EP0534525B1 - Waschmittelpulver und Verfahren zu deren Herstellung - Google Patents

Waschmittelpulver und Verfahren zu deren Herstellung Download PDF

Info

Publication number
EP0534525B1
EP0534525B1 EP92202764A EP92202764A EP0534525B1 EP 0534525 B1 EP0534525 B1 EP 0534525B1 EP 92202764 A EP92202764 A EP 92202764A EP 92202764 A EP92202764 A EP 92202764A EP 0534525 B1 EP0534525 B1 EP 0534525B1
Authority
EP
European Patent Office
Prior art keywords
composition
citric acid
weight
composition according
detergent
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
EP92202764A
Other languages
English (en)
French (fr)
Other versions
EP0534525B2 (de
EP0534525A2 (de
EP0534525A3 (en
Inventor
Galip Akay
Andrew Paul Unilever Research Chapple
Peter Robert Unilever Research Garrett
Peter Cory Unilever Research Knight
John William H. Unilever Research Yorke
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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=10702133&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0534525(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0534525A2 publication Critical patent/EP0534525A2/de
Publication of EP0534525A3 publication Critical patent/EP0534525A3/en
Application granted granted Critical
Publication of EP0534525B1 publication Critical patent/EP0534525B1/de
Publication of EP0534525B2 publication Critical patent/EP0534525B2/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the present invention relates to detergent powders intended for use in drum-type fabric washing machines.
  • the invention is of especial applicability to detergent powders containing no, or reduced levels of, phosphate builders and to powders of high bulk density, which have a tendency to dispense poorly.
  • the invention also relates to a process for preparing these detergent powders.
  • US-A-4,414,130 discloses detergent compositions comprising an effervescent material which promotes dissolution and dispersion of the detergent particles.
  • the detergent particles may comprise sodium carbonate or bicarbonate and that the balance of the composition may include citric acid.
  • the present invention provides a granular detergent composition having a bulk density of from 650 to 1100 kg/m 3 and comprising anionic and/or nonionic surfactants, from 5 to 30% by weight of sodium carbonate and/or -bicarbonate and/or sesquicarbonate, other builder material, and from 1 to 15% by weight of particulate citric acid, whereby more than 80% by weight of the citric acid has a particle size which is in the range of from 350 to 1500 ⁇ m.
  • the invention also provides a process for preparing this composition, wherein the citric acid is added as a separate granular component to a granular detergent base composition.
  • the first aspect of the invention is a granular detergent composition having a bulk density of from 650 to 1100 kg/m 3 , preferably from 700 to 1100 kg/m 3 .
  • the composition comprises a base composition to which particulate citric acid, and optionally a foam depressing agent, has been added.
  • the base composition may be prepared by spray-drying and dry-mixing/agglomeration. For obtaining high bulk densities, it is preferably prepared by dry-mixing/agglomeration.
  • the base composition contains one or more anionic and/or nonionic surfactants, and builder material.
  • the base composition preferably also comprises sodium carbonate and/or sodium bicarbonate and/or sodium sesquicarbonate.
  • the granular composition of the invention may further contain any of the materials conventionally included in detergent compositions. These are described in more detail below.
  • the surfactant component is the surfactant component
  • the total amount of surfactant present in the composition of the invention will generally range from 5 to 40 % by weight, more preferably from 10 to 30% by weight, and especially from 12 to 20% by weight. These figures are typical for fully formulated detergent compositions, and as a spray-dried or dry-mixed/agglomerated base forms only part of such a composition the surfactant content of that base, as a percentage, may of course be higher.
  • the invention is of especial applicability to compositions containing anionic and nonionic surfactants.
  • the amount of anionic surfactant present is desirably at least 3% by weight, and may suitably be in the range of from 3 to 30% by weight, these figures again being based on the fully formulated composition.
  • Anionic surfactants are well known to those skilled in the art. Examples of suitable anionic surfactants include alkylbenzene sulphonates,particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -C 15 primary alkyl sulphates; sodium salts of fatty acids (i.e. soaps); olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic surfactants are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, generally with 5 to 25 units of ethylene oxide (i.e.: 5-25 EO) per molecule, and the condensation products of aliphatic ( C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 3-40 EO.
  • alkyl polyglycosides and glucose ethers and esters may be effectively used as nonionic surfactants.
  • the sodium carbonate and/or bicarbonate and/or - sesquicarbonate may be added to the base composition but is preferably present in it.
  • the amount of this material present in the composition of the invention is in the range of from 5 to 30% by weight based on a fully formulated detergent composition. In zeolite built detergent powder according to the invention this amount is preferably in the range of from 5 to 15% by weight, whereas in detergent powder including a calcite/sodium carbonate builder system this amount is preferably in the range of from 15 to 30% by weight.
  • the citric acid is a separate granular component and needs to be added to the base composition.
  • the amount of particulate citric acid needed to obtain the desired good dispensing characteristics and storage stability is in the range of from 1 to 15% by weight, preferably from 2 to 12% by weight, more preferably from 3 to 10% by weight, based on a fully formulated composition.
  • more than 80% by weight of the particulate citric acid has a particle size of from 350 to 1500 ⁇ m, preferably from 350 to 1000 ⁇ m, a particle size range of 350-750 ⁇ m being most preferred.
  • the composition according to the invention includes at least one further builder material capable of reducing the level of free calcium ions in the wash liquor and preferably providing the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
