising: i) at least 50 %, preferably at least 60 %, by weight of a chelant; ii) from 1 % to 25 %, preferably from 5 % to 10 %, by weight of a alkali metal, or alkaline earth metal sulphate; and iii) preferably less than 10 % by weight free moisture.

Description

SPRAY-DRIED COMPONENT COMPRISING CHELANT
The present invention relates to a spray-dried component comprising a chelant, in particular diethylene triamine penta(methylene phosphonic acid) or its salts. Such components are useful in granular detergent products, and also as intermediate products in the manufacture of bar soap, detergent tablets and other detergent forms such as extrudates, agglomerates and the like.
US-A-4 259 200, issued on March 31, 1981, discloses phosphonates complexed with calcium, magnesium, zinc or aluminium ions, the molar ratio of metal ion to phosphonate being at least 1 :1. It is disclosed that the magnesium and the phosphonate can be premixed in any suitable solvent, including water, optionally mixed with other detergent components and spray-dried. Improved storage stability in bleaching compositions is sought.
EP-A-0 225 309, published on June 10th, 1987, discloses the addition of salts of alkali or alkaline earth metals into particles comprising diethylene triamine penta(methylene phosphonic acid) for the purpose of improving free-flow and storage properties. The amount of sulphate is 60% to 200% of the dry weight of the chelant, corresponding to a weight ratio of metal ion salt to chelant of from 0.6: 1 to 2: 1. Preferred water content after spray-drying is less than 10% by weight of the particle.
The prior art does not suggest that spray-dried components may be prepared having a high chelant content (at least 50% by weight) and which still maintain good free-flowing properties.
The object of the present invention is to provide a spray-dried component which is in the form of a free-flowing particle with high chelant activity Summary of the Invention
This object is achieved by a spray-dried component comprising: i) at least 50%, preferably at least 60%, by weight of a chelant; ii) from 1% to 25%, preferably from 5% to 10%, by weight of a alkali metal, or alkaline earth metal sulphate; and iii) preferably less than 10% by weight free moisture.
The chelant is preferably a phosphonic or succinic acid, or salt of phosphonic or succinic acid, more preferably the chelant is selected form the group consisting of diethylene triamine penta(methylene phosphonic acid), ethylene diamine-N,N'-disuccinic acid, or mixtures, or salts thereof.
The alkaline earth metal is preferably magnesium.
Detailed Description of the Invention
The spray-dried component of the present invention comprises a chelant. Chelants are used, for example in detergent compositions, for their ability to complex with metal irons such as iron and/or manganese forming soluble chelates. Suitable chelants can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally- substituted aromatic chelants and mixtures thereof.
Useful amino carboxylates include ethylenediaminetetracetates ("EDTA"), N- hydroxyethylethylene diaminetriacetates, nitrilotriacetates, ethylene diamine tetraproprionates, triethylene tetraaminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.
Useful amino phosphonates include ethylenediaminetetrakis (methylenephosphonates), sold as DEQUEST®. Preferably these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Particularly preferred chelants are diethylene triamine penta(methylene phosphonic acid) ("DTPMP") and ethylene diamine tetra(methylene phosphonic acid) (EDTMP).
Polyfunctionally-substituted aromatic chelants are also useful in the components herein. See US-A-3 812 044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzeπes such as l,2-dihydroxy-3,5-disulfobenzene.
A preferred biodegradable chelant for use herein is ethylene diamine-N,N'-disuccinate ("EDDS"), especially the [S,S] isomer as described in US-A-4 704 233, issued on November 3, 1987, to Hartman and Perkins.
Magnesium, aluminium or zinc sulphates are preferred for use in the present invention, magnesium sulphate being the most preferred. Epsom salts; MgSO4 . 7H2O, i.e. the hydrated, crystalline form of magnesium sulphate with seven moles of water is particularly preferred.
The chelants used in the present invention may be conveniently provided from commercially available sources in aqueous solution. Typical commercially available solutions have a chelant activity of from about 40% to about 60% by weight. The spray- dried component may be produced by mixing such an aqueous solution with the required amount of the sulphate, with the addition of more water if necessary to reduce total solids content, and then forming granules by spraying the solution into a conventional counter- current or co-current spray-drying tower. In the tower water is evaporated by hot gas, usually hot air, preferably to a level of less than 10% by weight of free moisture in the finished spray-dried component.
Optionally the spray-dried granules may pass through further drying and/or cooling steps in conventional process equipment, such as a fluid bed. Oversize and fines fractions are normally removed, for example, by passing the granules over vibrating screen.
Further processing including additional granulation steps, agglomeration or compaction, as well as dry mixing with other components may be to provide finished products such as detergent powders, bar soaps and tablets. Examples
Example 1 Example 2
DTPMP 80 84
MgSO4 . 7H2O 10 5
Sodium chloride 5 6
Free moisture 5 5
DTPMP is hepta sodium salt of diethylene triamine penta(methylene phosphonic acid)
MgSO4 . 7H2O is Epsom salts
All levels are % by weight unless otherwise specified
The spray-dried component produced in these examples have a bulk density of from 500 g/1 to 700 g/1. The component absorbs very little moisture after manufacture (e.g. from atmospheric humidity) and hence flowability and caking problems are minimsed or eliminated even in environments of high temperature and high humidity.

