EP0796911B1 - Spray-dried detergent component comprising chelant - Google Patents

Spray-dried detergent component comprising chelant Download PDF

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Publication number
EP0796911B1
EP0796911B1 EP96200801A EP96200801A EP0796911B1 EP 0796911 B1 EP0796911 B1 EP 0796911B1 EP 96200801 A EP96200801 A EP 96200801A EP 96200801 A EP96200801 A EP 96200801A EP 0796911 B1 EP0796911 B1 EP 0796911B1
Authority
EP
European Patent Office
Prior art keywords
spray
chelant
weight
dried component
component according
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
Application number
EP96200801A
Other languages
German (de)
French (fr)
Other versions
EP0796911A1 (en
EP0796911B2 (en
Inventor
Scott John Donoghue
Achille Jules Edmond Doumen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES96200801T priority Critical patent/ES2177718T5/en
Priority to DK96200801T priority patent/DK0796911T3/en
Priority to DE69621584T priority patent/DE69621584T3/en
Priority to PT96200801T priority patent/PT796911E/en
Priority to EP96200801A priority patent/EP0796911B2/en
Priority to AT96200801T priority patent/ATE218611T1/en
Priority to BR9708333A priority patent/BR9708333A/en
Priority to ARP970101151A priority patent/AR006349A1/en
Priority to JP09534515A priority patent/JP3093283B2/en
Priority to US09/155,161 priority patent/US5958866A/en
Priority to CN97194764A priority patent/CN1119403C/en
Priority to PCT/US1997/004651 priority patent/WO1997035953A1/en
Priority to CA002249268A priority patent/CA2249268C/en
Publication of EP0796911A1 publication Critical patent/EP0796911A1/en
Publication of EP0796911B1 publication Critical patent/EP0796911B1/en
Publication of EP0796911B2 publication Critical patent/EP0796911B2/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • 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, and agglomerates.
  • 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
  • a spray-dried component comprising:
  • 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 ammonium
  • 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).
  • DTPMP diethylene triamine penta(methylene phosphonic acid)
  • ETMP ethylene diamine tetra(methylene phosphonic acid)
  • 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 dihydroxydisulfobenzenes such as 1,2-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 sulphates are preferred for use in the present invention.
  • 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.
  • 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/l to 700 g/l.
  • 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.

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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)

Description

  • 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, and agglomerates.
  • 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 dihydroxydisulfobenzenes such as 1,2-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 sulphates are preferred for use in the present invention. 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/l to 700 g/l. 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 (6)

  1. A spray-dried component comprising:
    i) chelant;
    ii) from 1% to 25% by weight of a 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 of a 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.
EP96200801A 1996-03-23 1996-03-23 Spray-dried detergent component comprising chelant Expired - Lifetime EP0796911B2 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
ES96200801T ES2177718T5 (en) 1996-03-23 1996-03-23 DETERGENT DRYING COMPONENT BY SPRAYING THAT INCLUDES COMPLAINANT.
DK96200801T DK0796911T3 (en) 1996-03-23 1996-03-23 Spray-dried detergent component comprising chelating agent
DE69621584T DE69621584T3 (en) 1996-03-23 1996-03-23 Chelating agent-containing spray-dried detergent ingredient
PT96200801T PT796911E (en) 1996-03-23 1996-03-23 A DETERGENT DRY DETERGENT COMPONENT FOR SPRAY SPRAY CONTAINING A QUELATING AGENT
EP96200801A EP0796911B2 (en) 1996-03-23 1996-03-23 Spray-dried detergent component comprising chelant
AT96200801T ATE218611T1 (en) 1996-03-23 1996-03-23 SPRAY DRIED DETERGENT INGREDIENTS CONTAINING CHELATING GENERS
JP09534515A JP3093283B2 (en) 1996-03-23 1997-03-21 Spray-dried ingredients containing chelating agents
ARP970101151A AR006349A1 (en) 1996-03-23 1997-03-21 DETERGENT COMPONENT, DRYED BY ASPERSION, INCLUDING CHEATING AGENT.
BR9708333A BR9708333A (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelator
US09/155,161 US5958866A (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant
CN97194764A CN1119403C (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant
PCT/US1997/004651 WO1997035953A1 (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant
CA002249268A CA2249268C (en) 1996-03-23 1997-03-21 Spray-dried component comprising chelant

Applications Claiming Priority (1)

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

Publications (3)

Publication Number Publication Date
EP0796911A1 EP0796911A1 (en) 1997-09-24
EP0796911B1 true EP0796911B1 (en) 2002-06-05
EP0796911B2 EP0796911B2 (en) 2005-07-13

Family

ID=8223811

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96200801A Expired - Lifetime EP0796911B2 (en) 1996-03-23 1996-03-23 Spray-dried detergent 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
BR9914297B1 (en) * 1998-08-27 2010-10-19 process for producing a free flowing stable solid chelating composition, and a free flowing solid stable aminocarboxylate chelator.
AU1311200A (en) * 1998-10-05 2000-04-26 Procter & Gamble Company, The Process for delivering chelant agglomerate into detergent composition for improving its storage stability, flowability and scoopability
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

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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
CA1048888A (en) * 1974-11-04 1979-02-20 Witco Chemical Corporation Anticaking of linear alkyl aryl sulfonate detergents
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
BR8001956A (en) * 1979-04-06 1980-11-25 Unilever Nv CLEANING AND CLEANING COMPOSITION
GR75249B (en) * 1980-05-10 1984-07-13 Procter & Gamble
GB8504489D0 (en) † 1985-02-21 1985-03-27 Monsanto Europe Sa Aminomethylenephosphonate compositions
GB8529409D0 (en) * 1985-11-29 1986-01-08 Monsanto Europe Sa Aminomethylenephosphonate compositions
DE69108927T2 (en) * 1990-11-14 1995-12-14 Procter & Gamble METHOD FOR PRODUCING OXYGEN BLEACHING SYSTEMS CONTAINING PHOSPHATE-FREE DISHWASHER COMPOSITIONS.
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

Also Published As

Publication number Publication date
JP3093283B2 (en) 2000-10-03
EP0796911A1 (en) 1997-09-24
DE69621584T3 (en) 2006-06-01
CN1219197A (en) 1999-06-09
ES2177718T3 (en) 2002-12-16
WO1997035953A1 (en) 1997-10-02
JPH11507098A (en) 1999-06-22
DE69621584D1 (en) 2002-07-11
PT796911E (en) 2002-10-31
EP0796911B2 (en) 2005-07-13
BR9708333A (en) 1999-08-03
DK0796911T3 (en) 2002-09-30
ATE218611T1 (en) 2002-06-15
CA2249268A1 (en) 1997-10-02
DE69621584T2 (en) 2003-01-16
CN1119403C (en) 2003-08-27
AR006349A1 (en) 1999-08-25
CA2249268C (en) 2002-02-05
ES2177718T5 (en) 2005-12-01

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