  • the total level of the detergency builder may be from 10% to 70% by weight, preferably from 25% to 50% by weight of the detergent composition.
  • Preferred builders are ion exchange builders such as the crystalline (zeolite) or amorphous alkali metal alumino-silicates.
  • organic and inorganic polymers may be present, for example, polycarboxylate polymers such as polyacrylates, acrylic-maleic copolymers such as SOKALAN types of polymers may be present.
  • polycarboxylate polymers such as polyacrylates
  • acrylic-maleic copolymers such as SOKALAN types of polymers
  • Other preferred builder systems are precipitant builders such as those containing calcite and sodium carbonate as described in EP-A-267,042.
  • the detergent composition according to the invention is preferably essentially free of phosphates-containing builders such as orthophosphates and alkali metal tripolyphosphates.
  • citric acid and sodium (bi)carbonate and/or sodium sesquicarbonate preferably results in a reduction in the residue of at least 10 percentage points, most preferably at least 20 percentage points.
  • an improvement of this magnitude can only be observed if the control powder exhibits poor dispensing properties.
  • the present invention is therefore especially applicable to powders which, without citric acid and sodium (bi)carbonate and/or -sesquicarbonate, give dispenser residues of at least 20% by weight.
  • the powder is a zero-phosphate composition built with amorphous or crystalline (zeolite) sodium alumino-silicate; and/or if it has a bulk density of at least 650, preferably of at least 700 kg/m 3 .
  • zeolite amorphous or crystalline sodium alumino-silicate
  • the granular detergent composition of the invention preferably also contains one or more foam depressing agents.
  • Silicone oil based compositions containing high or low viscosity silicone oil, particularly high viscosity silicone oil, may be effectively used as antifoaming agents.
  • bleaches are the oxygen bleaches, for example in the form of an inorganic persalt, preferably with a precursor, or as a peroxy acid compound. From an environmental point of view, the most preferred bleach compound is percarbonate. Effective amounts of these bleach compounds present in the detergent composition of the invention range from 5 to 20% by weight, preferably from 10 to 20% by weight.
  • the powder of the invention may contain sodium silicate.
  • High levels of silicate can in themselves have a beneficial effect on dispensing, as well as on powder structure and prevention of machine corrosion, but are undesirable in powders containing alumino-silicate because the two components react together to form insoluble siliceous species.
  • the present invention enables the dispensing behaviour of zeolite-built powders to be improved without a corresponding increase in the level of insoluble material. Accordingly, the invention is of especial applicability to powders containing less than 10% by weight, more especially less than 5% by weight, of sodium silicate.
  • fluorescers include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, bleach activators, and bleach stabilizers. These may be included in the spray-dried base powder or postdosed according to their known suitability for undergoing spray-drying processes and their compatibility with other slurry ingredients.
  • a phosphate-free detergent base powder was prepared, by slurry-making, spray-drying and subsequently densifying in a Lödige "Recycler/ploughshare", as described in EP-A-367,339, to form the following nominal composition: Parts LAS 8.3 Nonionic EO 6.7 Soap 1.8 Zeolite 4A 28.0 Sokalan CP5 4.5 Carbonate 8.5 Minor ingredients + moisture 14.8 To this base powder, the following components were postdosed: Parts Silicone 0.4 Percarbonate 20.0 TAED 5.0 Carbonate 2.0 The bulk density of the detergent powder obtained was 850 kg/m 3 .
  • citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
  • the dispensing properties of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine using 100 g powder, and 5 litres of water at 20°C flowing in over a period of 1 minute.
  • Other samples were stored during 6 weeks in wax-laminated cartons at 28 °C and 70% RH, and thereafter tested in the Philips washing machine.
  • Table 1 shows the resulting dispenser residues. TABLE 1 1 2 3 4 Parts citric acid added 0 1 2 3 Dispenser Residue (%) 80 50 0 0 Dispenser Residue after After storage for 6 weeks 80 65 10 0
  • the bulk density of the detergent powder obtained was 850 kg/m 3 .
  • citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
  • Samples of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine, as described above. Other samples were stored during 6 weeks in wax-laminated cartons at 28°C and 70% RH, and thereafter tested in the Philips washing machine.
  • Table 2 shows the resulting dispenser residues. TABLE 2 5 6 7 8 9 Parts citric acid added 0 2 4 6 8 Dispenser Residue (%) 80 70 40 0 0 Dispenser Residue after Storage for 6 weeks (%) 80 70 40 10 0
  • citric acid of which more than 80% by weight has a particle size in the range of 50-100 ⁇ m was added at several levels. Samples of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine, as described above. Other samples were stored during 4 weeks in wax laminated cartons at 37°C and 70% RH, and thereafter tested in the Philips washing machine. Table 3 shows the resulting dispenser residues. TABLE 3 A B C D E Parts citric acid added 0 0.5 1 2 4 Dispenser Residue (%) 80 15 0 0 0 Dispenser Residue after Storage for 4 weeks (%) 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80
  • citric acid of which more than 80% by weight has a particle size in the range of 1500-2000 ⁇ m was added at several levels. Samples of the thus obtained compositions were tested as described above for Comparative Examples A-E. Table 4 shows the resulting dispenser residues. TABLE 4 F G H I Parts citric acid added 0 2 4 8 Dispenser residue (%) 80 70 53 35 Dispenser residue after Storage for 4 weeks (%) 80 80 80 80 80 80
  • particulate citric acid of which more than 80% by weight has a larger partical size than according to the present invention is not very effective at improving dispensing, neither immediately after preparation of the detergent powder nor after storage for 4 weeks.