Claims

WHAT IS CLAIMED IS:
1. A spray-dried component comprising: i) chelant; ii) from 1% to 25% by weight ofa alkali metal, or alkaline earth metal sulphate; and iii) free moisture characterised in that the spray dried component comprises at least 50% by weight of a chelant.
2. A spray-dried component according to claim 1 comprising: i) at least 60% by weight of chelant; ii) from 5% to 10% by weight ofa alkali metal, or alkaline earth metal sulphate; and iii) less than 10% by weight free moisture.
3. A spray-dried component according to either claim 1 or claim 2 wherein the chelant is a phosphonic or succinic acid, or salt of phosphonic or succinic acid, or mixtures thereof.
4. A spray-dried component according to claim 3 wherein the chelant is selected form the group consisting of diethylene triamine penta(methylene phosphonic acid), ethylene diamine-N,N'-disuccinic acid, salts of diethylene triamine penta(methylene phosphonic acid), salts of ethylene diamine-N,N'-disuccinic acid, or mixtures thereof.
5. A spray-dried component according to any of the previous claims wherein the alkaline earth metal is magnesium.
6. A spray-dried component according to claim 5 wherein the alkaline erth metal sulphate is in the hydrated, crystalline form of MgSO4 . 7H2O.
PCT/US1997/004651 1996-03-23 1997-03-21 Spray-dried component comprising chelant WO1997035953A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA002249268A CA2249268C (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant
US09/155,161 US5958866A (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant
JP09534515A JP3093283B2 (en) 1996-03-23 1997-03-21 Spray-dried ingredients containing chelating agents
BR9708333A BR9708333A (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelator

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP96200801.7 1996-03-23
EP96200801A EP0796911B2 (en) 1996-03-23 1996-03-23 Spray-dried detergent component comprising chelant

Publications (1)

Publication Number Publication Date
WO1997035953A1 true WO1997035953A1 (en) 1997-10-02

Family

ID=8223811

Family Applications (1)

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PCT/US1997/004651 WO1997035953A1 (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant

Country Status (12)