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Körnige Reinigungsmittelzusammensetzung einer Schüttdichte von 650 bis 1100 kg/m3, die anionische und/oder nichtionische grenzflächenaktive Mittel, 5 bis 30 Gew.-% Natriumcarbonat und/oder -bicarbonat und/oder -sesquicarbonat, weitere Buildermaterialien sowie 1 bis 15 Gew.-% teilchenförmige Citronensäure umfaßt, wobei mehr als 80 Gew.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 1500 µm aufweisen.
  2. Zusammensetzung nach Anspruch 1, wobei mehr als 80 Vol.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 1000 µm aufweisen.
  3. Zusammensetzung nach Anspruch 2, wobei mehr als 80 Gew.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 750 µm aufweisen.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die Zusammensetzung ein schaumunterdrückendes Mittel umfaßt.
  5. Zusammensetzung nach Anspruch 4, wobei das schaumunterdrückende Mittel ein hochviskoses Siliconöl ist.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die Zusammensetzung eine Bleichmittelkomponente umfaßt.
  7. Zusammensetzung nach Anspruch 6, wobei die Bleichmittelkomponente Natriumpercarbonat ist.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, wobei das weitere Buildermaterial Natriumalumosilicat umfaßt.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei die Zusammensetzung im wesentlichen keine Phosphate enthält.
  10. Verfahren zur Herstellung der Zusammensetzung nach Anspruch 1, wobei die Citronensäure als getrennte körnige Komponente einer körnigen Reinigungsmittelgrundlagenzusammensetzung zugesetzt wird.
EP92202764A 1991-09-27 1992-09-11 Waschmittelpulver und Verfahren zu deren Herstellung Expired - Lifetime EP0534525B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9120657 1991-09-27
GB919120657A GB9120657D0 (en) 1991-09-27 1991-09-27 Detergent powders and process for preparing them