Country Link
EP (1) EP0796911B2 (en)
JP (1) JP3093283B2 (en)
CN (1) CN1119403C (en)
AR (1) AR006349A1 (en)
AT (1) ATE218611T1 (en)
BR (1) BR9708333A (en)
CA (1) CA2249268C (en)
DE (1) DE69621584T3 (en)
DK (1) DK0796911T3 (en)
ES (1) ES2177718T5 (en)
PT (1) PT796911E (en)
WO (1) WO1997035953A1 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2329188A (en) * 1997-09-11 1999-03-17 Procter & Gamble Detergent composition containing a stabilised percarboxylic bleaching system
WO2000012463A1 (en) * 1998-08-27 2000-03-09 The Dow Chemical Company Stable free-flowing solid chelants
BR9914614A (en) * 1998-10-05 2001-10-02 Procter & Gamble Process for supplying chelating agglomerate to a detergent composition to improve its storage stability, flowability and collection capacity
US6451224B1 (en) 1999-07-21 2002-09-17 The Dow Chemical Company Stable free-flowing solid chelants
US6635612B1 (en) 1999-10-01 2003-10-21 The Procter & Gamble Company Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability
EP1281676A1 (en) * 2001-08-01 2003-02-05 NV Solutia Europe S.A. Solid free-flowing phosphonate composition and method of use
US7423005B2 (en) * 2003-11-20 2008-09-09 Ecolab Inc. Binding agent for solidification matrix
ES2579217T3 (en) * 2010-04-23 2016-08-08 The Procter & Gamble Company Particle

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4259200A (en) * 1979-04-06 1981-03-31 Lever Brothers Company Bleaching and cleaning compositions
US4666623A (en) * 1985-02-21 1987-05-19 Monsanto Europe S.A. Granular aminomethylenephosphonate
EP0225309B1 (en) * 1985-11-29 1990-09-19 Monsanto Europe S.A./N.V. Aminomethylenephosphonate compositions
US5292446A (en) * 1990-11-14 1994-03-08 The Procter & Gamble Company Nonphosphated automatic dishwashing compositions with oxygen bleach systems and process for their preparation

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
SE374762B (en) † 1968-03-04 1975-03-17 Monsanto Co
US3717589A (en) † 1970-09-17 1973-02-20 Monsanto Co Sodium nitrilotriacetate and processes for producing same
IL47489A (en) * 1974-11-04 1978-07-31 Witco Chemical Corp Non-caking linear alkyl aryl sulfonate detergent compositions
GB1513550A (en) † 1975-05-05 1978-06-07 Unilever Ltd Hard surface cleaning compositions
US4105573A (en) † 1976-10-01 1978-08-08 The Procter & Gamble Company Dishwasher detergent composition
GR75249B (en) * 1980-05-10 1984-07-13 Procter & Gamble
FR2677370A1 (en) * 1991-06-05 1992-12-11 Nln Sa Sequestering agent for liquid detergent compositions; liquid detergent compositions containing the said sequestering agent
EP0678572A1 (en) † 1994-04-20 1995-10-25 The Procter & Gamble Company Detergent powder compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4259200A (en) * 1979-04-06 1981-03-31 Lever Brothers Company Bleaching and cleaning compositions
US4666623A (en) * 1985-02-21 1987-05-19 Monsanto Europe S.A. Granular aminomethylenephosphonate
EP0225309B1 (en) * 1985-11-29 1990-09-19 Monsanto Europe S.A./N.V. Aminomethylenephosphonate compositions
US5292446A (en) * 1990-11-14 1994-03-08 The Procter & Gamble Company Nonphosphated automatic dishwashing compositions with oxygen bleach systems and process for their preparation

Also Published As

Publication number Publication date
DE69621584T2 (en) 2003-01-16
ES2177718T3 (en) 2002-12-16
AR006349A1 (en) 1999-08-25
EP0796911A1 (en) 1997-09-24
DK0796911T3 (en) 2002-09-30
CN1119403C (en) 2003-08-27
ATE218611T1 (en) 2002-06-15
JP3093283B2 (en) 2000-10-03
CA2249268C (en) 2002-02-05
DE69621584T3 (en) 2006-06-01
EP0796911B2 (en) 2005-07-13
CA2249268A1 (en) 1997-10-02
ES2177718T5 (en) 2005-12-01
BR9708333A (en) 1999-08-03
PT796911E (en) 2002-10-31
JPH11507098A (en) 1999-06-22
CN1219197A (en) 1999-06-09
DE69621584D1 (en) 2002-07-11
EP0796911B1 (en) 2002-06-05

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