Publications (4)

Publication Number Publication Date
EP0534525A2 EP0534525A2 (de) 1993-03-31
EP0534525A3 EP0534525A3 (en) 1993-09-01
EP0534525B1 true EP0534525B1 (de) 1996-12-27
EP0534525B2 EP0534525B2 (de) 2007-10-10

Family

ID=10702133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92202764A Expired - Lifetime EP0534525B2 (de) 1991-09-27 1992-09-11 Waschmittelpulver und Verfahren zu deren Herstellung

Country Status (9)

Country Link
EP (1) EP0534525B2 (de)
JP (1) JPH05202398A (de)
AU (1) AU651732B2 (de)
BR (1) BR9203769A (de)
CA (1) CA2078718C (de)
DE (1) DE69216191T3 (de)
ES (1) ES2097860T3 (de)
GB (1) GB9120657D0 (de)
ZA (1) ZA927383B (de)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994028098A1 (en) † 1993-05-26 1994-12-08 Unilever Plc Detergent compositions
GB9324129D0 (en) * 1993-11-24 1994-01-12 Unilever Plc Detergent compositions and process for preparing them
SK280571B6 (sk) * 1993-11-24 2000-03-13 Unilever Nv Časticová detergentná zmes
WO1997024423A1 (en) * 1995-12-28 1997-07-10 Rhone-Poulenc Surfactants & Specialties, L.P. Processes for producing solid surfactant compositions with enhanced dissolution rates
GB9600547D0 (en) * 1996-01-11 1996-03-13 Reckitt & Colman Inc Improved compositions containing organic compounds
DE19603760A1 (de) * 1996-02-02 1997-08-07 Henkel Kgaa Feste Reinigungsmittelzubereitungen
ID16215A (id) † 1996-03-11 1997-09-11 Kao Corp Komposisi deterjen untuk mencuci pakaian
AU715795B2 (en) * 1996-03-15 2000-02-10 Access Business Group International Llc Free flowing agglomerated nonionic surfactant detergent composition and process for making same
GB2315761A (en) * 1996-07-31 1998-02-11 Procter & Gamble Detergent composition comprising a particulate acid source and an alkaline source
CA2255594C (en) * 1996-05-17 2002-07-23 The Procter & Gamble Company Detergent composition
GB2315763A (en) * 1996-07-31 1998-02-11 Procter & Gamble Preparation of an agglomerated detergent composition comprising a surfactant a an acid source
US6162784A (en) * 1996-07-31 2000-12-19 The Procter & Gamble Company Process and composition for detergents
DE19704229A1 (de) * 1997-02-06 1998-08-13 Henkel Kgaa Cobuilderhaltiges Additiv für Wasch- oder Reinigungsmittel
GB2323384A (en) * 1997-03-20 1998-09-23 Procter & Gamble A detergent composition
EP0872544A1 (de) † 1997-04-14 1998-10-21 The Procter & Gamble Company Trockene Brausegranulate und dessen Verwendung in granulierten Zusammensetzungen
GB9711356D0 (en) 1997-05-30 1997-07-30 Unilever Plc Particulate detergent composition
DE69817811T2 (de) 1997-05-30 2004-04-01 Unilever N.V. Rieselfähige körnige waschmittelzusammensetzungen
GB9711359D0 (en) 1997-05-30 1997-07-30 Unilever Plc Detergent powder composition
GB9711350D0 (en) * 1997-05-30 1997-07-30 Unilever Plc Granular detergent compositions and their production
DE19723616A1 (de) * 1997-06-05 1998-12-10 Henkel Kgaa Granulares Waschmittel
WO1999063047A1 (en) * 1998-06-04 1999-12-09 Kao Corporation Surfactant composition
DE19847281A1 (de) * 1998-10-14 2000-04-20 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit organischen Oligocarbonsäuren
DE19854083A1 (de) * 1998-11-24 2000-05-25 Henkel Kgaa Citronensäurehaltiges Waschmittel
GB2344597A (en) * 1998-12-08 2000-06-14 Procter & Gamble Effervescence components
US6683043B1 (en) 1998-12-08 2004-01-27 The Procter & Gamble Company Process for manufacturing effervescence components
MXPA02008373A (es) * 2000-02-28 2002-12-13 Procter & Gamble Composiciones antimicrobianas acidas para el tratamiento de alimentos y superficies que contactan alimentos y metodos para la utilizacion de las mismas.
GB0006037D0 (en) 2000-03-13 2000-05-03 Unilever Plc Detergent composition
GB0115552D0 (en) 2001-05-16 2001-08-15 Unilever Plc Particulate laundry detergent composition containing zeolite
GB0125212D0 (en) 2001-10-19 2001-12-12 Unilever Plc Detergent compositions
DE10163603B4 (de) * 2001-12-21 2006-05-04 Henkel Kgaa Verfahren zur Herstellung builderhaltiger Tensidgranulate

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1374105A (en) * 1970-12-03 1974-11-13 Scherico Ltd Effervescent compositions
GB1515299A (en) * 1974-08-28 1978-06-21 Unilever Ltd Stabilisation of sodium percarbonate
US4231887A (en) * 1979-06-26 1980-11-04 Union Carbide Corporation Zeolite agglomerates for detergent formulations
US4414130A (en) * 1976-08-17 1983-11-08 Colgate Palmolive Company Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
EP0367339A2 (de) * 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3653914A (en) * 1970-03-20 1972-04-04 Alberto Culver Co Production of tablets
US3920586A (en) * 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
US4129526A (en) * 1977-07-14 1978-12-12 The Lion Fat & Oil Co., Ltd. Granular detergent compositions and a process for producing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1374105A (en) * 1970-12-03 1974-11-13 Scherico Ltd Effervescent compositions
GB1515299A (en) * 1974-08-28 1978-06-21 Unilever Ltd Stabilisation of sodium percarbonate
US4414130A (en) * 1976-08-17 1983-11-08 Colgate Palmolive Company Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them
US4231887A (en) * 1979-06-26 1980-11-04 Union Carbide Corporation Zeolite agglomerates for detergent formulations
EP0367339A2 (de) * 1988-11-02 1990-05-09 Unilever N.V. Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"Proceedings of the second World Conference on Detergents, American Oil Chemists'Society,1987,p.177-180 *
Hoffman la Roche sales brochure on citric acid on the market in 1988; Jungbunzlauer sales brochure on citric acid on the market before 1991 ADM sales brochure on citric acid, confirmed by ADM to be of essentially the same specification as the citric acid on the market before 1991; and CEH market research report on citric acid,of 1996, *
Ind.Enp.Chem.Process Des-Der,Vol.9,n°3,pp363-367(1970) *
JP-62-62889(published 19 March 1987), and translation into English. *
prior use evidence of Ariel Ultra D product *
prior use evidence of Cheer ZM product *

Also Published As

Publication number Publication date
JPH05202398A (ja) 1993-08-10
DE69216191T3 (de) 2008-03-13
DE69216191T2 (de) 1997-06-05
BR9203769A (pt) 1993-04-20
GB9120657D0 (en) 1991-11-06
EP0534525B2 (de) 2007-10-10
DE69216191D1 (de) 1997-02-06
AU2535592A (en) 1993-04-01
AU651732B2 (en) 1994-07-28
CA2078718A1 (en) 1993-03-28
CA2078718C (en) 2003-12-09
ES2097860T3 (es) 1997-04-16
EP0534525A2 (de) 1993-03-31
EP0534525A3 (en) 1993-09-01
ZA927383B (en) 1994-03-25

Similar Documents

Publication Publication Date Title
EP0534525B1 (de) Waschmittelpulver und Verfahren zu deren Herstellung
EP0451894B2 (de) Granulare Detergenszusammensetzungen mit hohem Schüttgewicht und Verfahren zu ihrer Herstellung
US5616550A (en) Process for the continuous production of a granular detergent
EP0544492B1 (de) Teilchenförmige Waschmittelzusammensetzungen
EP0425277A2 (de) Reinigungsmittel
EP0652940B1 (de) Waschmittelzusammensetzungen
EP0451893B1 (de) Teilchenförmige bleichende Detergenszusammensetzung
US5736502A (en) Process for preparing detergent compositions
US4478735A (en) Process for producing granular detergent composition
EP1387882B1 (de) Teilchenförmiges waschmittel mit zeolith
EP0337523A1 (de) Waschmittelpulver und Verfahren zu deren Herstellung
HU219203B (en) Particulate detergent composition and process for producing thereof
EP0870008B1 (de) Verfahren zur herstellung von granularen waschmittelkomponenten oder -zusammensetzungen
EP0692018B1 (de) Flüssige reinigungsprodukte
EP0436240B1 (de) Verfahren zur Herstellung von Reinigungsmitteln hoher Dichte mit verbesserten Verteilungseigenschaften
GB2053998A (en) Particulate bleach composition
US5990073A (en) Process for the production of a detergent composition
EP1085080B1 (de) Oberflaechenaktive zusammensetzung
EP0492679B1 (de) Waschpulver
EP1436378B1 (de) Waschmittelzusammensetzungen enthaltend kaliumcarbonat und verfahren zu ihrer herstellung
US20030114347A1 (en) Detergent compositions
CA2078789A1 (en) Liquid cleaning products
JP2003096500A (ja) 粉末洗剤組成物及びその製造方法
EP0290209A1 (de) Sprühgetrocknetes Material für Detergenszusammensetzungen
HK1014263B (en) Particulate detergent compositions

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: 19940302

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19951215

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19961227

Ref country code: LI

Effective date: 19961227

Ref country code: CH

Effective date: 19961227

REF Corresponds to:

Ref document number: 69216191

Country of ref document: DE

Date of ref document: 19970206

ET Fr: translation filed
ITF It: translation for a ep patent filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970327

ET Fr: translation filed

Free format text: CORRECTIONS

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2097860

Country of ref document: ES

Kind code of ref document: T3

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19970925

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

R26 Opposition filed (corrected)

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 19970925

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PLAW Interlocutory decision in opposition

Free format text: ORIGINAL CODE: EPIDOS IDOP

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PLAY Examination report in opposition despatched + time limit

Free format text: ORIGINAL CODE: EPIDOSNORE2

PLBC Reply to examination report in opposition received

Free format text: ORIGINAL CODE: EPIDOSNORE3

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060926

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060930

Year of fee payment: 15

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

27A Patent maintained in amended form

Effective date: 20071010

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): CH DE ES FR GB IT LI NL SE

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080121

ET3 Fr: translation filed ** decision concerning opposition
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080917

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080929

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20081031

Year of fee payment: 17

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

Effective date: 20070911

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090911

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100531

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: 20090930

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100401

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: 20090911